Energy & Environmental Science: Accepted Manuscript

View Article Online
Energy &
View Journal
Environmental
Science
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: S. De, J. Zhang, R.
Luque and N. Yan, Energy Environ. Sci., 2016, DOI: 10.1039/C6EE02002J.
This is an Accepted Manuscript, which has been through the

Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after

acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the

Information for Authors.
Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/ees
Page 1 of 34 Please
Energy do not adjust margins
& Environmental Science
View Article Online
DOI: 10.1039/C6EE02002J
Journal Name
Energy & Environmental Science Accepted Manuscript

ARTICLE
Published on 15 September 2016. Downloaded by Simon Fraser University on 15/09/2016 16:25:29.
Ni-based bimetallic heterogeneous catalysts for energy and

environmental applications
Received 00th January 20xx, a a b a
Accepted 00th January 20xx Sudipta De, Jiaguang Zhang, Rafael Luque and Ning Yan *
DOI: 10.1039/x0xx00000x Bimetallic catalysts have attracted extensive attention in a wide range of applications in energy production and
environmental remediation due to their tunable chemical/physical properties. These properties are mainly governed by a
www.rsc.org/
number of parameters such as compositions of the bimetallic systems, their preparation method, and their
morphostructure. In this regard, numerous efforts have been made to develop “designer” bimetallic catalysts with specific
nanostructures and surface properties as a result of recent advances in the area of materials chemistry. The present
review highlights a detailed overview on the development of nickel-based bimetallic catalysts in energy and environmental
applications. Starting from a materials science perspective in order to obtain controlled morphologies and surface
properties, with a focus on the fundamental understanding of these bimetallic systems to make a correlation with their
catalytic behaviors, a detailed account is provided on the utilization of these systems in the catalytic reactions related to
energy production and environmental remediation. We include the entire library of nickel-based bimetallic catalysts for
both chemical and electrochemical processes such as catalytic reforming, dehydrogenation, hydrogenation,
electrocatalysis and many other reactions.
Broader context
To address the increasing energy demand while mitigating environmental concerns, numerous research efforts have been devoted to finding out the most
sustainable routes for energy production. Catalysis can offer attractive solutions to such processes, with the possibility to design highly effective advanced
catalytic systems as the basis of future industrial implementation. Bimetallic catalysts emerged as materials of a new category, which often show electronic
and chemical properties different from their monometallic counterparts; thus offering an opportunity to design new catalysts with enhanced selectivity,
activity, and stability. Since the infancy of bimetallic catalysts in the 1960’s, an enormous number of catalysts have been explored, most of which were based
on noble metals as main component. However, the industrial application of these noble metal catalysts is limited by their exceptionally high prices and low
availability, which has turned the attention towards more abundant transition metal-based catalysts. Nickel is the most widely used element among the
transition metal-based catalysts and has the highest ability to form bimetallic systems with other metals. As a result, the library of bimetallic Ni catalysts has
been enriched very rapidly in the last decade. The proposed contribution provides an overview of recent progress in the design of bimetallic nickel-based
catalysts for energy production and environmental remediation. Design aspects of the catalysts and the fundamental understanding of their catalytic
properties are also critically discussed.
minimizing waste generation and energy requirements. Metal-

1. Introduction based catalysts, in this regard, have shown immense
importance in a wide range of diverse catalytic applications
Population increase, urbanization, and rising living standards
with high efficiency. However, fine-tuning of the structure and
have rapidly increased global energy consumption and
property of these catalysts is highly desirable to meet the
environmental burdens in the last half century. Energy
stringent requirements in energy and environment
consumption is expected to continue to grow dramatically in
applications.
the coming years along with associated environmental issues.
Nickel is one of the most widely used elements in metal
Although there is no universal solution to solve all energy and
based catalyst (see Fig. 1). It is the fourth most abundant
environment-related problems,1 catalysis certainly plays a
transitional metal on earth after Fe, Ti and Zr. It currently costs
critical role in the design of efficient processes and systems
at 3.8 USD/lb, which is only 1/5000 the price of gold. In fact,
able to maximize the value of starting materials while
nickel has a long history in modern catalysis—its first
th
application as a hydrogenation catalyst date back to the 19
century which led to the Nobel Prize in Chemistry in 1912.
Afterwards Ni was found to be active in a number of
processes, in particular in hydrogenation and reforming
reactions. Despite the huge success and wide applications of Ni
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please
& Environmental Science Page 2 of 34
View Article Online
DOI: 10.1039/C6EE02002J
ARTICLE Journal Name
catalyst in industry, single component Ni catalysts are not able reactions related to energy and to a less extent environment,
to meet the activity, selectivity, and stability requirements in which reflects the growing concern of bimetallic
many emerging applications related to energy and heterogeneous catalysis in these domains. This contribution

environment. aims to provide a critical overview of the entire library of Ni-
based heterogeneous bimetallic catalysts with their recent
syntheses protocols in view of their applications in a wide
range of chemical processes. A rationalized approach is
provided to identify suitable metal combinations that may be
able to provide improved activities in selected applications
compared to conventional and/or presently reported systems.

Different energy-related catalytic processes will be discussed
where the influence on modification of Ni catalysts by other
metals and their relation to their catalytic properties will be
introduced. Additionally, a brief discussion on the fundamental
approach by using classical theories of chemistry (such as d-
band theory) to understand the origin of improved efficiency
and stability of the bimetallic systems will also be provided.
Recently, several reviews based on homogeneous Ni-based
complexes were published focusing mainly on the C–C
coupling reactions.7, 8 Two excellent reviews based on
heterogeneous Ni-based catalysts were published focusing
exclusively on reforming reactions.9, 10 Nevertheless, to the
best of our knowledge, there is no review on bimetallic Ni-
based catalysts providing detailed discussion on energy and
environment applications. We hope this contribution will be a
good addition to existing literature, and will provide useful
information for future research.
2. Preparation of bimetallic Ni catalysts

A number of factors are responsible for the structure of the
Fig. 1 Fact sheet showing the historical background, physical properties and uses of bimetallic catalysts (see Fig. 2). Presently, there are many well
nickel.
established methods for preparing bimetallic catalysts (either
2, 3
unsupported colloidal NPs or supported bimetallic NPs).
Bimetallic catalysts, which often show electronic and Choice of methods often depends on the desired surface and
chemical properties that are distinct from those of their parent bulk structure of the catalysts. For instance, co-impregnation
metals, may offer enhanced performance. Since the process is mainly used to get supported bimetallic or alloy type
pioneering and systematic work by Exxon Research and materials. On the other hand, sequential impregnation method
Engineering in the early 1960s, the library of bimetallic is often adopted to get core-shell type materials, where a less
catalysts has been significantly enriched, particularly in the active metal (generally 3d transition metal) core is prepared
past two decades. Among all bimetallic catalysts, platinum- first and then the active metal (generally noble metal) is
group metals constitute the most studied catalyst deposited onto it. Wet impregnation methods are widely
2, 3
component. However, high cost and low availability limit applicable for syntheses of bimetallic catalysts with well-
their applications in large scale processes. Therefore, attention 11, 12
controlled shape, size, and composition. Various wet-
was paid to nickel, a low-cost alternative, which has similar chemical schemes have been applied to synthesize bimetallic
electronic properties and can perform many of the same NPs. They can be classified into two categories according to
4-6
elementary reactions as palladium or platinum. In fact, Ni is the formation mechanisms: seed-mediated growth and one-
known for its high alloying efficiency with all noble metals as pot co-reduction. The two strategies are similar by their
well as many transition metals in different mass ratios, which fundamental principles. In the seed-mediated growth process,
makes it easier to develop a wide range of composition- the metal seeds of comparatively inactive metal are first
dependent bimetallic Ni systems for diversified catalytic prepared and then dispersed in a solution of active metal
applications. Recently, there are many reports on the facile precursor. Controlled reduction of the second metal forms
synthesis of bimetallic Ni systems, which have shown the uniform layers over the seeds and a core-shell structure is
potential to replace expensive noble metal catalysts in terms obtained. In the one-pot co-reduction method, two metallic
of catalytic activity and stability. precursors are added at the same time. In this case, the
After a detail survey of recent publications on bimetallic Ni, reduction potentials of the metals play a key role to determine
we found that the majority of them were focused on catalytic the final architecture. Two possibilities arise here: (1) metals
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Page 3 of 34 Please
View Article Online
DOI: 10.1039/C6EE02002J
Journal Name ARTICLE
with similar reduction potential are reduced simultaneously

and form an alloyed structure, and (2) metals with different
reduction potential are reduced in a successive manner and

form a core-shell structure. However, there is no
straightforward relation between reduction kinetics and
reduction potential. The reduction kinetics also depends on
the synthesis conditions applied. For example, the use of
surfactants, stronger reducing agents (such as NaBH4) or high
temperature solvothermal processes can simultaneously
reduce metals with different reduction potential resulting in an

13-16
alloyed structure. Alongside the wet impregnation
processes, much attention has been paid to colloidal chemistry
to synthesize unsupported NPs with controlled size, shape, and
stability.17 While colloidal chemistry is highly applicable
Fig. 3 Possibility of alloy formation of Ni with other elements in the periodic table
towards the syntheses of noble metal bimetallic systems, its
(Figure generated from data in Ref. 18).18
application in 3d transition metals is less studied.
Structural modification largely enhances the capability in

tuning the catalytic performance; therefore it is important to
have the knowledge of surface structure and properties of the
catalysts to derive the relationship between their structural
features and catalytic activity. In the past decade, significant
efforts have been given towards advanced characterization
techniques (e.g., Auger electron spectroscopy (AES), X-ray
photoelectron spectroscopy (XPS), extended X-ray absorption
fine structure (EXAFS), low-energy electron diffraction (LEED)
etc.) as well as theoretical calculations (e.g., density functional
theory (DFT)) to understand the surface properties of
2, 3, 19, 20
bimetallic systems. To reveal the origin of the novel
catalytic properties, bimetallic surfaces have also gained a
considerable amount of interest for surface science
21-23
research. Since the characterization methods for bimetallic
2, 3
systems are already discussed in some excellent reviews, we
Fig. 2 Factors responsible for the formation of different bimetallic structures.
would like to pay our attention in discussing how different
structures of bimetallic Ni catalysts are obtained depending on
their synthesis method.
Apart from the preparation methods, another factor that
determines the structure of a bimetallic system is the relative 2.1 Core-shell structure
position of two metals in the periodic table. A solid solution or
In principle, bimetallic core-shell structures can be obtained
miscible system is formed when the two metals are very close
either by seed-mediated growth or by one-pot co-reduction of
in the periodic table. For example, nickel is miscible with Co,
metallic precursors. In particular, for bimetallic Ni@noble
Cu, Rh, Pd, and Ir at any proportions as observed from Fig. 3,
metal core-shell structure, Ni serves as core and the noble
and therefore can easily form alloys. The metals which are
metal serves as shell. This kind of structure is generally
farther from nickel generally form intermetallic compounds.
prepared by seed-mediated growth process, where Ni cores
For example, Pt forms different intermetallic compounds with
are prepared by reducing its salt precursor prior to the
Ni at different specific ratios among which Pt3Ni is the most
deposition of noble metal on their surface. In most cases,
stable and very well known for the electrocatalytic 24,
capping ligands are used in this step to prevent aggregation.
applications. Although the predicted structure can be derived 25
It should be noted that the one-pot co-reduction method
from the experimental data presented in the periodic table, it
cannot form this structure because of the higher reduction
is not necessary that the final structure would be similar to
potential of noble metals than Ni. In this case, noble metals
that of the predicted one. Different variable structures can
will be reduced first and Ni will be deposited subsequently as
also be obtained by using controlled preparation method. The
shell over the noble metal core.
reduction potential of the metal plays a crucial role to result in
The reverse structure, i.e. noble metal@Ni core-shell, can
a definite structure since in most cases the bimetallic catalysts
be obtained in a one-pot sequential reduction. For example,
are prepared by reducing their salt precursors. In fact, multiple
the preparation of Au@Ni core-shell NPs with varying Ni shell
factors need to be considered to make a relationship between
thicknesses was reported by mixing both metal precursors in
the predicted and experimentally obtained structure of a 26
one-pot in the presence of oleylamine and 1-octadecene.
bimetallic system.

Please
View Article Online
DOI: 10.1039/C6EE02002J
Reduction of Au precursor to Au NPs was achieved by using to prepare IrNi@IrOx core-shell NPs from IrNix precursor
30, 31
NaBH4 as the reducing agent at room temperature. At an alloys. Ni rich bimetallic Ir-Ni NPs were first prepared using
increased temperature (210 °C), the as-formed Au seeds acted a conventional polyol method involving 1,2-tetradecanediol as

as the nucleation sites on which nickel ions were reduced. The reducing agent and oleylamine along with oleic acid as capping
different shell thicknesses could be controlled by using ligands. The hybrid IrNi@IrOx core-shell materials were
different ratio of two precursors. Because of the higher prepared in two ways (Fig. 4). In the first approach, the IrNix
electron density, noble metal cores sometimes induce the NP precursor alloys (PA-IrNix) were electrochemically
27
reduction of Ni, which is termed as noble-metal induced dealloyed to form metallic core-shell NPs (“D-IrNix”) with Ir
reduction where no external reducing agent is required. enriched surface, and subsequently they were selectively
surface oxidized to form “SO-IrNi@IrOx” metal oxide core-shell

NPs. Alternatively, the dealloying and oxidation could be
performed directly in one step to obtain DO-IrNi@IrOx.
2.2 Alloyed structure

Alloy systems are formed when two metal atoms have a
homogeneous distribution in one particle. Some metals are
thermodynamically more stable when mixing together, while
for others the reaction kinetics must be rigidly controlled to
produce alloyed structure. One approach is to use strong
reducing agents that reduce all metal precursors
Scheme 1 Schematic illustration for the synthesis of cubic Pd–Ni–Pt core-sandwich-
shell NPs.28 (Copyright 2014 American Chemical Society).
simultaneously to form homogeneous mixture of metals. For
example, bimetallic Ni–Fe alloy NPs could be formed using
NaBH4 as reducing agent to reduce Ni2+ and Fe2+ ions in an
Core-multishell is a more complex architecture in this
aqueous solution containing cetyltrimethylammonium chloride
category, which is well known for its good optical and
29 (CTAB) as surfactant, although these two metals cannot be
electronic properties. More precise kinetic control over the
mixed with random ratio thermodynamically.13, 32
reaction is required to achieve the structure. Recently, well-
Appropriate selection of surfactant or counterions adjust
shaped Pd–Ni–Pt core-sandwich-shell NPs were synthesized
the redox potentials of metals through specific adsorption or
using cubic and octahedral Pd substrates in the aqueous phase
coordination, leading to simultaneous reduction of different
at low temperature with a cationic surfactant as capping agent
28 metal ions.33 Surfactants can also play a key role to direct the
and hydrazine as the reducing agent. The combination of
reaction and crystal growth pathways to yield particles with a
shaped Pd substrates and mild reduction conditions directed
desired geometry. For example, the (111) surface-dominant
overgrowth of Ni and Pt in an oriented, layer-by-layer fashion.
Pt3Ni alloy nanocrystals – the best-known catalyst for oxygen
Scheme 1 demonstrates how Pd cubes function as shaped
reduction reaction (ORR) – can be prepared by reducing the
crystal substrates to catalyze and direct the oriented
metal precursors by CO in the presence of oleylamine (OAm)
overgrowth of Ni. Pt ions were added after the Ni overgrowth
and oleic acid (OA) as capping ligands.34, 35
to “trap” the metallic Ni phase and complete the layer-by-layer
Well-faceted nanocrystal alloys were also reported to form
synthesis of the shaped ternary metal NPs.
without any capping agents. Carpenter et al. reported the
solvothermal synthesis of ORR active Ni–Pt alloy catalysts
using a mild reducing agent, N,N-dimethylformamide, which
also served as the solvent.15 The effect of temperature on the
reduction kinetics of the metal precursors was studied. It was
observed that Ni(acac)2 was more difficult to reduce than
Pt(acac)2 and did not react up to 150 °C. The temperature was
further increased to 200 °C and 90% Ni reduction was
observed. Another controlled reaction with only Ni precursor
at the same temperature showed merely 42% Ni reduction,
suggesting that the presence of Pt and/or Pt(acac)2 enhances
the deposition of Ni. The converse also appeared to hold
Fig. 4 Synthetic protocol for the preparation of SO-IrNi@IrOx and DO-IrNi@IrOx
hybrid core-shell NP catalysts. Precursor IrNi alloys (“PA-IrNi”, and alloy scheme
because the apparent reaction onset temperature of the
on left, blue: Ni, grey: Ir) are stepwise (SO) or directly (DO) dealloyed and surface mixed precursor solution (115 °C) was lower than that of the
oxidized. “D-IrNix” denotes the dealloyed stage.30 (Copyright 2014 Royal Society Pt(acac)2-only solution (137 °C). These observations suggest
of Chemistry). that the free energy of formation of the Ni–Pt alloy NPs from
the reaction mixture is more negative than the free energy of
Post-modification of an alloy precursor through dealloying formation of platinum NPs from the same solution. Another
and surface oxidation is another way to make core-shell probable reason could be that under the reaction conditions Pt
structure. The method was recently applied by Strasser group proto-particles of only a few atoms were formed initially and

Page 5 of 34 Please
View Article Online
DOI: 10.1039/C6EE02002J
acted as seed crystals for subsequent Ni and Pt3Ni deposition, bimetallic catalyst fabricated by electrochemically dealloying a
41
which was also supported by the previous finding by Deivaraj Pd20Ni80 alloy in an acid solution at a low applied potential.
et al. that the reduction of Ni ions by hydrazine at room The key advantage of this process is that the residual Ni in the

36
temperature requires the presence of Pt nuclei. The method nanoporous alloy could be easily controlled by tuning
was recently extended to prepare trimetallic Pt-Ni-Co alloy NPs dealloying potentials. The electrochemical dealloying was also
37
at 130 °C. applied to make nanoporous Ni–Pt alloy NPs with hierarchical
42
Alongside the wet chemistry methods, gas phase synthesis structure and high surface area.
38
has also been reported for bimetallic Ni alloys. As a
‘‘bottom–up’’ approach, the gas phase method is more
complex since it starts from atomic-level precursors and needs

better control over nucleation and growth of nanocrystals. The
advantage of this method is that it does not require any
reducing agent or surfactant. Lin and Sankaran reported a
plasma-assisted scalable method for the synthesis of NiCu
alloys from the vapors of organometallic precursors,
bis(cyclopentadienyl)nickel [Ni(Cp)2] and copper
acetylacetonate [Cu(acac)2].38 By carefully combining precursor
vapors and varying the flow rates, a wide range of Scheme 2 Schematic illustration of the synthesis of Ni@Pt core-shell nanotube
arrays.43 (Copyright 2012 Wiley-VCH).
compositionally controlled alloyed NPs (less than 5 nm) with
narrow size distributions were obtained.
Apart from the dealloying process, templating pathways
2.3 Porous structure can also be used to generate porous structure. For example,
Generally, bimetallic alloys form crystalline particles with very porous Ni@Pt core-shell nanotubes were prepared via
43
low surface areas, which is a limitation for applications in electrodeposition method using ZnO nanorods as template.
catalytic processes. The surface area is one of the crucial Scheme 2 describes the synthetic pathway to the well-defined
factors for good catalytic performance. As such, porous porous Ni@Pt core-shell nanotube arrays. ZnO nanorod arrays
structured alloys – which have the advantages of high surface were first synthesized on conductive substrates utilized as
area, high gas permeability, high mass diffusion ability and low templates. Then, the electrodeposition of Ni layers was carried
density – are more promising in catalytic applications than out on the surfaces of the ZnO nanorods to prepare ZnO@Ni
their solid counterparts. In 1927, Murray Raney produced core-shell nanorod arrays, and Pt thin layers were further
porous Ni (Raney Ni) by selective leaching of a block of Ni–Al deposited on the surfaces of the Ni shells to prepare
alloy (NiAl3 and Ni2Al3) with concentrated sodium hydroxide;39 ZnO@Ni@Pt triple-layered core-shell nanorod arrays. Finally,
this has been used as a heterogeneous catalyst for more than porous Ni@Pt core-shell nanotube arrays were synthesized
80 years due to its low cost and high catalytic activity. After from the ZnO@Ni@Pt triple-layered core-shell nanorod arrays
this report, chemical dealloying became a widely accepted by dissolving ZnO in a weak alkali solution. This method is
route to develop many porous alloys and is still used in many facile and suitable for large-scale and low-cost production
applications. Wang et al. developed a facile chemical under mild conditions in the absence of organic surfactants.
dealloying process to produce porous NPs using
nanocrystalline alloys as precursors.40 The non-noble metal
components were selectively dissolved with an excess amount
of concentrated nitric acid to leave a nanoporous residue. This
general pathway could be applied to any nanocrystalline alloys
of noble and non-noble metals (such as Ni–Pt, Ni–Rh) to
produce corresponding nanoporous NPs with increased
surface areas and narrow pore-size distributions.
Recently, an electrochemical dealloying technique was
reported with an improved and more selective process for
leaching of an alloy precursor material to form porous alloys.
The dealloying mechanism is based on the selective dissolution
Fig. 2 Scheme and corresponding TEM images of the coordination-assisted oxidative
of the less-noble component from a binary or multicomponent
etching process. (a) Initial solid Ni–Pt polyhedra. (b) Ni–Pt frame@MOF intermediates I.
solid solution at a potential at which the remaining more- (c) Ni–Pt frame@MOF intermediates II. (d) Final Ni–Pt frame@MOF. The scale bars, 50
noble component is free to diffuse along the surface by which nm. (Insets are the magnified TEM images. The scale bars, 5 nm).44 (Copyright 2015
3D porosity evolves. The process intrinsically forms a core– Nature Publishing Group).
shell nanoporous structure where the surface is passivated by
the more-noble component and the interior of the ligaments An analogous method was reported to prepare Ni–Pt
maintain a significant residual fraction of the less-noble framework structure using a metal-organic framework as
component. Chen et al. reported a nanoporous PdNi (np-PdNi) template (Fig. 5).44 In the first step, Ni-enriched truncated

Please
View Article Online
DOI: 10.1039/C6EE02002J
octahedral Ni–Pt alloy was prepared through a surfactant- effect of two metal species. The chief principle underlying the
assisted solvothermal method, which was then dispersed in d-band theory is that the binding energy of an adsorbate to a
N,N-dimethylformamide containing an appropriate amount of metal surface is largely dependent on the electronic structure

dihydroxyterephthalic acid and autoclaved at 110 °C for 12 h of the surface itself. The metal d-band hybridizes with the
to form Ni–Pt frame@Ni-MOF. Finally, the Ni–Pt frame@Ni- bonding (σ) orbital of the adsorbate to form bonding (d-σ) and
MOF was dispersed in dilute acetic acid to decompose Ni-MOF, antibonding (d-σ)* states (Fig. 6a). For the metals we are
resulting the formation of bare Ni–Pt frame. This is an example concerned with, the (d-σ) state is full, but the extent of filling
of using combined top-down and bottom-up strategies, where of the (d-σ)* state depends on the local electronic structure of
2+
organic linkers captured the abandoned Ni ion during the the metal at the surface, i.e. the surface density of states. An
dealloying process, to build a shell of MOFs on the surface of increased filling of the antibonding (d-σ)* state corresponds to
Ni–Pt alloy in situ. a destabilization of the metal-adsorbate interaction and hence
weaker binding, which induces higher activity.
2.4 Others
Apart from the discussions above (i.e., core–shell, alloy and
porous structures), some other structures are also reported for
bimetallic Ni catalysts. For example, hollow bimetallic (Ni/Au,
Ni/Ag, Ni/Pt, and Ni/Pd) spheres were synthesized via a
decomposition and reduction route by using hollow nickel
hydroxide spheres as precursor.45 Hollow Ni(OH)2
microspheres were first prepared through a hydrothermal
method and subsequently calcined in air to produce NiO
sphere. Hollow metallic nickel spheres were then obtained by
H2 reduction of NiO hollow spheres. Different hollow bimetallic
spheres were then obtained via a replacement reaction route
by using hollow metallic Ni spheres and the corresponding
noble metal precursors, where the Ni spheres acted as a
sacrificial template. The driving force of these reactions comes
from the large standard reduction potential gap between the
Ni2+/Ni redox pair (–0.25 V vs. standard hydrogen electrode
(SHE)) and the Mx+/M redox pair (1.00 V for AuCl4−/Au, 0.80 V
for Ag+/Ag, 0.74 V for PtCl62−/Pt, and 0.83 V for Pd2+/Pd vs. Fig. 3 (a) Hybridization of d-band of metal and σ orbital of adsorbate. (b) d-Band center
with respect to Fermi level and dissociative absorption energy as a function of Pd
(SHE), respectively).
content (Figure generated from data in Ref. 48).48
3. Modification of surface properties in bimetallic Taking Ni–Pd nanoalloy system as an example, the d-band
theory can be applied to determine the effect of Pd on pure Ni
Ni catalysts: Fundamental understanding 48
in the hydrogenation reaction. The energy with which
Understanding the origins of the novel catalytic properties of hydrogen is bound to the metal surface—a decisive factor in
bimetallic surfaces has gained considerable interest in catalytic activity—strongly depends on the Ni/Pd ratio. The
fundamental surface science research. Two critical factors can nanoalloys containing approximately equal amounts of Ni and
be considered. First, the formation of heteroatom bonds Pd show a higher catalytic activity than pure particles of either
changes the electronic environment of the metal surface, metal, and the weakest binding and Gibbs free energies of
thereby modifying its electronic structure through the ligand hydrogen adsorption (close to zero) are calculated. This result
effect. Second, the geometry of the bimetallic structure is can also be explained by the d-band model (Fig. 6b). The d-
typically different from that of the parent metals (e.g., the band center of the mixed Ni–Pd(111) surface is at lower
average metal–metal bond lengths change, resulting in the energies than that of the pure Ni(111) and Pd(111) surface,
strain effect that can modify the electronic structure of the which is in accordance with the higher Ediss of Ni–Pd(111) and
46
metal through changes in orbital overlap). Theoretical hence the higher activity. The same observation has been
approaches, such as density functional theory (DFT), have made for metal clusters of different sizes as well as for bulk
recently been extensively applied for better understanding of surfaces, and therefore is of general applicability.
the surface properties and design principles of different Another example is the well-known Ni–Pt system for ORR
47
bimetallic systems. In this section, we will emphasize the process. The oxygen binding energy on the catalyst surface is a
fundamental roles of added guest metals to modify the key descriptor to determine the ORR activity. Due to the high
catalytic behavior of the host metal. oxophilic nature, Pt binds oxygen too strongly, implying that its
In a bimetallic system, the catalytic reactivity depends on d-band center is too high. Alloying Ni and Pt in specific
the combining electronic effect of two metal components. d- composition lowers the d-band center by both altering the
Band theory can be applied to understand the combining electronics and inducing a degree of irregularity in the Pt

Page 7 of 34 Please
View Article Online
DOI: 10.1039/C6EE02002J
lattice, which subsequently causes the binding to oxygen reason behind the observation that subsurface Pt–Ni–Pt
46
weaker than that on Pt. structure works better in hydrogenation reactions, while the
The geometry of Ni in the bimetallic catalysts is also a key surface Ni–Pt–Pt structure is suitable for oxidation or

factor governing catalytic activities. In general, two possibilities reforming reactions.
arise when Ni is alloyed with a noble metal: Ni either remains
on the surface of the noble metal or it diffuses inside to form a
subsurface region. To explore this fundamental structural 4. Catalysis applications of bimetallic Ni catalysts
modification, bimetallic Ni–Pt has been widely studied. Ni Since Ni has similar electronic properties as Pd and Pt, its
atoms underneath the surface Pt layer are thermodynamically application is widely explored in similar reactions as the other
stable in ultra-high vacuum environment and under two. Here we will critically discuss recent advances on
hydrogenation reactions, exhibiting good activity and stability. bimetallic Ni catalysts where both noble metals (Ru, Rh, Ir, Pd,
In other types of reactions, such as oxidation, Pt, Au, and Ag) and transition metals (Fe, Co, and Cu) have
dehydrogenation, and reforming, Ni-terminated surfaces are been used as guest metal counterpart (see Fig. 8). However, in
generally favored. The segregation energy (Eseg) for transition some cases Ni also acts as a guest metal or promoter to modify
metal alloys is considered as the thermodynamic driving the catalytic activity of reactive noble metals. One issue with
potential to move the subsurface admetal from the bulk to the Ni-based bimetallic catalysts is that Ni is often partially
surface of the host metal. Ruban et al. performed DFT oxidized when exposed on catalyst surface due to its relatively
calculations of the values of Eseg for admetal atoms (M) on low reduction potential. However, oxidation of Ni is not
many host substrates (H).49 If Eseg is sufficiently negative, the necessarily detrimental since Ni in the oxidized form can
admetal segregates to the surface to produce the M–H–H enhance catalytic performance by changing geometric and/or
monolayer structure. If Eseg is sufficiently positive, the surface electronic environment of the second metal. For this reason,
layer is dominated by the host metal, leading to the formation we will include those examples in the discussion even if not
of the H–M–H subsurface monolayer structure. both metal elements are in the metallic state.
Fig. 7 (a) Dependence of the ratio of XPS Ni 2p intensity to XPS Pt 4f intensity and (b)
reversible change in surface structure of Ni–Pt transition metal NPs with the oxidation
and reduction cycles.50 (Copyright 2009 Elsevier).
Besides determining the relationship between Eseg and

structure, it is important to study the influence of adsorbates
on surface segregation using different adsorbates (such as
hydrogen and oxygen), to predict the favorable structure Fig. 8 Different guest metals in bimetallic NiM catalysts and their corresponding
responsible for a particular type of reaction. Taking the catalytic applications.
particular case of bimetallic Ni–Pt system, the segregation of

subsurface Ni was verified under ambient pressure using X-ray This section will be divided into two subsections focusing
absorption near edge structure (XANES) under in situ on applications in energy and in environment, respectively.
conditions.51 Using a polycrystalline Pt foil as the substrate, the The first section is further divided by the type of energy
Ni atoms were found to undergo inward diffusion upon carriers, including hydrogen, hydrocarbons, oxygenates, and
exposure to H2 and surface segregation after exposure to O2. electricity, whereas the second section on environmental
This reversible behavior was also applicable to bimetallic Ni–Pt remediation is categorized by the type of targeted pollutants.
NPs.50 Fig. 7 shows the XPS Ni/Pt intensity ratio, which Wherever possible, we will compare the catalytic activities of
oscillates with the oxidation–reduction cycles. The XPS results bimetallic Ni catalysts with their monometallic counterparts,
indicate that the Ni–Pt NPs surface is NiO-rich in oxidizing and provide reasons for the improved activities on the basis of
gases and Pt-terminated in reducing gases. In turn, such their electronic and geometric configuration. We will also look
structural changes modify the catalytic performance in both into fundamental studies of bimetallic Ni catalysts in order to
hydrogenation and oxidation reactions, and could be the main understand the catalytic mechanisms at the molecular level.

Please
View Article Online
DOI: 10.1039/C6EE02002J
4.1 Energy production significant efforts have been made on the formulation of
4.1.1 Production of H2 as energy carrier. Hydrogen is foreseen to bimetallic Ni catalysts during the last decade, with major
become a major energy carrier in the future.
52, 53
The establishment research focused on how to prevent catalyst deactivation by

of a sustainable hydrogen-based energy infrastructure forces us to carbon deposition. In this section, we will include some
specific examples of those bimetallic systems and discuss the
develop clean/renewable hydrogen production, efficient hydrogen
fundamental role of each component to overcome this issue.
storage, and convenient distribution. Catalysis is not only essential
4.1.1.1.1 Reforming of hydrocarbons. Steam reforming
for hydrogen production, but also plays an important role in
and dry reforming of light hydrocarbons, such as methane,
hydrogen storage. Numerous research efforts have been made on
54 butane etc., provide a promising method for hydrogen
the storage of H2 by both physical and chemical approaches. In

production. Although, steam reforming of methane yields
physical storage, H2 remains in physical forms i.e., as gas, synthesis gas with the high H2 : CO ratio of about 3 : 1, dry
supercritical fluid, adsorbate, or molecular inclusions. Although (CO2) reforming of methane has certain advantages since it
physical storage by means of pressurizing could hold higher utilizes two abundantly available green-house gases to
hydrogen densities, it is complicated by several safety concerns and produce industrially important syngas and can reduce net
57
logistical obstacles. Limitation with other physical H2 storage emissions of these gases. However, compared to H2O
approaches (such as using adsorbing materials) is the low storage reforming, CO2 reforming causes more severe coke formation
capacity. Conversely, chemical H2 storage offers high storage because of increased C/H molar ratio in the feedstock.
performance due to the strong binding of hydrogen and the high Therefore, the development of a coke-resistant catalyst is the
storage densities. In recent years, hydrogen storage materials and major challenge for CO2 reforming of hydrocarbons.
55 56 Dry reforming of methane (DRM) has been investigated
methods – including metal hydrides, metal–organic frameworks,
57 over both noble (Rh, Ru, Pd and Pt) and non-noble metal (Ni,
on-board reforming of hydrocarbon into hydrogen, and organic
70, 71
materials58 – have been investigated extensively. In all cases, Co and Fe) based catalysts. In spite of the high cost, noble
catalytic materials are of immense importance to make the process metal catalysts have drawn attention for their superior coking
effective and highly feasible. Noble metal catalysts work excellently, resistance, higher stability, and activity especially for higher
temperature applications (> 750 °C). Among different noble
but bimetallic Ni catalysts with small amount of noble metals were
59-61 metals, Rh has been identified as the best candidate with the
recently shown to be very promising as well. In this section, we
following trend observed in the catalytic activity and stability
will discuss the developments of bimetallic Ni catalysts in different
of a series of alumina supported noble metal catalysts: Rh/α-
hydrogen production processes such as catalytic reforming, 72
Al2O3 > Ru/α-Al2O3 > Ir/α-Al2O3 > Pd/α-Al2O3 > Pt/α-Al2O3.
dehydrogenation, water-gas shift (WGS) reaction, and
The addition of a small amount of Rh in Ni catalyst,
electrocatalysis. encouragingly, further enhanced catalytic activity without any
4.1.1.1 Catalytic reforming. Catalytic reforming is a widely coke formation. According to Rostrup-Nielsen, the coke
used technique for the production of hydrogen from different resistance of Ni-based catalysts can be enhanced by enhancing
resources such as natural gas, oil, coal, alcohols etc. the adsorption of steam (in case of steam reforming process)
Specifically, high-temperature steam reforming of or CO2, by enhancing the rate of the surface reaction, or by
hydrocarbons (i.e., methane at over 800 °C) accounts for a decreasing the rate and degree of methane activation and
significant portion of worldwide commercial hydrogen 73
dissociation. Various promoters such as alkali or alkaline
60 71
generation (about 50%). Another potential application of earth metals can be used to achieve this. However, major
steam reforming is on-board hydrogen generation for fuel-cell research has been focused on noble metals as promoters
62
powered vehicles. Noble metals are known to be the best because of their high activity and excellent coking resistance. It
catalysts for hydrocarbon and alcohol reforming due to their has been proved that carbon formation occurs less on noble
57, 63, 64
greater ability to break C–C bonds. However, recent metals than on Ni, mainly because the lower solubility of
attention has been slightly shifted to 3d transition metals, carbon in noble metals favors the gasification of carbon. In
preferably Ni-based catalysts, which are also effective in fact, many previous works have reported that Ni catalysts can
10
breaking C–H and C–C bonds. Nevertheless, nickel-based exhibit high efficiency and better resistance against carbon
catalysts are very sensitive to deactivation by sintering and 74
deposition when modified with noble metals such as Pd,
65 75-83 84, 85 86-91 92 93-97 98-100
carbon deposition. Unfortunately, both desired reforming Pt, Ru, Rh, Ir, Au, and Ag. The effects of
reaction and undesired coke deposition are plausibly initiated these secondary noble metals are diverse; they may function
66
by the same elementary hydrocarbon activation step, and to reduce and stabilize the metal particle size of the Ni
under steam-reforming conditions metal surfaces are covered 75, 77, 78 101
catalysts (e.g., Pt, Rh ), to tailor the ensemble size of
with various CHx intermediates. Without a fast steam 98 93 93
Ni catalysts (e.g., Ag, Au ), to block the step sites (e.g., Au ),
gasification step to convert these intermediates to CO and H2, or to modify the surface electronic properties of the Ni
these adsorbed CHx species on Ni can undergo further 93
catalysts (e.g., Au ). The modification of Ni catalysts with
dehydrogenation, polymerization, and rearrangement into noble metals was reviewed in some early reviews and it has
67
highly stable carbon. It has been reported that the addition been demonstrated as a promising approach to design
of noble metals to Ni catalysts can promote the reducibility of 6,
catalysts with excellent performances for methane reforming.
68, 69 9, 102, 103
Ni, and stabilize it during the catalytic process. Indeed, We will mainly focus on the fundamental role of noble

Page 9 of 34 Please
View Article Online
DOI: 10.1039/C6EE02002J
metals to alter the catalytic and coke resistance properties of The main products from steam reforming over the Ni/MgAl2O4
the bimetallic Ni systems. catalyst without the Ag component were H2, CO, CO2, and CH4,
A landmark paper by Nørskov and co-workers reported with a small amount of C2~. However, the addition of Ag

that Au/Ni surface alloy on the Ni particles (supported on reduced the degree of carbon deposition and improved the H2
MgAl2O4) was active for steam reforming and more resistant product selectivity by eliminating the formation of all C2~
93
towards carbon formation than pure Ni catalyst. The catalyst products. The unmodified Ni/MgAl2O4 catalyst experienced a
was designed based on the fact that when Au is added to any strong Ni sintering at high temperature. It was also proved that
of the low index Ni surfaces, an alloy is formed in the first the catalytic performances differed according to the order in
104
atomic layer. Since the Au atoms have a high electron which the metal precursors were added. Fig. 9 illustrates the
density, the neighboring Ni atoms experience an enhanced phase changes of different catalysts during the butane
electron density and a higher effective coordination number reforming process. Simultaneous addition of Ag/Ni depressed
simultaneously. The advantage of Ni surface modification by the NiAlO3 spinal structure and induced catalytic deactivation
Au can be determined by two factors: (i) the ability of the due to their strong sintering. When Ag was added between Ni
surface to activate hydrocarbon molecules and (ii) the and Al, deactivation was reduced significantly, while
tendency of the surface to bind C and form graphite. The simultaneously improving the catalytic activity.
abstraction of first H atom from CH4 is considered as the rate-
limiting step in the steam-reforming process over pure Ni
catalysts. The addition of Au on Ni surface could slightly
increase the energy barrier of CH4 dissociation step, as
confirmed by DFT calculations and experimental methods.
Therefore, Au impeded CH4 dissociation as expected. However,
when the effect of Au addition was considered for the second
factor, i.e. tendency to bind C, it was observed that Au-
modified Ni surface had much lower ability to adsorb C. On the
pure Ni surface, the most stable adsorption site was the
threefold hexagonal close-packed site. However, the threefold
sites adjacent to a gold atom were unstable, and even the
threefold sites that were next nearest neighbors to the Au
atoms were substantially destabilized. The effect of Au on
atomic C adsorption was thus considerably stronger than the
effect on CH4 activation, and eventually led to a coke resisting
Fig. 9 Expected phase transformation in the butane reforming mechanism before and
catalyst without much compromising of the activity.
after butane reforming reaction.99 (Copyright 2010 Elsevier).
Bimetallic Ni–Pt catalysts behave in a similar way to that of
Ni–Au. In a recent work, supported Ni/Pt bimetallic NPs with
In addition to carbon deposition on the catalysts, sulfur
controlled surface composition and structure were prepared.81
poisoning is another serious issue, which is often seen during
The surface restructuring of the bimetallic catalysts upon
the steam reforming of hydrocarbons due to sulfur
thermal treatment was investigated, which demonstrated the 105
contaminants. Bimetallic Ni–Rh catalyst on CeO2–Al2O3
structure evolution of the bimetallic NPs from Pt monolayer
support exhibited better sulfur tolerance than their
island-modified Ni NPs to core–shell bimetallic NPs composed
monometallic counterparts at 550 °C, although the catalytic
of a Ni-rich core and Ni/Pt alloy shell. The surface modification
performance of bimetallic catalyst was inferior compared with
of the Ni-based catalysts by adding Pt atoms effectively 106
the pure Rh catalyst. Unlike Ni catalyst, Rh catalyst
enhanced the catalytic activities and resistance towards
dramatically improved the sulfur tolerance upon increasing the
carbon formation in the dry reforming process. To assess the
temperature to 800 °C. The superior sulfur tolerance of the Rh
surface and bulk structure according to the Pt/Ni elemental
catalyst at this high temperature could be associated with its
composition, a series of alumina-supported Ni/Pt bimetallic
better capability in sulfur oxidation than Ni, which formed
NPs with various Pt coverages were prepared and tested. DFT
different sulfur species on metal surface. It was observed that
calculations suggested that the addition of Pt on the Ni surface
the metal sulfide and organic sulfide were the dominant sulfur
might facilitate the CH oxidation pathway and inhibit the
species on the Ni catalyst, while sulfonate and sulfate
carbon oxidation pathway. This led to enhanced catalytic
predominated on the Rh catalyst. The presence of sulfur
activity and suppressed carbon formation as the Pt coverage
induced the formation of nickel sulfide which suppressed the
increased.
carbon gasification and caused severe carbon deposition on
Modification by Ag follows a different mechanism to
the Ni catalyst at 800 °C. This could be one of reasons for the
improve the catalytic and coke resistance properties of Ni
lower activity of bimetallic Rh–Ni catalyst than pure Rh.
catalysts. Kang et al. reported a Ni/Ag/MgAl2O4 catalyst
Along with the use of noble metal promoters, 3d transition
containing equimolar amounts of Ni and Ag for the steam
99 metals, especially Fe, Co and Cu, also improved the activity and
reforming of butane. During butane reforming, the Ag and Ni
coke resistance properties in the methane reforming
components played a role in the oxidation of the feed gases.

Please
View Article Online
DOI: 10.1039/C6EE02002J
107-115
reaction. In a recent study, a series of bimetallic Fe- and consequently suppress the methanation reaction, whereas
Ni/MgAl2O4 catalysts with Fe/Ni ratios between 0 and 1.5 were Co would enhance the dissociation of CO on the Ni surface.
107
examined for methane dry reforming at 650–800 °C. In H2-

TPR, Fe2O3 and NiO were reduced above 700 °C to form a Fe-Ni
alloy, constituting the active phase for the methane dry
reforming reaction (Fig. 10). This alloy remained stable in a
flowing gas stream of CO2 during reoxidation until 627 °C, but
was decomposed to metallic Ni and Fe3O4 above this
temperature. The process of dry reforming on Ni–Fe could be
described by the Mars–van Krevelen mechanism, where CO2

oxidizes Fe to FeOx and CH4 is activated on Ni sites to form H2
and surface carbon. This surface carbon was oxidized by FeOx
lattice oxygen to produce CO, thereby reducing the probability
of carbon deposition.
Fig. 11 Model depicting the dynamic transformations of the Ni containing phase upon
activation and steam reforming of ethanol for both Ni/CeO2 and Ni–Pt/CeO2
127
catalysts. (Copyright 2016 Elsevier).
Incorporation of noble metals such as Pt, Rh can

simultaneously improve the reforming activity and prevent the
117, 127-133
catalyst deactivation. Aqueous phase reforming of
Fig. 10 Schematic diagram of Ni–Fe alloy formation, during H2-reduction, and
ethylene glycol over supported Ni–Pt/C and Ni–Pt/γ-Al2O3
107
decomposition, during CO2 oxidation. (Copyright 2015 American Chemical Society). catalysts revealed that enhanced activity of the bimetallic
129
catalysts was correlated to changes in the catalyst structure.
4.1.1.1.2 Reforming of oxygenates. The production of H2 Under the reaction conditions, Ni segregated to the surface of
from renewable resources such as ethanol and other small the catalysts, resembling Ni-terminated bimetallic surfaces
molecule oxygenates (i.e., acetone, glycerol, ethylene glycol that were more active than Pt as identified in theoretical and
etc.) has received a special attention in recent years.
116-122 experimental studies on model surfaces. In the very recent
Among different metal catalysts investigated, late transition work, Moraes et al. investigated the effect of Pt addition on
metals such as Ni, Co, Pt, and Ru remain as the major active the performance of a Ni/CeO2 catalyst for low temperature
127, 133
components for their high activity in breaking C–H and C–C steam reforming of ethanol. Based on different
bonds.
123
Although, oxygenates reforming require characterization techniques, they provided an explanation
comparatively lower temperature than hydrocarbons, coke addressing why Ni/CeO2 deactivated more extensively than
formation on the metal surface is more inclined to take place. Ni–Pt/CeO2. In a first step, both catalysts are able to
In a recent review article, Li and Gong explained the different decompose the ethoxy species, the dehydrogenated species
possible pathways of alcohol reforming on oxide and (acetaldehyde, acetyl species), and the acetate species into H2,
supported metal catalysts, where the metal surface is CO, and CHx. Following that, there are two possibilities: (i) the
proposed to be the primary active site for the reforming CHx species can be hydrogenated and desorbs as methane or
10
process. In the case of Ni, carbon deposition becomes severe may react with water producing H2 and CO or, (ii) these CHx
123
upon the aggregation of Ni particles.
124
Therefore, the metal species may be further dehydrogenated to carbon.
dispersion and inhibition of metal sintering are critical in the Therefore, when the rate of this reaction pathway is higher
development of an efficient nickel reforming catalyst. than the rate of desorption of CHx species as CH4, carbon is
Skeletal Ni is considered as a highly active catalyst due to accumulated over the surface and the catalyst deactivates. In
its considerable nickel dispersion and large exposed surface situ X-ray absorption studies revealed the formation of a nickel
area. Gong et al. reported low-temperature steam reforming carbide phase during the reforming process over Ni/CeO2
of ethanol using skeletal Ni (Ni-Al alloy powder prepared from catalyst, which was associated with amorphous carbon
50 wt% Ni and 50 wt% Al)-based catalysts in combination with deposition and catalyst deactivation. The addition of Pt to
different assistant metals such as Pt, Cu, and Co.
125
It was Ni/CeO2 catalyst promoted the decomposition of
observed that three different assistant metals play different dehydrogenated and acetate species to hydrogen, methane,
roles in the reaction; Pt and Cu suppress the methanation and CO and carbonate species (Fig. 11). The segregated Pt
enhance H2 production, while Co promotes the methanation effectively produced reactive hydrogen species by dissociative
and increases CH4 selectivity. It has been proved that adsorption of hydrogen and spillover of adsorbed hydrogen
dissociative adsorption of CO is generally suppressed from left atoms to the Ni surface. These highly reactive hydrogen atoms
to right and from 3d to 5d in the periodic table of transition- hydrogenated the adsorbed carbon precursor species, which
metal elements.
126
Therefore, it can be rationalized that Cu eventually desorbs as methane. As such, the segregation of Pt
and Pt could suppress the dissociation of CO on the Ni surface, on the surface of the Ni particles minimized the formation of
nickel carbide and promoted catalyst stability.

Page 11 of 34 Please
View Article Online
DOI: 10.1039/C6EE02002J
Journal Name

ARTICLE
Table 1 Catalytic performance of bimetallic Ni catalysts in the reforming reaction of hydrocarbons and oxygenates.
Catalyst M/Ni Synthesis method Reaction T (°C) Catalytic performance Note Ref.
(wt/wt)
76
Ni-Pt/γ-Al2O3 0.33 IWI DRM 700 69% CH4 conv. Ni increased the electron-withdrawing ability of Pt
79
Ni-Pt/γ-Al2O3 0.05 IWI DRM 750 78% CH4 conv. carbon deposition was markedly lowered
Ni-Pt@Hol S-1 0.34 IWI DRM 800 >70% CH4 conv., GHSV 72 L g−1 hollow silicalite shell prevented coke deposition on 82
−1
h encapsulated Ni
74
Ni-Pd/ZrO2-La2O3 0.25 IWI DRM 700 73% CH4 conv. –
86
Ni-Rh/Al2O3 0.33 IWI DRM 700 87% CH4 conv. segregation of metals led to the formation of Ni-rich
surface alloy
90
Ni-Rh/CeO2-Al2O3 0.1 IWI DRM 750 85% CH4 conv. higher activity and stability due to the presence of the
+4 +3 δ+
redox couple Ce /Ce and Rh0/Rh
89
Ni-RhCe2Zr1.51 0.1 pseudo sol–gel DRM 800 >90% CH4 conv. Ce–Zr mixed oxide support increased the gasification of
surface coke
97
Ni-Au/MgAl2O4 0.057 IWI DRM 800 100% CH4 conv. Au prevented the formation of carbon nanotubes
108
Ni-Co/CeO2-ZrO2 1.5 DP, HT DRM 800 >55% CH4 conv. defective CeO2–ZrO2 crystalline lattice increased carbon
oxidation
−1 109
Ni-Co/ZrO2 1.0 IWI DRM 750 90% CH4 conv., GHSV 150 L g Co produced more H2 and maintained the reduced state
−1
h of Ni
−1 112
Ni-Co/MSN 1.0 in situ electrolysis DRM 783 97% CH4 conv., GHSV 38.7 L g Co induced the formation of spinel-type NiCo 2O4 solid
−1
h solution to result d-electron transfer from Co to Ni
107
Ni-Fe/MgAl2O4 0.7 IWI DRM 800 51% CH4 conv. surface carbon oxidized FeOx lattice oxygen
88
Ni-Rh/CeZrO2 0.017 IWI SR of n-butane 680–740 H2 yield 10.6 mol/mol n-butane oxidized Ni and Rh species increased the activity
85
Ni-Ru/CeO2-Al2O3 0.1 sol–gel ATR of n- 750 H2 yield 1.6 mol/mol n-dodecane high activity due to high dispersion, high metal area and
dodecane high reducibility of Ni

99
Ni-Ag/MgAl2O4 0.11 IWI SR of n-butane 700 100% butane conv., 68% H2 yield addition of Ag increased H2 selectivity by reducing C2~
products
130
Ni-Pt/CeO2-Al2O3 0.08 IWI SRE 500 60.8% H2 yield Ni cleaved C–C bond, Pt hydrogenated the coke
precursors (CxHy)
119
Ni-Pt/CeO2-Al2O3 0.17 IWI APR of glycerol 240 86% H2 yield Ni modified crystallite and electronic structure of Pt
117
Ni-Rh/Y2O3-Al2O3 0.13 IWI SRE 402 44.9% H2 yield Lewis acidic NiAl2O4 phase decreased coke formation
134
Ni-Cu/ZrO2 0.54 DP OSR of 360 60% H2 yield high activity due to bimetallic and support effect
methanol
135
Ni-Cu/ZrO2 0.33 urea co- SRE 600 84% H2 yield Cu enhanced the WGS reaction and favored
precipitation acetaldehyde decomposition and reforming over the
ethanol dehydrogenation
136
Ni-Cu/MWNT 0.08 reflux APR of glycerol 240 72% H2 yield Cu suppressed undesirable methanation reaction
IWI: incipient wet impregnation; DP: deposition-precipitation; HT: hydrothermal; DRM: dry reforming of methanol; SRE: steam reforming of ethanol; ATR: auto-thermal
reforming; OSR: oxidative steam reforming; APR: aqueous phase reforming.
Among the noble metal-free catalysts, bimetallic Ni–Cu Apart from the dry reforming and steam reforming
catalysts are one of the most studied bimetallic systems for processes, another promising alternative way to produce
116, 119, 134, 135, 137-142
ethanol steam reforming. It has been shown syngas is the partial oxidation of methane (POM) and other
that the addition of Cu in Ni catalysts highly promotes the WGS hydrocarbons. POM is an exothermic catalytic process in which
137
reaction to instantly convert the adsorbed CO into CO2. methane is converted to form H2 and CO in presence of limited
Furthermore, Cu addition induces the decomposition of amount of oxygen (or air). Compared to the early success of
CH3CHO, which is one of the intermediates in coke formation methane steam reforming, catalytic partial oxidation remained
139
process. almost unexplored until 1990. Since the first reports by Huszar

Please
View Article Online
DOI: 10.1039/C6EE02002J
et al. and Gavalas et al., a significant amount of research has Pt(111) surface was predicted to be a catalytically active
143
been carried out on Ni/Al2O3. However, deactivation surface. According to the calculation, Ni–Pt–Pt(111) bimetallic
−1
occurred in all cases due to the formation of NiAl2O4. surface has a nitrogen binding energy of 130.7 kcal mol ,

−1
Furthermore, carbon deposition was another major issue on slightly lower than that of Ru (141.6 kcal mol ), and is a
nickel catalysts, which reduced the number of active sites of potentially active catalyst. While on the other hand, the
the catalysts. It was observed that both support and promoter subsurface configuration, Pt–Ni–Pt(111), and the parent
had a considerable effect on the activity and stability of the metals, Pt(111) and Ni(111), were expected to have lower
144
catalysts. Al2O3 could be replaced by other supports such as activities because of the weaker nitrogen binding energies
−1
La2O3, MgO, SiO2, CeO2, ZrO2, and TiO2, which act as promoters (87.5, 102.1 and 113.8 kcal mol respectively). This was
and to reduce the sintering of active Ni phase into the support. verified using temperature-programmed desorption and high-
Different bimetallic Ni catalysts consisting of noble metals such resolution electron energy loss spectroscopy experiments. 3 L
145 146-149 150 151 −6
as Pt, Ru, Rh, and Ir as well as non-noble metals (where L indicates Langmuir, 1 L = 1 × 10 torr s) of ammonia
149, 152, 153 154
such as Co, Cu, lanthanides (Pr, Gd, Lu),155 and was dosed at 350 K, then the temperature was ramped at a
156
actinides (Th, U) have been studied. In all cases, the added heating rate of 3 K s−1 and desorption of nitrogen was
second metals exhibited increased reducibility and higher coke monitored using a mass spectrometer. The Ni–Pt–Pt surface
resistance of the catalysts as observed in the bimetallic Ni was the only one that showed activity towards ammonia
catalysts for reforming reactions. decomposition under these conditions, as indicated by the
4.1.1.2 Production of H2 through dehydrogenation and peak at 626 K (Fig. 12). This confirmed the model predictions
hydrolysis. Developing hydrogen storage materials is essential of the Ni–Pt–Pt surface being active towards ammonia
for a viable hydrogen economy. An ideal hydrogen storage decomposition based on an optimal nitrogen binding energy
material should satisfy several technical requirements. These and the other three surfaces being inactive due to a nitrogen
include: sufficiently high volumetric and gravimetric capacities, binding energy that was too low. The activity of the Ni–Pt–Pt
facile release of hydrogen at a reasonably low temperature, surface was also compared with Ru(0001) surface. In a
and efficient regeneration at a practical temperature.59, 157 previous study of ammonia decomposition on Ru(0001), an
Hydrides of boron and nitrogen have drawn significant interest exposure of 3,500 L of ammonia was dosed at 500 K to achieve
because they are light atoms with high gravimetric hydrogen a nitrogen saturation coverage.165 In comparison, saturation
capacities. In addition, hydridic B–H and protic N–H bonds can coverage was achieved with 3 L at 375 K on the Ni–Pt–Pt
thermally or catalytically dissociate to yield hydrogen. Many surface. The significantly lower dosing temperature and
chemical storage materials such as ammonia, ammonia- ammonia exposure clearly indicated that the overall
borane, hydrazine, hydrazine-borane, formic acid etc., are dehydrogenation barrier was much lower for the bimetallic
reported, where two main processes, dehydrogenation and surface. Along with the success of Ni–Pt catalyst, noble metal-
hydrolysis, are generally involved in the production of H2. free Ni-based bimetallic catalysts (such as Ni–Fe alloy NPs,
4.1.1.2.1 Dehydrogenation of ammonia. Decomposition of core–shell Ce–NiO@SiO2 etc.) were also explored for the
ammonia has recently gained increased attention due to the decomposition of ammonia.166, 167 However, the temperature
potential for ammonia to be used as a hydrogen storage applied in these cases was very high (773–1073 K) to achieve a
medium. Ammonia can be liquefied easily at a pressure of 8 high conversion.
atm at 20 °C, leading to high energy densities. As a result of its
high hydrogen storage capacity, ammonia can serve as a fuel
to provide COx free hydrogen through catalytic
decomposition.158 It has been shown that the heat of nitrogen
chemisorption is a good descriptor for ammonia synthesis and
decomposition.159, 160 The binding energy of the nitrogen atom
to the surface must be strong enough for dehydrogenation of
the NHx species to occur, but sufficiently weak that the
nitrogen recombines to desorb from the surface to complete
the catalytic cycle. Initial studies on single-metal catalysts
showed that Ru is the most active decomposition catalyst,161
but it is expensive and therefore not employable for large scale
application. Later on, studies on bimetallic catalysts showed
that Co–Mo is even more active than Ru, which triggered more
exploration on a series of transition metal-based bimetallic
systems that can potentially replace the precious single noble
Fig. 12 Ammonia decomposition on different Ni–Pt surfaces. TPD results of
metals.159, 160
nitrogen desorption from the decomposition of ammonia on Pt(111), Pt–Ni–Pt,
Vlachos et al. reported an interesting, rational approach to Ni–Pt–Pt and a Ni(111) film.162 (Copyright 2010 Nature Publishing Group).
designing bimetallic Ni catalysts with comparable ammonia
162-164
decomposition activity as to that of Ru. Using
microkinetic modeling combined with DFT studies, Ni–Pt–

View Article Online
DOI: 10.1039/C6EE02002J
−1
4.1.1.2.2 Hydrolysis of ammonia borane. Although higher than that of monometallic Ru NPs (31.5 min ). The
ammonia is easily available and can be stored safely, for on- same group reported NixRu1–x (x = 0.56–0.74) alloy NPs with
board applications it is desirable for the storage materials to different Ni/Ru ratios among which Ni0.74Ru0.26 sample

169
be able to release hydrogen at moderate temperature. performed as the best catalyst for AB hydrolysis. The
Consequently, an air stable compound ammonia borane hydrolysis activation energy for the Ni0.74Ru0.26 alloy catalyst
−1
(NH3BH3, AB), which has a hydrogen capacity of 19.6 wt%, was approximately 37 kJ mol , which is considerably lower
−1
which is well above the US Department of Energy targets than the values measured for monometallic Ni (≈ 70 kJ mol )
59 −1
(2015) of a gravimetric density (9 wt%), and can be and Ru NPs (≈ 49 kJ mol ). The value is also lower than
−1
catalytically hydrolyzed at room temperature, received previously reported Ni@Ru (≈ 44 kJ mol ) and most of the
170
considerable attention. noble metal-containing bimetallic NPs reported in literature.
There are many reports on Ni-noble metal catalytic Ru@Ni core–shell NPs supported on graphene were
systems for the hydrolysis of AB. Noble metal containing synthesized via one-step in situ co-reduction, affording a TOF
hollow bimetallic (Ni/Au, Ni/Ag, Ni/Pt, and Ni/Pd) catalysts value of 340 min−1.171 The number is much higher than the
were prepared via a decomposition and reduction route and reversed Ni@Ru NPs, which could be due to the presence of
tested for hydrogen generation from AB.45 Ni/Pt catalyst was more reactive Ru in the shell.
most active among all the combinations. In another study, Ni–Au NPs of 3–4 nm diameter embedded in silica
same results were found using the combination of Pt and nanospheres were prepared by in situ reduction in an aqueous
transition metals such as Fe, Co and Ni.168 Ni–Pt NPs with a solution of NaBH4/NH3BH3. Compared to monometallic
ratio of 1:4 exhibited the best catalytic activity. The Ni Au@SiO2 and Ni@SiO2, the as-synthesized Ni–Au@SiO2
oxidation state in Ni–Pt NPs seems to be responsible for the catalyst showed higher catalytic activity and better durability
corresponding catalytic activity in AB decomposition. As in the hydrolysis of ammonia borane, generating a nearly
confirmed by XANES study, Ni remains in metallic state in Ni– stoichiometric amount of hydrogen at 18 °C.172 Triple-layered
Pt (1:4) NPs but higher oxidation state of Ni is found in Ni–Pt Ag@Co@Ni core–shell NPs containing a silver core, a cobalt
(1:1) NPs and Ni–Pt (4:1) NPs leading to reduced catalytic inner shell, and a nickel outer shell were prepared by an in situ
performance (Fig. 13). chemical reduction method.173 Compared with its bimetallic
core–shell counterparts, this catalyst showed higher catalytic
activity for the hydrolysis of AB. Ni–Co double shells
surrounding the silver core in the special triple-layered core–
shell structure provided increasing amounts of active sites on
the surface to facilitate the catalytic reaction.
Fig. 14 Effect of Fe/Ni molar ratio in the hydrogen production from AB. Inset
shows the TON versus Ni content.174 (Copyright 2015 Wiley-VCH).
Fig. 13 (a) Normalized absorption spectra at the Ni K-edge for the corresponding 3d transition metal-based catalysts comprising of Ni were
Pt–Ni catalysts with three different ratios, pure Ni NPs, and references of Ni foil,
also explored for the hydrolysis of AB with good activity, where
Ni NPs, and NiO. (b) Hydrogen evolution of hydrolysis of AB aqueous solution
(0.5 wt%, 5 mL) catalyzed by pure Pt NPs, pure Ni NPs, and Pt–Ni NPs with
Ni–Fe and Ni–Cu combinations were found to be most
different ratios under ambient atmosphere.
168
(Copyright 2014 American active.174-177 Xu and coworkers reported magnetically
Chemical Society). recyclable Fe1–xNix nano-alloy catalysts which exhibited Pt-like
high catalytic activity.175 Kim et al. prepared bimetallic NiCu
Chen et al. reported ultra-small magnetic Ni@Ru core–shell nanorods (NRs) incorporated on carbon nanofibers (NFs) that
24
NPs, showing enhanced activity in the hydrolysis of AB. A TOF showed superior catalytic activity toward H2 release from AB
−1
value of 114 min was achieved for Ni@Ru NPs which was as well as excellent recyclability and chemical stability.177 The

Please
View Article Online
DOI: 10.1039/C6EE02002J
−1
activation energy (~28.9 kJ mol ) for the reaction was very low Although the catalytic activity of this Rh–Ni catalyst is very
over the catalyst. Recently, CeO2 supported bimetallic Ni–Fe impressive, the use of high amount of Rh (80 mol% in Rh4Ni) is
NPs were reported as efficient noble-metal-free catalysts for not appealing from an economical point of view. Therefore,

174
AB hydrolysis. The catalyst comprises highly dispersed and the same group synthesized Ni–Pt and Ni–Ir catalysts with
partially oxidized amorphous Ni–Fe NPs stabilized by strong much lower noble metal content (7 mol% Pt and 5 mol% Ir,
interaction with the CeO2 support by Ni–O–Ce and Fe–O–Ce respectively) and achieved similar results as that of Ni–Rh
180, 188
bonding. The influence of the Fe/Ni ratio on catalytic activity catalysts. The surfactant-assisted process enhanced the
revealed a volcano-shaped relationship with a maximum at activity by suppressing the agglomeration of NPs, without
Fe/Ni = 1:1 (Fig. 14). The volcano-shaped activity order clearly affecting the bimetallic compositions of the NPs.
suggested that the formation of a uniform FeNi alloy structure

(at Fe/Ni = 1:1) on the surface of CeO2 and the synergistic
effect originated from the integration of Fe with Ni.
4.1.1.2.3 Dehydrogenation of hydrazine and hydrazine
borane. Anhydrous hydrazine (N2H4) is another promising
hydrogen storage material because of its high H2 content (12.5
wt%) and its liquid state at room temperature. However, direct
use of anhydrous hydrazine is restricted because it is
extremely toxic, highly reactive, and potentially explosive.
Therefore, hydrous hydrazine (N2H4∙H2O) is often used due to
safety concerns. Complete decomposition of hydrazine yields
only hydrogen and nitrogen according to the following
equation:
Fig. 15 Selectivity for hydrogen generation from hydrous hydrazine (0.5 M)
N2H4 → N2 (g) + 2H2 (g) [∆H = −95.4 kJ mol−1] (1) catalyzed by RhxNiy (x = 0–64; y = 0–16) with Rh/N2H4 = 1:10 at room
temperature.13 (Copyright 2009 American Chemical Society).
Meanwhile, hydrazine can also incompletely decompose into
ammonia and nitrogen, as follows:
In spite of the quantitative selectivity, sluggish reaction
3N2H4 → 4NH3 (g) + N2 (g) [∆H = −157 kJ mol−1] (2) kinetics is a major issue in the hydrazine decomposition. In the
From the perspective of hydrogen storage, reaction (1) above discussed work by Xu et al., addition of surfactants
must be selectively promoted and reaction (2) restrained. The during the preparation of NPs makes it difficult to separate
dissociation pathways depend significantly on the catalyst and catalysts from the reactants and also significantly reduces the
reaction conditions. Initial research findings showed that noble reaction rate.13, 180, 188 Wang et al. reported a surfactant-free
metals such as Ir and Rh were highly effective for the method to prepare a supported catalyst by depositing Ni–Rh
decomposition of hydrazine.178, 179 However, the hydrogen NPs on graphene oxide, where the support played a key role to
selectivity is highly dependent on the reaction conditions obtain highly dispersed Ni–Rh NPs.183 Ni–Rh catalysts prepared
(mainly temperature) and the nature of the catalysts. Earlier this way exhibited 100% H2 selectivity and remarkably high
studies achieved maximum hydrogen selectivity up to only activity to complete the decomposition reaction of hydrous
43.8%, which was due to these two competing reactions hydrazine within only 49 min in the presence of NaOH at room
during the decomposition. Later on, non-noble metals such as temperature, which was more than three times faster than
179, 200,
Ni were incorporated to reduce the material cost and Ni-based that of the previously reported single metallic catalysts.
bimetallic catalysts such as Ni–Ir,180, 181 Ni–Rh,13, 182-187 Ni–Pt,14, 201
188-197
and Ni–Pd,198, 199 exhibited superior catalytic Luo et al. proposed a facile liquid impregnation approach
performance to their monometallic counterparts. for the immobilization of ultrafine bimetallic Ni–Pt NPs inside
194, 195
Xu and coworkers reported that the combination of Rh, Pt, and the pores of MIL-101 (Fig. 16). Highly dispersed
Ir with Ni could catalyze the complete decomposition of bimetallic Ni–Pt NPs with different compositions were
hydrous hydrazine at room temperature with 100% H2 obtained that showed remarkable activity, selectivity, and
selectivity.13, 180, 188 A surfactant-assisted co-reduction process durability towards hydrogen generation from aqueous alkaline
was applied to synthesize bimetallic Rh–Ni catalysts with solution of hydrazine. The catalysts showed composition
different Rh/Ni ratios. Despite nickel itself being inactive to the dependent catalytic activity among which Ni88Pt12@MIL-101
reaction, the presence of nickel drastically enhanced H2 exhibited the highest catalytic activity, with the turnover
13 −1 −1
selectivity to a maximum of 100% at Rh/Ni = 4:1 (Fig. 15). frequency (TOF) value of 375.1 h at 50 °C and 65.2 h at
Physically mixed Rh NPs and Ni NPs with the same Rh/Ni ratio room temperature. The same group reported Ni–Pt NPs
−1
did not show any activity enhancement over Rh, confirming dispersed on MIL-96 which exhibited a TOF of 114.3 h and
the role of bimetallic synergistic effect. Alloying of Rh and Ni 100% hydrogen selectivity at room temperature with a
193
led to a modification of the catalyst surface and tuned the composition of Ni64Pt36/MIL-96. In both cases, excellent
interactions of Rh with the N–N and N–H bonds as well as the catalytic performances were due to the synergistic effect of
stability of reaction intermediates on the catalyst surface. the metal organic framework (MOF) support and Ni–Pt NPs,

View Article Online
DOI: 10.1039/C6EE02002J
−1 202
since Ni–Pt NPs supported on other conventional supports – (TOF = 528 h ) at room temperature. Wei and co-workers
such as SiO2, carbon black, γ-Al2O3, poly(N-vinyl-2-pyrrolidone) synthesized bifunctional Ni–Fe-alloy/MgO catalyst containing
203
(PVP), and the physical mixture of Ni–Pt and MIL-96 – both an active center and a solid base center. The catalyst

exhibited inferior catalytic activity. Unfortunately, the exact showed comparable activity to most reported noble metal
nature of the interaction between metal NPs and MOF was not catalysts, exhibiting 100% conversion and 99% H2 selectivity at
clear. When comparing the activities of the two catalysts, room temperature. The strongly basic MgO support excluded
Ni88Pt12@MIL-101 and Ni64Pt36/MIL-96, MIL-96-supported the requirement of externally added base (such as NaOH),
catalyst showed better activity at room temperature. This which was used in many other studies to increase activity.
could be understood by the structures of these two MOF Hydrazine borane (N2H4BH3, HB) is another H2 storage
materials. The pore size in MIL-96 is about 1.2 nm, which is material which has a gravimetric hydrogen storage capacity of
much smaller than that of MIL-101 (2.9 nm). As a result, most 15.4 wt% and can be easily prepared by mixing sodium
of the metal NPs are expected to stay on the surface of MIL-96 borohydride and hydrazine hemisulfate at room temperature.
instead of going inside the pores. Therefore, it is expected that The aqueous solution of HB is stable against spontaneous
Ni–Pt NPs on the surface of MIL-96 are more exposed towards hydrolysis. Similar to hydrazine, efforts were made on the
the substrate molecules. However, at increased temperature dehydrogenation of HB using bimetallic Ni catalysts.205-207 A
(50 °C), Ni88Pt12@MIL-101 catalyst showed increased activity, series of Ni-based bimetallic systems were investigated with
which could likely be due to the higher diffusion of substrate Pt, Ru, Rh, or Ir as the second metal. The results showed that
through the pores and better contact with the Ni–Pt NPs most of Ni1–xMx nanocatalysts outperformed the monometallic
located inside the pores. In a recent work, Luo and Cheng Ni, Pt, Ru, Rh, and Ir catalysts.206 The best performance
reported ultrafine monodisperse bimetallic Ni–Pt NPs on achieved was 5.1 ± 0.05 mol (H2 + N2) per mol(HB) with
graphene by co-reduction of nickel acetylacetonate and Ni0.89Rh0.11 and Ni0.89Ir0.11. Using Ni0.89Pt0.11 NPs, 5.79 ± 0.05
platinum acetylacetonate with borane-tert-butylamine in equiv (H2 + N2) per HB could be released, corresponding to H2
oleylamine.191 The catalyst with a composition of selectivity as high as 93 ± 1%.205 The Ni1–xPtx NPs were capable
Ni84Pt16/graphene exhibited the highest TOF of 415 h−1 with to hydrolyze the BH3 group of HB and then decompose the
100% hydrogen selectivity at 50 °C. N2H4 group at 50 °C, whereas the monometallic Ni and Pt were
inactive for the second reaction. Xu and co-workers reported a
sodium-hydroxide-assisted reduction approach to synthesize
ultrafine surfactant-free bimetallic Ni–Pt NPs supported on
nanoporous carbon, Maxsorb MSC-30.207 The catalyst
exhibited remarkable catalytic activity towards complete
dehydrogenation of hydrazine borane with 100% H2 selectivity
at room temperature. It has been found that the catalytic
activity and H2 selectivity were strongly dependent on the
Ni/Pt ratio (Fig. 17). Both monometallic Ni and Pt
nanocatalysts showed activity for hydrogen release by
hydrolysis of the BH3 group in HB only, whereas the Ni1–
xPtx/MSC-30 nanocatalysts with platinum contents in the range
of 15–70 mol% exhibited high catalytic activities and 100%
hydrogen selectivity with 5.95 ± 0.05 equiv (H2 + N2) per HB
Fig. 16 (a) Synthesis of NiPt@MIL-101 Nanocatalysts. (b) Time course plots and released. NaOH served as an efficient dispersing agent to
(c) durability test for the decomposition of aqueous solution of hydrazine over
control the particle size during the formation of NiPt NPs and
NiPt@MIL-101 with NaOH (0.5 M) at 50 °C, (catalyst = 0.1 g; N2H4∙H2O = 0.1
mL).194 (Copyright 2014 American Chemical Society).
also played an important role as a catalyst promoter.
Development of noble-metal-free catalyst is of economic

advantage and crucial for promoting the potential application
of hydrazine as a hydrogen storage material. Many groups
reported Ni–Fe combination as an effective catalyst for the
32, 202-204
dehydrogenation of hydrous hydrazine. Xu et al.
reported a high-performance bimetallic Ni–Fe alloy NPs for
complete and selective decomposition of hydrous hydrazine
32
under moderate conditions. The H2 selectivity was 80% at 50
°C and 100% at 70 °C in the presence of 0.5 M NaOH, but the
catalyst was inactive at room temperature. Tang et al. Fig. 17 (a) Volume of the generated gas (H2 + N2) versus time and (b) Pt-content
prepared monodispersed Ni3Fe single-crystalline nanospheres dependence of n(H2 + N2)/n(HB) for the dehydrogenation of HB over Ni–Pt/MSC-
2 −1 30 with different Ni/Pt molar ratios prepared with NaOH (nmetal/nHB = 0.1, 30
on carbon with a specific surface area of 182.3 m g which
°C).207 (Copyright 2014 American Chemical Society).
resulted in 100% H2 selectivity and exceedingly high activity

Please
View Article Online
DOI: 10.1039/C6EE02002J
Journal Name

ARTICLE
Table 2 Catalytic performance of bimetallic Ni catalysts in the H2 production via dehydrogenation/hydrogenolysis of chemical H2 storage materials.
Catalyst M/Ni Synthesis method H2 storage T (°C) Conv. (%)/H2 TOF Note Ref.
(wt/wt) material sel. (%)
Ni@Ru NPs 1.73 seeded growth NH3-BH3 RT – 114 min−1 Ni seeds resulted heterogeneous nucleation of Ru NPs to 24
form smaller size
Ru@Ni/graphene 0.23 co-reduction NH3BH3 RT – 340 min−1 catalyst was magnetically recyclable 171
−1 208
RuCuNi/CNTs 1:1:1 co-reduction NH3BH3 RT – 311 min trimetallic synergistic effects
−1 209
Pd10Ni6@MIL-101 3.3 co-reduction NH3BH3 RT – 83 min bifunctional effects between Ni-Pd alloy NPs and the host
of MIL-101
13
Ni-Rh NPs 7.01 co-reduction N2H4∙H2O RT 100/100 – alloying resulted high reducibility of each metal
183
Ni-Rh/graphene 7.57 co-reduction N2H4∙H2O RT 100/100 – high activity due to synergistic effect of graphene support
and Ni-Rh NPs and promotion effect of NaOH

182
Ni-Rh/graphene 0.19 co-reduction N2H4∙H2O 50 100/100 – high activity even at very low noble-metal content
184
Rh/Ni@SiO2 NPs 0.21 thermal hydrolysis N2H4∙H2O RT 100/99 – catalyst was magnetically recyclable
−1 185
Ni66Rh34@ZIF-8 0.9 liquid impregnation N2H4∙H2O 50 100/100 140 h high activity due to synergistic molecular-scale alloying
effect and promotion effect of ZIF-8

−1 187
Rh55Ni45/Ce(OH)CO3 2.23 co-reduction N2H4∙H2O 50 100/100 395 h high activity due to strain and ligand effects between Rh
and Ni
180
Ni0.95Ir0.05–B 0.17 co-reduction N2H4∙H2O RT 100/100 – high activity at very low Ir content
181
NiIr0.059/Al2O3 0.2 DP N2H4∙H2O 30 100/99 – Ni-Ir alloy might tune the interaction strength between
N2H4 and catalyst

199
Ni60Pd40 NPs 1.21 co-reduction N2H4∙H2O RT 100/100 – NaOH acted as promoter for complete N2H4 decomposition
189
NiPt0.057/Al2O3 0.19 DP N2H4∙H2O 30 100/98 – enhanced reaction rate due to weak interaction between
surface Ni atoms and adspecies produced

−1 197
Ni3Pt7/graphene 7.76 co-reduction N2H4∙H2O RT 100/100 68 h strong interaction of Ni-Pt alloy with graphene
−1 194
Ni88Pt12@MIL-101 0.44 liquid impregnation N2H4∙H2O RT 100/100 65 h activity was highly composition dependent
−1 191
Ni84Pt16/graphene 0.66 co-reduction N2H4∙H2O RT 100/100 133 h high activity due to ultrafine size, narrow size distribution
and synergistic effect between Ni and Pt

−1 192
Ni60Pt40/CeO2 2.22 one-pot EISA N2H4∙H2O 30 100/100 293 h enrichment of strongly basic sites and high resistance to
alkaline solution of the CeO2

−1 193
Ni64Pt36/MIL-96 1.83 liquid impregnation N2H4∙H2O RT 100/100 114 h excellent activity due to the synergistic effect of MIL-96
support and Ni-Pt NPs

32
Ni-Fe NPs 0.95 co-reduction N2H4∙H2O 70 100/100 – catalyst was inactive at room temperature but active at
higher temperature in presence of NaOH

−1 202
Ni3Fe/C 0.32 co-reduction N2H4∙H2O RT 100/100 9.26 min catalyst started to deactivate because of the oxidation of
Ni and Fe
203
Ni-Fe/MgO 0.63 calcination– N2H4∙H2O RT 100/99 – high activity due to Ni–Fe synergistic effect and the strong
reduction basicity of MgO
DP: deposition-precipitation. EISA: evaporation-induced self-assembly.
4.1.1.3 Production of H2 through WGS reaction. Water gas temperature shift (with Fe2O3/Cr2O4 catalyst) and low-
shift reaction (WGS) is a reversible exothermic reaction in temperature shift (with Cu/ZnO/Al2O3 catalyst).210 For the low-
which carbon monoxide reacts with water (steam) to form temperature copper-based WGS catalysts, the first step (H
carbon dioxide and hydrogen (Eqn. 3). WGS is an important abstraction from H2O) is rate-limiting for the entire process.
reaction typically used during and after reforming to increase Therefore, much importance have been given to develop new
the yield of H2. CO is oxidized by H2O to produce an additional WGS catalysts with high activity toward H2O dissociation at
mole of H2 with CO2 as a waste gas. Generally, a two-step WGS low temperatures.211
reactor is employed in large-scale industrial plants: high-

View Article Online
DOI: 10.1039/C6EE02002J
o 220
CO (g) + H2O (g) → CO2 (g) + H2 (g) [∆Hm (298.15 K) = −41.2 enhanced on Ni–Cu alloy at high temperature. The Ni–
−1
kJ mol ] (3) Cu/CeO2 catalyst with Ni/Cu ratio of one exhibited high
A micro-kinetic model based on a redox mechanism was reaction rate with the least methane formation due to the

employed to study the trend of low-temperature WGS formation of Ni–Cu alloy phase. Strong CO adsorption strength
reactivity on a series of transition metals.
212
The model at high adsorption temperature implied that the formation of
suggested that the catalytic reactivities of Cu and Ni were Ni–Cu alloy prevents the dissociation of CO. At the same time,
superior to other metals, and thereafter the experimental it can prevent the formation of carbon species ‘‘formate’’,
analysis further proved that Cu and Ni are the most promising which could block the reaction active site and produce
metal components for the WGS.213 In fact, Ni was even more methane as an undesired side product. It is noteworthy that
reactive toward H2O than Cu in the WGS process,214 which the surface lattice oxygen mobility of ceria could be activated
indicated that introducing Ni component to the Cu-based with the formation of Ni–Cu alloy particularly at high reaction
catalysts may lower the barrier of H2O splitting and ultimately temperatures.
accelerate the WGS process at low temperatures. 4.1.1.4 Production of H2 through electrocatalysis.
One of most important detrimental factors in WGS process Electrocatalytic splitting of water is expected to play a key role
is the dissociation of CO which leads to the formation of CH4. in the future sustainable production of hydrogen from
In addition to the high H2O dissociation activity of Ni, it also electricity. The process can be divided into two half-redox
has a high activity towards CO activation. Therefore, an reactions, hydrogen evolution reaction (HER) on cathode and
optimum concentration of Ni is required to achieve high WGS oxygen evolution reaction (OER) on anode. The key challenge
selectivity by minimizing the undesired methanation reaction. in electrocatalytic water splitting is the anodic OER because of
Zhao et al. performed detailed DFT calculations to study H2O its high overpotential and sluggish surface kinetics on virtually
and CO dissociations on a set of Ni–Cu bimetallic surfaces all known materials. Currently, typical catalysts used in water
aiming at exploring the optimal Ni ensemble on Cu(111) for an splitting reactions are mostly based on noble metals such as
efficient WGS process.215 Fig. 18 illustrates the favorable Pt, Ru, Ir, and their alloys/compounds, among which Ir oxide is
process on different bimetallic Ni–Cu catalysts with different one of the most appropriated polymer electrolyte membrane
compositions. It was found that Ni additives in the Cu(111) electrolyzer OER catalysts providing excellent activity and
surface layer including a Ni monomer remarkably enhance stability.224-228 However, Ir is extremely rare element with
water splitting. As for CO dissociation on the three selected abundance 10 times lower than Pt, and therefore the amount
CuNi surfaces (Ni monomer, dimer, and trimer-α), the reaction of Ir required must be reduced to a minimum to make its
barrier on the Ni monomer was as high as the value on pure application feasible on a large scale.
Cu(111), implying that C–O breaking was unfavorable on the Ni
monomer. In contrast, CO dissociation on the Ni dimer and
trimer-α was highly promoted, and the calculated barriers
were very close to that on pure Ni(111). The conclusion from
these studies is that increasing Ni loading can induce the
promotional effects on C–O bond breaking to facilitate the
undesired methane yield. Therefore, bimetallic Ni–Cu catalysts
with highly dispersed Ni ensembles containing lower Ni
concentration are desirable for better activity and selectivity
toward WGS.
Fig. 19 (a) Scheme of the oxygen evolution reaction on the IrOx shell of IrNiOx
core–shell NPs supported on Meso-ATO. (b) Electrocatalytic oxygen evolution
Fig. 18 Different dissociation mode on bimetallic Ni–Cu surface with different Ni reaction (OER) activities of IrNiOx core–shell NPs supported on mesoporous ATO
ensembles in WGS process.215 (Copyright 2012 American Chemical Society). (IrNiOx/Meso-ATO-T), pure Ir NPs supported on carbon (IrOx/C), and on
commercial ATO (IrOx /com.-ATO) measured using linear sweep voltammetry. (c)
Ir-mass-based activity at η = 280 mV overpotential of IrOx/C, IrOx/com.-ATO, and
In the last few years, WSG reaction has been extensively IrNiOx/Meso-ATO-T.31 (Copyright 2015 Wiley-VCH).
studied over the bimetallic Ni–Cu system where the main
concern was to suppress the methanation reaction by Recently, Strasser’s group derived dealloyed metal–oxide
increasing the CO adsorption.216-223 In a recent study, hybrid IrNi@IrOx core–shell NPs to provide substantial
experimental analyses such as CO-TPR-MS, CO-TPD-MS and in advances toward more efficient and less expensive electrolytic
situ DRIFTS have proved that the CO adsorption can be 30
water splitting. IrNi@IrOx NPs were synthesized from IrNix

Please
View Article Online
DOI: 10.1039/C6EE02002J
precursor alloys through selective surface Ni dealloying and OER activity curve with a maximum at high Ni contents (67–79
controlled surface oxidation of Ir. The final materials contained at%) (Fig. 20a). The intuitive model for the formation of the
a nanometer scale, almost pure IrOx surface, while the inner active state of the catalytic surface suggested that the

core region became increasingly metallic and enriched with Ni. coverage of reactive surface hydroxyls serves as a useful
The catalysts showed 3-fold activity enhancement for the descriptor for OER activity (Fig. 20c). During the
electrochemical OER process over IrO2 and RuO2 benchmark electrocatalytic OER protocol, Ni is leached from these oxides,
catalysts on a noble metal mass basis. In the next report yielding Ir-rich oxides. Consequently, oxygen atoms lose
published by this group, the catalysts were modified by binding partners and take up protons from the electrolyte to
introducing a support, where core–shell IrNix@IrOx NPs form surface hydroxyl groups. Upon Ni leaching the surface OH
supported on high-surface-area mesoporous antimony-doped fraction increased significantly up to 67 at% initial Ni content
tin oxide (IrNiOx/Meso-ATO) were synthesized from bimetallic (Fig. 20b). Interestingly, the surface-specific OER activity
IrNix precursor alloys (PA-IrNix/Meso-ATO) using revealed a rather similar trend as the OH fraction, i.e. both
electrochemical Ni leaching and concomitant Ir oxidation.31 increased with increasing Ni content and reached saturation at
The work was designed based on the structural hypothesis 67 at% Ni. These results demonstrated that the ratio of weakly
regarding the active catalyst/support couple, with the OER bonded surface hydroxyls is directly related to the surface
proceeding at thin IrOx shells on Ir-low/Ir-free cores, thereby specific catalytic OER activity of Ir oxides.
reducing the required Ir amount significantly (Fig. 19). The Apart from Ir-based bimetallic systems, recent studies also
materials were annealed at different temperature (T = 180, focused on cheap metal based catalysts for OER.230-233 In a
250, 300, 400, 500 °C) and the effects of thermal treatment on recent work, 3d transition metal layered double hydroxide
the atomic structure of the PA-IrNix/Meso-ATO-T and on the (LDH) nanosheets based on Ni and Fe were synthesized and
OER activity of the obtained core–shell catalysts were supported on conductive graphene oxide.231 The catalytic
investigated (Fig. 19). The IrNiOx/Meso-ATO-T catalysts with T activity of Ni–Fe LDH catalysts increased with the increase of
≤ 300 °C were significantly more OER active on both geometric Fe content, and reached the highest value for Ni2/3Fe1/3-rGO
surfaces and Ir mass basis compared to the IrOx/C and composition. The synergistic effect was originated from the
IrOx/com.-ATO benchmarks. In fact, the lower annealing face-to-face interfacial hybridization of redoxable LDH
temperature maintained the desired IrNi metallic alloy phase nanosheets and conductive graphene at a molecular scale in
and the Ni content in the particle core remained high. It is the superlattice structure.
assumed that, as a result of this, electronic and/or strain 4.1.2 Production of hydrocarbons from COx. Production of
effects modified the chemisorption and reactivity of hydrocarbon fuels from CO2 and CO has become an emerging
intermediates at the surface. In contrast, the catalysts technology in recent years.234-238 CO2 has covered about 82%
annealed at 400 °C and 500 °C showed significantly lower OER of total Greenhouse gases (GHGs), and therefore use of CO2 as
activities due to the phase segregation into a mixture of NiO a raw material can mitigate this issue pretty well. CO2 is non-
and Ir-rich nanophases. toxic, non-corrosive, nonflammable, inexpensive, abundant,
and it can be safely stored in liquid form under mild pressure.
Methanation and Fischer-Tropsch (FT) processes are the
general catalytic pathways applied in the production of
hydrocarbons from CO2 and CO. The basic mechanism for
these two reactions is same in their first and rate determining
step, which is the cleavage C–O bond. In the following step,
they follow different pathway, where C–H bond formation
takes place for methanation reaction and C–C bond formation
takes place for FT reaction to increase the carbon chain length.
The product distribution in these two reactions depends on
the catalyst composition and reaction conditions. For example,
Ni is considered to be one of the best catalysts for
methanation reaction, whereas Fe, Co and Ru are suitable for
FT process. Low to moderate temperatures (150–300 °C) favor
the FT process by the elongation of carbon chain length, while
Fig. 20 (a) Electrocatalytic measurements of OER activity and stability of Ni–Ir
mixed oxide films with different Ir to Ni ratios. (b) Hydroxyl group (OH) fraction increase in temperature leads to the formation of methane in
to the total oxide related oxygen (hydroxyl groups and both lattice oxygen higher yield.
species) as determined by XPS. (c) Model of Ni leaching from the surface of Ni–Ir −1
mixed oxides.229 (Copyright 2015 American Chemical Society).
CO2 + 4H2 → CH4 + 2H2O [ΔH298 K = −165 kJ mol ] (4)
−1
CO + 3H2 → CH4 + H2O [ΔH298 K = −206 kJ mol ] (5)
The same group reported Ni–Ir mixed oxide thin film (2n + 1) H2 + n CO → CnH(2n+2) + n H2O (6)
catalysts for the OER with an unprecedented 20-fold
229 According to the thermodynamics, methanation of CO2 and
improvement in Ir mass-based activity over pure Ir oxide.
CO is the most advantageous reaction as it is considerably
Initial variation of the Ir to Ni ratio resulted in a volcano type

View Article Online
DOI: 10.1039/C6EE02002J
faster than other reactions which form hydrocarbons or The increase of Fe content led to enhancement of the water
239
alcohols. However, the process needs effective catalysts to gas shift reaction and hydrocarbon production. Therefore,
occur. In fact, a huge number of studies have been performed achieving the optimum ratio of two metals is important in

on the design of effective methanation catalysts during the order to get maximum CH4 yield. Pandey and Deo studied CO2
240-242
past years. Since the earliest work by Sabatier and methanation over different oxide supports (such as Al2O3,
Senderens in 1902, nickel-based catalysts have been ZrO2, TiO2, SiO2 and Nb2O5) containing bimetallic Ni–Fe catalyst
241 251
considered as the most active for the methanation process. in the ratio of 3:1. It was observed that the relative
In 1975, M. A. Vannice compared the specific activity and enhancement in yield for the most active catalyst of each
product distributions of group VIII metals dispersed on Al2O3 in series was support dependent, and the maximum
the production of hydrocarbons from H2–CO mixtures and enhancement was achieved over the Al2O3 supported
found that CO methanation could occur readily over these catalysts. The authors proposed that the maximum
243, 244
metals. The specific activity followed the order of Ru >> enhancement for the Al2O3 supported catalysts was due to the
Fe > Ni > Co > Rh > Pd > Pt > Ir, and the reaction rate of CO ability of the support to adsorb CO2. However, the effect of
methanation was observed to be closely related to CO CO2 adsorption on the supported catalysts was not studied to
dissociation. Among all of these catalysts, Ni supported on support the statement.
Al2O3 is one of the most widely studied catalysts in
methanation reactions due to its high performance-cost ratio.
However, the performance of Ni catalysts toward methanation
is dependent on various parameters such as the effect of
support, Ni loading, presence of a second metal and the the
preparation method. In this section, we will focus our
discussion on the influence of second metals in the activity of
various Ni-based catalysts for the methanation of CO2 and CO.
In the earlier section of the dry reforming process, we have
discussed that conventional Ni-based catalysts suffer from
severe catalyst deactivation due to carbon deposition as a
result of CO2 methanation reaction. The same strategy is also
applied here to overcome this problem, where the addition of
Fig. 21 Conversion of CO2 and yield for CH4 in the methanation of CO2, plotted as
second metal such as Fe, Zr, Co, Cu, Mn, La, Y, and Mg has
a function of Ru content of 35Ni5FexRuAX catalysts.256 (Copyright 2013 Elsevier).
been attempted to enhance the stability and catalytic activity
of the nickel-based catalysts.245-255 Hwang et al. reported the
Among the noble metals, Ru shows the highest activity for
effect of second metal (M = Fe, Zr, Ni, Y, and Mg) in
CO2 methanation and therefore it has been used to promote
mesoporous Ni (35 wt%)–M (5 wt%)–alumina xerogel (denoted
the catalytic efficiency of Ni catalysts.256, 257 The effect of Ru
as 35Ni5MAX) catalysts for methane production from CO2 and
content in the mesoporous Ni (35 wt%)–Fe (5 wt%)–Ru (x
H2.247 In the CO2 methanation reaction, yield for CH4 decreased
wt%)–alumina xerogel (denoted as 35Ni5Fex-RuAX) catalysts
in the order 35Ni5FeAX > 35Ni5ZrAX > 35Ni5NiAX > 35Ni5YAX 256
was investigated. Both conversion of CO2 and yield of CH4
> 35Ni5MgAX. This indicated that the catalytic performance
showed volcano-shaped trends with respect to Ru content,
was greatly influenced by the identity of the second metal in
which indicated that optimal Ru content was required for the
the CO2 methanation reaction. The CO dissociation energy and
maximum production of CH4 (Fig. 21). Metal surface area and
metal–support interaction of the catalyst played key roles in
the amount of desorbed CO2 of the catalysts also showed the
determining the catalytic performance of the 35Ni5MAX
same trends with respect to Ru content, which explained good
catalysts in the reaction, in which the 35Ni5FeAX catalyst
correlation between the catalytic performance and their
retained the most optimal CO dissociation energy and the
physicochemical properties. Zhen et al. reported CO2
weakest metal–support interaction, and exhibited the best
methanation over γ-Al2O3-supported bimetallic Ni–Ru NPs,
catalytic performance in terms of conversion of CO2 and yield
which were prepared by co-impregnation and sequential
for CH4. 257
impregnation methods. The catalytic activities were found
Iron has been widely used as second metal to the Ni
to be highly dependent on the preparation sequence. Catalysts
catalysts to improve the CO2 conversion and CH4 yield.248-251
prepared by co-impregnation method showed higher catalytic
The performance of the catalysts was highly dependent on the
activities, selectivities, and excellent stabilities for CO2
metal loading, nature of support and preparation methods. For
methanation. It was also found that the segregation
example, supported Ni–Fe catalysts containing 75 wt% of the
phenomenon of Ru occurred on the catalyst surface in the co-
total metal loading as Ni and 25 wt% as Fe showed a
impregnation method, by which more active Ni and Ru species
significantly better CO2 conversion and higher CH4 yield
250 (metallic Ru) could be provided on the surface of the catalyst.
compared to the Ni and Fe supported catalysts. Kang et al.
Based on the characterizations, a possible reaction mechanism
studied the effect of Fe metal on NiAl2O3 for CO2 methanation
was proposed, where the individual role of each metal site was
and their results showed that the Ni0.7Fe0.3/Al2O3 catalyst
248 explained (Fig. 22). In the first step, CO2 was dissociated and
achieved maximum carbon conversion and CH4 selectivity.

Please
View Article Online
DOI: 10.1039/C6EE02002J
activated to form carbon species (COads) on Ru species surface. major complexity in oxygenated biomass or biomass-derived
At the same time, H2 was dissociated into H on metallic Ni platform molecules relates to the comparable strength in C–O
surface. In the second step, carbon species (COads) was and C–C bonds, resulting in a remarkable challenge to achieve

dissociated into C and O on the catalyst surface. Finally, the C selective cleavage of one bond keeping the other intact. CO2 is
species could react with H to produce CH4 on metallic Ru, and another excellent platform for deriving oxygenate molecules
H and O atoms formed H2O. such as methanol, formic acid which serve as potential energy
234, 266
carriers. In this section, we will provide a brief account of
bimetallic Ni systems for the conversion of biomass
267
feedstocks and CO2 into energy carrier molecules via
different reaction pathways like hydrogenation,

hydrogenolysis, hydrodeoxygenation etc.
4.1.3.1 Hydrogenation of cellulose and glucose. Cellulose
and glucose can be directly converted to various polyols (e.g.,
ethylene glycol (EG), propylene glycol, sorbitol, mannitol)
through hydrogenation or hydrogenolysis over metal
catalysts.267 Gallezot et al. studied the effect of adding
promoters such as Sn, Mo, Cr and Fe to RANEY® Ni and found
that the addition of Cr increased the rate of glucose
Fig. 22 The proposed reaction mechanism of CO2 methanation over 10Ni–1.0Ru
catalyst.257 (Copyright 2014 Royal Society of Chemistry). hydrogenation up to 5 times.268 Cr(III) acted as a Lewis acid to
adsorb glucose and favor the nucleophilic attack on the carbon
The product selectivity is one of the major concerns in FT atom by H2 dissociated on Ni. Shrotri et al. reported an
process. In the FT process, the product composition primarily aqueous phase hydrolysis–hydrogenation process to convert
includes paraffins, olefins, and different classes of oxygenates cellulose to sorbitol using a bimetallic Ni–Pt catalyst.269
(alcohols in major fraction). Therefore, one of the primary Monometallic Ni catalysts showed little activity for the
interests in this research is to generate a higher olefin fraction, reaction, but addition of a small amount of Pt to Ni (Ni : Pt =
which can then be further oligomerized to generate the target 22:1 atom ratio) greatly enhanced catalyst activity. The
transportation fuel or chemicals and reduce/avoid the CH4 and bimetallic Ni–Pt catalysts supported on mesoporous alumina
CO2 formation from the syngas hydrogenation. In a recent gave a hexitol (sorbitol + mannitol) yield of 32.4% compared to
work by Ramasamy et al., a dual bed configuration has been 5% with pure Ni catalyst. The presence of Pt promoted the
introduced to convert oxygenates generated in the CO protonation of water and hydrogen, which could spill over to
hydrogenation process to produce targeted hydrocarbon Ni sites creating in situ acid sites to catalyze hydrolysis of
compounds.258 In the first reactor of the multi-step process, cellulose. In another report, hydrogenation of cellulose was
Ni–Co bimetallic catalyst containing total metal loading less performed over bimetallic Ni catalysts supported on
than 10 wt% was introduced, which produced 40% of short- mesoporous carbon (MC).270 By efficiently coupling the
chain olefinic compounds (C2–C7) along with 10% oxygenates. hydrolysis reaction and “in situ” hydrogenation of
An acidic alumina containing reactor was added followed by oligosaccharides, the hexitol yield reached 59.8%.
the Ni–Co containing reactor for the deoxygenation of Monometallic Ni catalyst (20%Ni/MC) produced 42.1% hexitol
oxygenates, which could effectively reduce the oxygenate yield at a cellulose conversion of 84.5%, while the addition of
products from 10% to 1.3%. Rh and Ir showed increasing activity, producing 59.8% and
57.5% hexitols respectively. The stability of the catalyst also
increased upon addition of promoters. Monometallic Ni
catalyst deactivated rapidly, and 20% yield to hexitols was
achieved after 5 cycles, while 4%Ir/4%Ni/MC retained its
4.1.3 Production of oxygenates as energy carrier. activity 4 cycles with yields around 60%.
Alongside the hydrocarbon-based fuels, a number of A highly active bimetallic Ni–Pt/ZSM-5 was reported for the
oxygenated compounds have drawn considerable attention hydrolytic hydrogenation of cellulose in hot-compressed
due to their excellent fuel properties. Although, the water.271 Ni–Pt NPs were formed with a Pt-enriched alloy
oxygenated compounds have lower energy density than the surface in the catalyst. A remarkable yield of hexitols (76.9%)
commonly used gasoline and diesel, some compounds have was obtained on Ni–Pt/ZSM-5 which was higher than the
higher research octane number (e.g., ethanol, DMF) and 52.7% obtained on Ni/ZSM-5 at similar conversion levels,
cetane number (e.g., DME), which make them suitable blends indicating the presence of a Pt-enriched alloy surface
for transportation fuels. There are numerous resources significantly enhances the selectivity to hexitols. The Ni–
containing oxygen functionalities, such as lignocellulosic Pt/ZSM-5 presented much higher hydrogenation activity
biomass, which are readily convertible to different oxygenate compared to Ni/ZSM-5. The H2-TPD of Ni–Pt/ZSM-5 showed
molecules via catalytic transformation.259-265 Nevertheless, that more H species migrate from the Pt-like sites to the Ni-like
selective biomass conversion is not simple because of high ones, which means that more activated hydrogen species can
oxygen content and presence of diverse functional groups. The participate in glucose hydrogenation.

View Article Online
DOI: 10.1039/C6EE02002J
The product distribution of cellulose high temperatures, which confirmed the poor hydrogenation
hydrogenation/hydrogenolysis process depends on the nature property of Fe. Meanwhile, the monometallic Ni/CNT catalyst
of the second metal used. For example, noble metals such as showed high conversion but poor selectivity under the same

Pt, Ru show improved hydrogenation properties along with Ni conditions. Scheme 3 represents the pathway of HMF
to produce mainly hexitols as observed in previous cases. In conversion over different catalysts, which shows that different
contrast, tungsten species are very effective for cellulose byproducts including decarbonylation product [5-
degradation due to their high activity breaking C–C bond and methylfurfural (MF)], ring hydrogenation product [2,5-
as a result, lower polyols (such as ethylene glycol) are obtained dimethyltetrahydrofuran(DMTHF)], ring-opening product [1,2-
272, 273
through the hydrogenolysis process. However, the yield hexanediol (HD)], and etherification product, were detected
of polyols with pure tungsten catalysts is low because of the over Ni/CNT. The combination of Ni and Fe in an appropriate
poor hydrogenation properties. Ni, in principle, can act here as atomic ratio of Ni/Fe (2.0) significantly increased the selectivity
a promoter to increase the hydrogenation ability to obtain to 2,5-furandimethanol or 2,5-dimethylfuran depending on the
ethylene glycol with higher yield. reaction temperature. The selectivities to 2,5-furandimethanol
4.1.3.2 Hydrogenation of furfurals and levulinic acid. and 2,5-dimethylfuran were as high as 96.1% at 383 K and
Biomass-derived platform molecules such as furfural, 5- 91.3% at 473 K, respectively. The improved selectivity could be
hydroxymethylfurfural (HMF) and levulinic acid (LA) are of attributed to the formation of Ni–Fe alloy species, which was
immense importance because these can be upgraded into beneficial to the selective cleavage of the C–O bond.
other useful chemicals and fuels by oxidation, hydrogenation,
aldol condensation, etherification and many other O
264, 274 O OH
reactions. Here we will focus on the hydrogenation and
HMF
hydrogenolysis, as these are the reactions where bimetallic Ni Hydrogenolysis
Decarbonylation + H2
catalysts can be used. CO H2O
2,5-Dimethylfuran (DMF) has received increasing attention O O O
as promising liquid transportation fuel lately. DMF can be HO HO OH O
obtained via selective hydrogenation of HMF over metal-based FDM MF
275
catalysts. However, obtaining high selectivity of DMF is
+ H2
challenging due to the highly reactive nature of HMF. HMF OH
O O
reductive chemistries include C=O bond reduction,
OH
hydrogenation of the furan ring as well as C–O hydrogenolysis. OH
MFM HD
Therefore, the catalysts must be carefully designed to perform
desired reaction to achieve the desired product. Huang et al. Reactions on Ni2-Fe1/CNTs
reported a highly efficient non-noble bimetallic catalyst based Reactions on Ni/CNTs O O
on nickel–tungsten carbide for the hydrogenolysis of HMF to
276 DMF DMTHF
DMF with excellent yields. Using different catalysts, metal
ratios and reaction conditions, a maximum DMF yield of 96% Scheme 3 Possible reaction pathway of HMF hydrogenation over different catalysts.277
(Copyright 2015 Wiley-VCH).
was obtained. To understand the role of Ni and W2C
components in the hydrogenolysis reaction, Ni/AC and W2C
were prepared and individually tested. Results suggested two Sitthisa et al. investigated SiO2-supported Ni and Ni–Fe
278
different roles for metals: Ni particles mainly contributed to bimetallic catalysts for the conversion of furfural. Furfuryl
hydrogenation activity while W2C offers an additional alcohol and furan were primary products over monometallic
deoxygenation activity. The W2C catalyst is well known for its Ni/SiO2, resulting from hydrogenation and decarbonylation of
bifunctional nature, which contains both acidic and metallic furfural. Comparatively, Fe–Ni bimetallic catalysts
sites, and can therefore catalyze both deoxygenation and predominantly produced 2-methylfuran (2-MF) with reduced
hydrogenation reactions. The addition of Ni was proved to be yields of furan and C4 products. Results proved that the
essential to increase the active hydrogen concentration to addition of Fe suppressed the decarbonylation activity of Ni
improve hydrogenation rates. Higher Ni loadings were also and at the same time promoted C=O hydrogenation (at low
shown to result in a remarkable improvement in the temperatures) and C–O hydrogenolysis (at high temperatures).
hydrogenolysis reaction upon increasing the hydrogenation The strong interaction between O (from the carbonyl group)
ability. Despite the in-depth studies in individual roles of the and the oxyphilic Fe atoms resulted in a preferential
two components, the interactions between Ni and W2C, and hydrogenolysis reaction on the bimetallic alloy. On the other
2
the structures and properties of the interface, remain elusive. hand, pure Ni surface promoted the conversion of η -(C, O)
Recently, carbon nanotube-supported bimetallic Ni–Fe (Ni– species into a surface acyl species, which was subsequently
Fe/CNT) catalyst was investigated for the selective decomposed to furan and CO. In another report, furfural was
hydrogenation and hydrogenolysis of HMF with H2 as a converted to cyclopentaone (CPO) over Ni–Cu bimetallic
279
hydrogen donor.
277
Two different metal components catalysts in an aqueous medium under H2 atmosphere.
presented different behaviors when used individually. The Furfuryl alcohol, 4-hydroxy-2-cyclopentenone and 2-
Fe/CNT catalyst showed low catalytic activity at both low and cyclopentenone were identified as three key intermediates

Please
View Article Online
DOI: 10.1039/C6EE02002J
during the transformation. Rearrangement of the furan ring in the reduction kinetics, the bimetallic catalysts showed core-
was independent of catalytic hydrogenation, starting from shell structure and Ni was enriched in the shell. XPS and XANES
furfuryl alcohol rather than furfural. The opening and closure studies confirmed the charge transfer from noble metals to Ni,

of the furan ring were closely related to the attack of the H2O which made Ni surface electron-enriched. In addition, the
molecule in the 5-position of furfuryl alcohol. Ni/SBA-15 core-shell bimetallic catalysts were formed in ultrasmall size,
catalyst produced 39% CPO selectivity at a furfural conversion typically much smaller than pure Ni catalyst (~2 nm for
of 46%, while on the Ni–Cu-50/SBA-15 catalyst (Cu : Ni = 50% Ni85Ru15 and Ni85Rh15, and ~4 nm for Ni7Au3), which afforded
in atomic ratio), nearly complete conversion of furfural was enhanced fraction of surface atoms. The as-prepared
achieved with 62% selectivity of CPO. Chen et al. recently bimetallic Ni catalyst showed an excellent synergistic effect in
reported liquid-phase hydrogenation of furfural using the hydrogenolysis of a lignin model compound, 2-phenoxy-1-
bimetallic Ni–Pd catalysts supported over TiO2–ZrO2 binary phenylethanol, plausibly due to an electron transfer from
280
oxides. Addition of small proportion of Pd directly noble metals to Ni. While pure Ni catalyst achieved a high
transferred the catalytic performance of supported Ni from selectivity to monomer products (desired hydrogenolysis
partial hydrogenation catalyst to total hydrogenation catalyst. products) with a low conversion, and pure Ru and Rh catalysts
Yield of the total hydrogenation product, tetrahydrofurfuryl exhibited high catalytic activity with low selectivity to desired
alcohol (THFA), was 93.4% using the catalyst with Ni–Pd mole monomer products, all the bimetallic core-shell catalysts
ratio of 5:1. demonstrated high conversion as well as high selectivity to
Levulinic acid is another important building block that can monomers. Our synthesized catalysts were also applied to the
be converted into various fuel units including ethyl levulinate hydrogenolysis of organosolv lignin and it was found that the
(EL), γ-valerolactone (GVL), and 2-methyltetrahydrofuran (2- bimetallic catalysts exhibited three to ten times higher activity
MeTHF).281 Hydrogenation of levulinic acid to GVL has than pure Ni, Ru, Rh, and Pd NPs.
attracted significant interest recently, as GVL can be used as Sometimes it is observed that the high activity of noble
fuel blend, as a solvent, or be converted into other liquid metals results in undesired aromatic ring hydrogenation,
fuels.282 Hydrogenation of LA was performed over a which is a severe problem in lignin hydrogenolysis. One
composition-tuned bimetallic Ni–Ru catalyst supported on possible way to address the issue is to modify the catalyst
ordered mesoporous carbons.283 Ru0.9Ni0.1–OMC catalysts through partially blocking the active sites that can hinder the
demonstrated unprecedented catalytic activity (TOF >2000 coordination of the aromatic rings on the catalyst surface.
h−1), producing 97% yield of GVL. The high activity of the Recently, we developed a few effective strategies to modify
catalyst could be ascribed to the homogeneous distribution the bimetallic catalyst surface thereby making it selective for
and strong metal-support interaction. Non-noble metal-based C–O bond hydrogenolysis over benzene ring hydrogenation. In
bimetallic Ni–Cu/Al2O3 catalyst exhibited synergetic effects the approach, the surface of highly active Rh nanoparticles was
allowing higher activity and improved selectivity compared to blocked by inactive NiOx, which segregates the surface terrace
the monometallic catalysts in the hydrogenation LA to 2- zones into smaller segments, thereby preventing the easy
MeTHF.284 The activity of the Ni-based catalytic system was access of Rh surface for benzene rings (Fig. 23).291 The
highly dependent on the solvent. Water resulted in high GVL introduction of NiOx did not exhibit pronounced electronic
yields but inhibited MTHF formation. In contrast, hydrogen interaction with Rh but significantly modified its geometric
donating solvents (such as 2-PrOH) facilitated the properties, inhibiting benzene ring hydrogenation without
transformation of highly stable GVL intermediate to MTHF. compromising the hydrogenolysis activity in aryl ethers. The
4.1.3.3 Lignin upgrading. Lignin has significant potential as second approach was to use an inert metal such as Ag to
a source for the sustainable production of fuels and bulk decorate active Ni catalyst surface, thus inhibiting the
chemicals. Hydrogenolysis of C–O linkages in lignin is regarded coordination and hydrogenation of aromatic rings.292 These
as an effective way to transform lignin into depolymerized are the examples of bimetallic systems where one component
aromatic platform compounds.259 Different bimetallic systems shows detrimental effect on the reactivity of other component
including noble metals combined with a transition metal (e.g., to achieve improved selectivity.
Fe, Ni, Cu, Zn or Sn) have also been identified as highly
selective for the removal of oxygen even under mild HDO
conditions.285, 286 Among the non-noble metal-based catalysts,
Ni catalysts have shown promising activity for the selective C–
O cleavage in lignin model compounds under mild reaction
conditions.287, 288 However, pure Ni-based catalysts are
unsatisfactory for β–O–4 C–O bond hydrogenolysis in real
lignin, due to both their limited activity (TOFs of 5–30 h−1) and
low dispersions.
In our recent work, we developed a series of core-shell
bimetallic catalysts, NiM (M = Ru, Rh, Pd, and Au), to achieve Fig. 23 Catalytic activity of NiOx/Rh NPs in the hydrogenolysis of C–O bond in lignin
better performance in the hydrogenolysis of lignin model model compound.291 (Copyright 2016 Elsevier).
289, 290
compounds and organosolv lignin. Due to the difference

View Article Online
DOI: 10.1039/C6EE02002J
Journal Name

ARTICLE
Table 3 Catalytic performance of bimetallic Ni catalysts in the valorization of biomass-derived feedstocks into fuels components.
Catalyst M/Ni Reactant Reaction conditions Key product(s) Conv. (%) /Yield (%) Note Ref.
(wt/wt)
272
Ni5–W25/SBA-15 5 cellulose 245 °C, 60 bar H2, 30 min ethylene glycol 100/75.4 W performed C–C cracking and Ni performed
hydrogenation
270
1%Rh-5%Ni/MC 0.33 cellulose 245 °C, 60 bar H2, 30 min hexitols (sorbitol + 100/59.8 noble metal enhanced hydrogenation and decreased
mannitol) dehydration of sugars to increase hexitol yield

269
Ni-Pt/Beta_75 0.17 cellulose 200 °C, 50 bar H2, 6 h hexitols (sorbitol + 51.3/36.6 Pt created in situ acid sites by protonation and H2
mannitol) spillover to catalyze the hydrolysis of cellulose

273
Ni-W/AC 4 cellulose 215 °C, 65 bar H2, 3 h ethylene glycol 88.4/43.7 W performed C–C cracking and Ni performed
hydrogenation
271
Ni-Pt/ZSM-5 0.06 cellulose 240 °C, 40 bar H2, 4 h hexitols 100/76.9 Pt showed remarkable hydrogen spillover and
inhibited the oxidation of Ni

293
Ni-Pd/SiO2 0.26 HMF 40 °C, 80 bar H2, 2 h BHTF 99/96 catalyst was more active than commercial Raney Ni
and more selective than Pd/C

276
7Ni-30W2C/AC 4 HMF 180 °C, 40 bar H2, 3 h DMF 100/96 Ni showed good hydrogenation ability, W2C showed
good HDO activity

277
Ni2-Fe1/CNTs 0.48 HMF 200 °C, 30 bar H2, 3 h DMF 100/91.3 Ni-Fe alloy selectively cleaved C–O bond
279
NiCu-50/SBA-15 0.54 furfural 160 °C, 40 bar H2, 4 h CPO 99/62 high selectivity of CPO was ascribed to the presence
of 2-cyclopentenone
294
CuNi@C 2.17 furfural 130 °C, 50 bar H2, 5 h CPO 99.3/96.9 porous carbon matrix acted as a supporter and
prevent the accumulation of metal particles

280
Ni-Pd/TiO2-ZrO2 0.36 furfural 130 °C, 50 bar H2, 8 h THFA 99/93.4 addition of Pd transferred the reaction selectivity
from partial hydrogenation to total hydrogenation

−1 283
Ru0.9Ni0.1−OMC 11.71 LA 150 °C, 45 bar H2, 2 h GVL 99/97 high TOF (>2000 h ), catalyst was recyclable up to 15
times
284
23Ni-12Cu/Al2O3 0.52 LA 250 °C, 70 bar H2, 5 h 2-MeTHF 100/56 bimetallic catalyst showed improved activity and
selectivity for 2-MeTHF
BHTF: 2,5-bis(hydroxymethyl)tetrahydrofuran. CPO: cyclopentanone. THFA: tetrahydrofurfuryl alcohol.
4.1.3.4 Conversion of CO2 to oxygenates. Small molecule hydrogenation.298 The activity was shown to be highly
oxygenates such as methanol, dimethyl ether, formic acid etc. composition dependent where Cu3Ni7/γ-Al2O3 catalyst
are considered as potential energy careers, which can be exhibited the highest methanol formation rate of 5.86 mmol/g
produced from CO2 through catalytic hydrogenation.234, 238 h, much higher than the commercial Cu/ZnO/Al2O3 catalyst at
Several catalytic systems have been studied for CO2 the same reaction conditions. The highest activity of Cu3Ni7/γ-
hydrogenation to methanol; among them Cu-based catalysts Al2O3 catalyst could be attributed to the larger specific surface
have long been recognized as the active catalyst area, smallest alloy particle size and the lower reduction
component.295 There are many reports where different temperature.
promoters have been introduced to improve the efficiency of A catalyst based on Ni–Pd alloy on a carbon nanotube-
Cu catalysts. Early studies have shown that Ni has a very good graphene support was used for the production of pure formic
promotional effect on Cu catalysts for methanol synthesis, acid via CO2 hydrogenation.299 The thermodynamics of the
where deposition of Ni leads to a dramatic increase in the rate pure FA formation from CO2 hydrogenation is not favorable
of methanol formation from CO, CO2, and H2.296 It was also (ΔG0298 K = +33 kJ mol−1) even at high temperature and
observed that the CuNi/SiO2 catalyst had the same level pressure, and therefore organic/inorganic bases are often
turnover frequency and a slightly higher selectivity to added to the reaction mixture to increase the conversions.300,
301
methanol than the best known industrially used Cu/ZnO/Al2O3 The authors claimed this to be the first ever report where
catalyst.297 Recently, bimetallic CuxNiy/γ-Al2O3 alloy catalysts the heterogeneously catalyzed reaction was carried out under
were studied for methanol synthesis from CO/CO2 milder conditions (40 °C and 50 bar) in water without any base

Please
View Article Online
DOI: 10.1039/C6EE02002J
additive. Nevertheless, the highest formic acid yield obtained using dealloying method where a Pd20Ni80 alloy was
41
was very low (1.92 mmol) with a turnover number of 6.4 and a electrochemically dealloyed in an acid solution. With ~9 at%
−4 −1
turnover frequency of 1.2 × 10 s . Based on previous results, Ni, the np-Ni–Pd bimetallic catalyst exhibited superior

a reaction mechanism for the formation of formic acid over electrocatalytic performances in oxygen reduction in
Ni–Pd alloy was proposed (Scheme 4). Noble metals (such as comparison with commercial Pd/C and nanoporous Pd (np-Pd).
Pt, Ru, Rh, and Pd, etc.) are active for splitting H2 into H The excellent electrocatalytic properties of the dealloyed np-
302
atoms, while transition metal (such as Ni) has high reactivity Ni–Pd appeared to arise from the combined effect of unique
303, 304
in CO2 reduction. DFT calculation also proved that CO2 is bicontinuous nanoporosity and bimetallic synergistic action.
adsorbed as a formate intermediate on Ni surface and Wang et al. synthesized Ni–Pd hollow NPs via a modified
consecutively reacts with subsurface H in Ni producing formic galvanic replacement method using Ni NPs as sacrificial
304 309
acid as the final product. The proposed mechanism was templates (Fig. 24). Compared with the commercially
derived based on the XPS results, which confirmed the available Pt/C or Pd/C catalysts, the synthesized Ni–Pd/C
electron transfer from Ni to Pd. The role of Ni/Pd atomic ratio exhibited superior electrocatalytic performance towards ORR
of Ni–Pd bimetallic system could also be explained from the process, which could be assigned to the unique hollow porous
mechanism. The experimentally optimized composition of Pd structure and changes in the electronic structures when a
(Ni/Pd = 2.33 for Pd3Ni7) was close to the ratio (Ni/Pd = 2) in second metal (Ni) was introduced. Recently, noble metal free
Scheme 4, which could explain why Pd3Ni7 composition catalyst based on bimetallic Ni–Fe layer double hydroxide
exhibited better performance than others. (NiFe-LDH) has been reported for fuel cell application.311 The
two-phase bifunctional oxygen reduction and evolution (ORR
and OER) electrocatalyst (physical mixture of NiFe-LDH and Fe–
N–C) exhibited the lowest combined OER/ORR overpotential
ever recorded in 0.1 M KOH.
Scheme 4 Proposed reaction mechanism of selective formation of HCOOH from CO2

hydrogenation over Ni–Pd bimetallic surface.299 (Copyright 2015 Royal Society of
Chemistry).
4.1.4 Production of electricity through fuel cell. Fuel cell is

an excellent example of a high capacity system that could
utilize an environmentally sustainable energy source. Many
varieties of fuel cells are currently available, but their working
principle is the same. Among different fuel cells, proton
Fig. 24 Schematic illustration of the formation of hollow Ni–Pd NPs and their ORR
exchange membrane fuel cells (PEMFCs) have attracted 309
activity. (Copyright 2013 American Chemical Society).
considerable attention due to their high efficiency, low
operation temperature, and environmentally benign
The direct methanol fuel cell is a class of PEMFC where
products.224, 305 Oxygen reduction reaction (ORR) is an
methanol is used as the fuel component to supply the protons.
important fundamental electrode reaction in PEMFCs for
The main reactions occurring within the methanol fuel cell are
energy storage and conversion devices based on oxygen
the cathodic oxygen reduction reaction (ORR) and the anodic
electrocatalysis, where oxygen is electrochemically reduced to
methanol oxidation reaction (MOR). Bimetallic 3d transition
water at the cathode in acidic or alkaline media. On the other 312 313-315 316, 317
metal catalysts such as Ni–Mn, Ni–Co, and Ni–Cu
hand, the fuel components (such as H2, methanol etc.) are
were explored for MOR with good electrochemical activities.
introduced at the anode to produce protons. In spite of the
Very recently, Cui et al. investigated the role of cobalt in
high importance of ORR, the sluggish reaction kinetics at the 315
bimetallic NimCon electrocatalyst for MOR. In their study, the
cathode side remains a bottleneck that requires further
composition, surface morphology, and the crystal phase
attention.306 To enhance the ORR kinetics, several attempts
structure of the bimetallic NimCon electrocatalysts significantly
were made to develop effective fuel cell catalysts in the last
changed with increased content of cobalt. The mechanism
two decades.307, 308
study based on electrochemical experiments and DFT
Because of the high price of Pt-based catalysts, less
calculations indicated that the doping of Co in NimCon can
expensive and more widely available Pd has recently been
significantly improve the surface coverage of the redox
exploited as the substitute of Pt for ORR.41, 309, 310 Chen et al.
species, weaken the CO adsorption, as well as adjust the
reported nanoporous Ni–Pd (np-Ni–Pd) bimetallic catalyst
CH3OH adsorption. Furthermore, the adsorption energies of

View Article Online
DOI: 10.1039/C6EE02002J
CH3OH adsorbed on Ni atom are higher than that on Co atom also act as a sulfur scavenger due to its high activity in H2S
326
(Fig. 25a), suggesting that CH3OH prefers to bind on Ni than Co removal.
for Ni3Co and Ni2Co2. This confirms a fast kinetic rate reaction Bimetallic Ni–Pd catalysts have been explored in CO

of CH3OH molecules on the surface of Ni3Co and Ni2Co2. The oxidation with higher activity than monometallic Pd
327-329
adsorption energies of CO adsorbed on Co are slightly higher catalysts. Ni–Pd nanoalloy catalysts exhibit remarkable
than that on Ni, indicating that CO prefers to bind on Co than tunability in terms of phase state, bimetallic composition, and
Ni. As shown in Fig. 25b, compared with other cases, Ni2Co2 atomic-scale structure, which are responsible for the origin of
has relatively low adsorption energy, resulting in less CO the structural synergy for CO oxidation reaction. Al2O3-
poisoning of catalysts. supported bimetallic Ni–Pd catalysts were recently tested in
CO oxidation to examine the effect of the nickel addition on

328
the activity and stability of Pd based catalyst. The improved
activity could be rationalized by an interaction between Pd and
Ni, which improved the reducibility of both Ni and Pd metals.
Apart from Pd, some excellent bimetallic catalysts based on
Pt and Au were also reported for CO oxidation.330-333 Mu et al.
reported supported sandwich type bimetallic Ni–Pt catalysts,
which demonstrated high activity to CO oxidation with 100%
CO conversion near room temperature.330 The Ni–Pt (111)
Fig. 25 (a) Adsorption energy of CH3OH adsorbed on NimCon (m + n = 4) clusters. (b) surface consisted of both surface 2D NiO1–x nanoislands and
Adsorption energy of CO adsorbed on NimCon (m + n = 4) clusters.315 (Copyright 2015 subsurface Ni atoms. The surface Ni oxide monolayer
American Chemical Society). nanoislands contained coordinatively unsaturated cations at
the island edges, which provided active sites for O2 dissociative
4.2 Environmental applications adsorption. On the other hand, the subsurface Ni atoms
Rapid developments in industrialization, population expansion, enhanced the elementary reaction of CO oxidation, with
and urbanization have largely contributed to severe pollution atomic O species produced at the edges of the surface oxide
to air. Carbon monoxide, short hydrocarbons (CxHy, especially islands. In another report on bimetallic Ni–Au catalyst, Au was
methane), different halogenated species, and nitrogen oxides the predominant species on the surface, while no surface Ni0
(NOx) are the main pollutants produced by industrial processes or NiO was observed.331 Based on the reduction potential
and vehicles running on petroleum fuels. Improving the air values of Ni2+/Ni and AuCl4−/Au (–0.25 V vs. 1.00 V), Au is
quality has been a hot research topic for the past few decades expected to be reduced first to form a core–shell structure
and many different paths have been taken to try and with Au as core. However, the synthesis protocol in this study
formulate a solution. Catalytic oxidation is one of most employed a dendrimer stabilization approach combined with
powerful ways for the remediation of air pollution, which can decanethiol extraction, which induced the system toward the
effectively convert the toxic compounds into less harmful and formation of Ni@Au core-shell NPs. Au is thermodynamically
more ecofriendly compounds. For example, a three way more stable on the particle surface due to its lower work
catalyst (TWC) is highly effective in this purpose which function than Ni. In this case, the difference was further
simultaneously removes CO, CxHy, and NOx by both oxidation enhanced by introducing a thiol containing extracting agent via
and reduction pathways. the formation of strong Au-S bonds, which provided additional
Oxidation: 2CO + O2 → 2CO2 driving force to bring Au to the NP surface. DFT calculations
indicated that the incorporation of Ni into Au slabs resulted in
Oxidation: CxH2x+2 + [(3x+1)/2]O2 → xCO2 + (x+1)H2O stronger adsorption of O and CO on Au surfaces. Kinetics
Reduction: 2NOx → xO2 + N2 studies also revealed that apparent activation energies
4.2.1 Oxidation of CO. Catalytic oxidation of CO and decreased by more than 50% and O2 reaction orders increased
hydrocarbons into CO2 is a major solution to remove them in from 0.2 to 0.9 after Ni incorporation. Despite the promotional
air depollution treatments. Platinum group metals are very effect, the addition of Ni reduced the relative number of active
active in CO oxidation.
318-320
In particular, Pd appeared to be a sites on the catalyst.
common choice of catalyst due to its high activity in the low- Bimetallic core–shell Au–Ni NPs supported on CeO2
temperature oxidation reactions and lower price compared support were studied for CO oxidation and compared with
with other noble metals. However, the deactivation of Pd their monometallic counterparts.333 As expected, Au/CeO2
catalysts during the long-term usage increased the demand in catalysts exhibited better catalytic performance than the
improvements of the existent catalysts. One possible solution Ni/CeO2 sample. However, Au–Ni/CeO2 was surprisingly more
of increasing the catalyst lifetime is the modification of existing active than the Au/CeO2 catalyst, even if the characterization
catalysts by addition of a second metal. Commonly, the second data proved that only nickel atoms are exposed on the surface
metal is chosen from groups 9–11 in the periodic table.321, 322 during the reaction. It was believed that Au atoms in the core
Among those metals, Ni has been proven to affect catalytic of the Au@Ni NPs induced an electronic effect on the local
activity for exhaust gas treatment.323-325 Additionally, Ni can density of Ni d states via the presence of core Au atoms (Fig.
334
26), similar to that proposed for Au–Ni surface alloys earlier.

Please
View Article Online
DOI: 10.1039/C6EE02002J
4.2.2 Oxidation of hydrocarbons. Few examples on

bimetallic Ni–Pd catalysts were reported for the removal of
325, 328, 329
hydrocarbon through oxidation. Three-way catalysts

based on Ni–Pd supported on Al2O3 were reported for the
325, 328
oxidation of C3H6 under stoichiometric conditions. A
recent study by Shen et al. investigated the role of different
preparation methods of Ni–Pd catalysts to induce different
structures of the catalysts with different activity for methane
329
combustion. The traditional impregnation–calcination
method produced monometallic Pd particles on a binary

NiAl2O4 support, and in this case, no improvement of activity
was observed as the Ni was consumed to form inactive NiAl2O4
spinel. In contrast, colloidal approach produced Pd and Ni NPs
Fig. 26 Modification of electronic d state of Ni by Au atoms in Au@Ni NPs.333 (Copyright on the parent Al2O3 support and exhibited better activity (Fig.
2013 American Chemical Society). 28). Furthermore, the addition of Ni to Pd during colloidal
synthesis prevented the over-growth of Pd NPs, thereby
Iron-nickel hydroxide–platinum nanoparticles were improving the stability against sintering at high-temperature
reported by Chen et al. for CO oxidation at room temperature oxidation processes.
with high efficiency.335 It was shown that Ni2+ played a key role
in stabilizing the interface against dehydration. In general, the
stability of Pt/Fe(OH)x catalyst was highly dependent on the
humidity of air. A decline in CO oxidation activity from 100% to
27% in 70 min occurred when the reaction was switched from
humid air to dry air. The proposed reason behind the decrease
in activity was the instability of the interfacial Fe3+-OH-Pt sites
with respect to dehydration, considering the fact that CO
oxidation is an exothermic process. Since Ni2+ can form a
stable layered structure of Ni(OH)2 with nearly perfect
octahedral coordination, it was incorporated into the Fe(OH)x
sub-monolayer to prevent the dehydration-induced loss of
Fe3+-OH-Pt sites. TiO2-supported Pt/FeNi(OH)x catalyst was
stable in the reaction stream for more than 28 h without any
decrease in activity at room temperature and achieved 100%
CO conversion (Fig. 27). The OH:O ratio in the Pt/FeNi(OH)x
catalyst was maintained at 5.3 even after a 2-hour heat
treatment at 453 K under reaction atmosphere. DFT and Fig. 28 Schematic diagram for the preparation of bimetallic Ni–Pd catalysts and their
isotope-labeling experiments revealed that the OH groups at catalytic performances in the methane combustion. Reaction conditions: 4100 ppm
the Fe3+-OH-Pt interfaces readily react with CO adsorbed methane, 5 mol% water, 1.1 bar pressure, 1.2 mg Pd, 7.6 mg Ni (0.029 wt% Pd and
329
0.190 wt% Ni loading in relevant catalysts, except for the 0.24 wt% Pd catalyst).
nearby to directly convert into CO2 and simultaneously
(Copyright 2015 American Chemical Society).
produce coordinatively unsaturated Fe sites for O2 activation.
4.2.3 Hydrodechlorination. Halogenated compounds

emitted into the atmosphere are responsible for the thinning
and shrinking of the ozone layer in the stratosphere. They are
also treated as severe hazards for the ground water pollution
even at very low concentration. Recent research has therefore
focused on the development of in situ methods for destroying
chlorinated and brominated organic molecules such as CCl4
(carbon tetrachloride), PCE (tetrachloroethylene), and TCE
(trichloroethylene) in ground- and surface-waters. Catalytic
hydrodechlorination (HDC) is regarded as an innovative
method for transforming toxic hazardous chlorinated organic
compounds into recyclable products or even to chemical
336
intermediates of commercial value. Although the catalysts
Fig. 27 Catalytic performances of TiO2-supported Pt/FeNi(OH)x NPs, Pt NCs, and
Pt/Fe(OH)x NPs as a function of time-on-stream. Reaction conditions: 1% CO; 16% O2; containing noble metals, such as Pd or Pt are very efficient
337, 338
−1 −1
N2 balance; T = 303 K; SV = 400 L g Pt h ; relative humidity = 50%; pressure = 0.1 materials for HDC reactions, they are not ideal due to
335
MPa. (Copyright 2014 American Association for the Advancement of Science). their high cost and very high ability to activate hydrogen that

View Article Online
DOI: 10.1039/C6EE02002J
leads to the formation of fully hydrogenated undesired such, these two entities did not exhibit strong interaction with
products during hydrodechlorination. On the other hand, each other. Therefore, the higher NO reduction activities
monometallic catalysts of pure 3d transition metals (such as observed for the (Ce,Zr)Ox-supported system could be

Fe, Ni, and Cu) are not highly effective for the removal of attributed due to the fact that active contacts between highly
chlorine and deactivate faster due to coke formation, metal dispersed Pd and (Ce,Zr)Ox were modified either through
sintering and oxidation. direct blocking by NiO-type entities or through a certain
Nickel is a good candidate to promote decrease in the Pd dispersion.
hydrodechlorination. Indeed, catalytic properties of Ni have
been investigated in the transformation of chlorinated
aromatic compounds such as chlorobenzene.

339, 340
In the case 5. Conclusions and perspectives
of vicinal chloroalkanes (such as 1,2-dichloropropane), The present contribution provides an overview on the design
employing Ni catalysts involved more severe reaction principles of different bimetallic nickel catalysts and their use
conditions, i.e. high temperature and high hydrogen pressure, in different types of catalysis processes related to energy
337
than those used for Pd and Pt catalysts. In this regard, Ni production and environmental applications. In most cases, the
catalysts modified by noble metals such as Pd, Ru, Ag and Au role of the bimetallic surface and the role of each metal
341-346
are advantageous, where noble metal shows high activity counterpart in the reaction have been critically discussed.
and Ni shows high selectivity. Simagina et al. reported liquid Some reactions were favored and proceed on specific surfaces
phase HDC of hexachlorobenzene over carbon supported Ni– of the bimetallic catalysts. Consequently, continued effort on
Pd bimetallic catalysts, where the catalyst was less active than the rational design of surface specific bimetallic catalysts, and
pure Pd catalysts for the complete conversion of the understanding of structure-activity relationships are
hexachlorobenzene to benzene, but presented a reasonable critical to achieve superior catalytic performances.
activity to obtain the compounds of interest, mono and di- In addition to an appropriate catalyst design based on
341
chlorobenzene. The degree of dechlorination was fundamental understanding, another major issue relates to the
proportional to the surface Pd concentration. Interestingly, stability of bimetallic catalysts under reaction conditions. It is
isolated Pd atoms located at the surface of Ni rich bimetallic often seen that at high reaction temperature (such as in the
particles were more active than those lying in larger reforming conditions), the high diffusion rate of Ni over noble
ensembles. metals causes the destruction of the original structure of the
Recently, bimetallic Ni–Cu catalysts were also tested for bimetallic catalysts and the loss of its initial activity. Diffusion
347-351
the HDC process to fully replace the use of noble metals. of Ni can be prevented by introducing a diffusion barrier layer
While hydrodechlorination of 1,2-dichloroethane over pure Ni for surface Ni metal atoms.
355, 356
For instance, replacing bulk
mainly produces ethane, increasing the Cu content in Pt with WC in Ni–Pt catalysts can retain the unique catalytic
bimetallic catalysts results in an increase in ethylene properties of bimetallic surfaces, i.e., the subsurface Pt–Ni–WC
selectivity. The specific consumption rate of 1,2- structure for hydrogenation and the surface Ni–WC
dichloroethane decreases when Cu loading increases, configuration for reforming reactions. We expect more such
however, the turnover frequency seems to be independent of systems to be developed in the future.
the surface composition of alloy particles. Coke and sulfur deposition are serious problems in
4.2.4 Others. NOx and SOx are among the other major hydrocarbon reforming processes. Although noble metals can
components causing the air pollution. Although there are a significantly improve the coke or sulfur resistant properties of
few reports on the catalytic materials for the removal of NOx Ni-based catalysts, the high cost limits their application in
352-354
and SOx, bimetallic Ni catalyst was rarely used in this industrial processes. Some efforts have been made with 3d
purpose. Three way catalysts Ni–Pd supported on different transition metals, but their stability at high temperature
oxides such as Al2O3, CeO2 and ZrO2 were reported for the conditions was not sufficient.
107, 110
One possible way to
324, 325
elimination of NO in stoichiometric conditions. The reduce catalyst cost without compromising the
activity of the catalysts was shown to depend strongly on the activity/stability could be the introduction of non-metal
support used. Whereas practically no differences were elements such as boron and phosphorus,
357
since nickel-
detected for the Al2O3-supported bimetallic catalyst in borides and phosphides have shown high activity and poison
comparison with the analogous monometallic Pd system, resisting property towards different hydrotreating
apparent differences appeared for (Ce,Zr)Ox-containing reactions.
357, 358
Alternatively, “noble-metal-like” compounds
catalysts. In-situ XANES experiments revealed there was no can be combined with Ni. For example, tungsten carbide (WC)
apparent modification of the Pd electronic properties after Ni could be a replacement for Pt since it exhibits “Pt-like”
incorporation, which seems to be contradictory to the behavior and possesses high chemically stability, resistance to
prediction by d-band theory. This is due to the unique poisoning, and high electronic conductivity.
359, 360
We believe
structural features of the catalyst. From nanoprobe energy- that the introduction of these non-metal additives can further
dispersive X-ray spectroscopy (EDX) analysis, Pd maintained a improve the catalytic properties of simple bimetallic Ni–M
particular trend in interacting with the Ce-Zr mixed oxide systems, which is certainly an interesting area with room for
component on the support, while Ni appeared to interact further developments.
preferentially with the alumina component on the support. As

Please
View Article Online
DOI: 10.1039/C6EE02002J
Acknowledgments 29. M. B. Gawande, A. Goswami, T. Asefa, H. Guo, A. V. Biradar,

D.-L. Peng, R. Zboril and R. S. Varma, Chem. Soc. Rev., 2015, 44,
We thank the Young Investigator Award from National 7540-7590.
University of Singapore (WBS: R-279-000-464-133) for the 30. H. N. Nong, L. Gan, E. Willinger, D. Teschner and P. Strasser,

financial support. Chem. Sci., 2014, 5, 2955-2963.
31. H. N. Nong, H.-S. Oh, T. Reier, E. Willinger, M.-G. Willinger, V.
Petkov, D. Teschner and P. Strasser, Angew. Chem. Int. Ed.,
Notes and references 2015, 54, 2975-2979.
32. S. K. Singh, A. K. Singh, K. Aranishi and Q. Xu, J. Am. Chem.
1. Energy Systems and Sustainability: Power for a Sustainable
Soc., 2011, 133, 19638-19641.
Future, Oxford Univerity Press, 2nd edn., 2012.

33. Y. W. Lee, M. Kim, S. W. Kang and S. W. Han, Angew. Chem.
2. F. Liao, T. W. B. Lo and S. C. E. Tsang, ChemCatChem, 2015, 7,
Int. Ed., 2011, 50, 3466-3470.
1998-2014.
34. J. Zhang, H. Yang, J. Fang and S. Zou, Nano Lett., 2010, 10, 638-
3. W. Yu, M. D. Porosoff and J. G. Chen, Chem. Rev., 2012, 112,
644.
5780-5817.
35. J. Wu, L. Qi, H. You, A. Gross, J. Li and H. Yang, J. Am. Chem.
4. D. Li, I. Atake, T. Shishido, Y. Oumi, T. Sano and K. Takehira, J.
Soc., 2012, 134, 11880-11883.
Catal., 2007, 250, 299-312.
36. T. C. Deivaraj, W. Chen and J. Y. Lee, J. Mater. Chem., 2003, 13,
5. K. Nagaoka, A. Jentys and J. A. Lercher, J. Catal., 2005, 229,
2555-2560.
185-196.
37. R. M. Arán-Ais, F. Dionigi, T. Merzdorf, M. Gocyla, M. Heggen,
6. D. Li, Y. Nakagawa and K. Tomishige, Appl. Catal. A: Gen.,
R. E. Dunin-Borkowski, M. Gliech, J. Solla-Gullón, E. Herrero, J.
2011, 408, 1-24.
M. Feliu and P. Strasser, Nano Lett., 2015, 15, 7473-7480.
7. S. Z. Tasker, E. A. Standley and T. F. Jamison, Nature, 2014,
38. P. A. Lin and R. M. Sankaran, Angew. Chem. Int. Ed., 2011, 50,
509, 299-309.
10953-10956.
8. H. Mu, L. Pan, D. Song and Y. Li, Chem. Rev., 2015, 115, 12091-
39. M. Raney, Journal, 1927.
12137.
40. D. Wang, P. Zhao and Y. Li, Scientific Reports, 2011, 1, 37.
9. C.-j. Liu, J. Ye, J. Jiang and Y. Pan, ChemCatChem, 2011, 3, 529-
41. L. Chen, H. Guo, T. Fujita, A. Hirata, W. Zhang, A. Inoue and M.
541.
Chen, Adv. Funct. Mater., 2011, 21, 4364-4370.
10. S. Li and J. Gong, Chem. Soc. Rev., 2014, 43, 7245-7256.
42. J. Snyder, I. McCue, K. Livi and J. Erlebacher, J. Am. Chem. Soc.,
11. H. Zhang, M. Jin and Y. Xia, Chem. Soc. Rev., 2012, 41, 8035-
2012, 134, 8633-8645.
8049.
43. L.-X. Ding, G.-R. Li, Z.-L. Wang, Z.-Q. Liu, H. Liu and Y.-X. Tong,
12. H.-l. Liu, F. Nosheen and X. Wang, Chem. Soc. Rev., 2015, 44,
Chem. Eur. J., 2012, 18, 8386-8391.
3056-3078.
44. Z. Li, R. Yu, J. Huang, Y. Shi, D. Zhang, X. Zhong, D. Wang, Y. Wu
13. S. K. Singh and Q. Xu, J. Am. Chem. Soc., 2009, 131, 18032-
and Y. Li, Nat Commun, 2015, 6.
18033.
45. R. Yi, R. Shi, G. Gao, N. Zhang, X. Cui, Y. He and X. Liu, J. Phys.
14. H.-L. Wang, J.-M. Yan, Z.-L. Wang, S.-I. O and Q. Jiang, J. Mater.
Chem. C, 2009, 113, 1222-1226.
Chem. A, 2013, 1, 14957-14962.
46. J. R. Kitchin, J. K. Nørskov, M. A. Barteau and J. G. Chen, Phys.
15. M. K. Carpenter, T. E. Moylan, R. S. Kukreja, M. H. Atwan and
Rev. Lett., 2004, 93, 156801.
M. M. Tessema, J. Am. Chem. Soc., 2012, 134, 8535-8542.
47. J. K. Norskov, T. Bligaard, J. Rossmeisl and C. H. Christensen,
16. Y. Wu, S. Cai, D. Wang, W. He and Y. Li, J. Am. Chem. Soc.,
Nat Chem, 2009, 1, 37-46.
2012, 134, 8975-8981.
48. L. Leppert, R. Kempe and S. Kummel, Phys. Chem. Chem. Phys.,
17. J. Gu, Y.-W. Zhang and F. Tao, Chem. Soc. Rev., 2012, 41, 8050-
2015, 17, 26140-26148.
8065.
49. A. V. Ruban, H. L. Skriver and J. K. Nørskov, Phy. Rev. B, 1999,
18. P. Nash, Phase diagrams of binary nickel alloys, ASM
59, 15990-16000.
International, 1991.
50. R. Mu, Q. Fu, H. Liu, D. Tan, R. Zhai and X. Bao, Appl. Surf. Sci.,
19. A. I. Frenkel, Chem. Soc. Rev., 2012, 41, 8163-8178.
2009, 255, 7296-7301.
20. J. C. Yang, M. W. Small, R. V. Grieshaber and R. G. Nuzzo,
51. C. A. Menning and J. G. Chen, J. Power Sources, 2010, 195,
Chem. Soc. Rev., 2012, 41, 8179-8194.
3140-3144.
21. C. T. Campbell, Annu. Rev. Phys. Chem., 1990, 41, 775-837.
52. K. Mazloomi and C. Gomes, Renew. Sust. Energ. Rev., 2012, 16,
22. J. Rodriguez, Surf. Sci. Rep., 1996, 24, 223-287.
3024-3033.
23. J. G. Chen, C. A. Menning and M. B. Zellner, Surf. Sci. Rep.,
53. A. Züttel, A. Remhof, A. Borgschulte and O. Friedrichs,
2008, 63, 201-254.
Philosophical Transactions of the Royal Society of London A:
24. G. Chen, S. Desinan, R. Nechache, R. Rosei, F. Rosei and D. Ma,
Mathematical, Physical and Engineering Sciences, 2010, 368,
Chem. Commun., 2011, 47, 6308-6310.
3329-3342.
25. S. Carenco, C.-H. Wu, A. Shavorskiy, S. Alayoglu, G. A.
54. U. Eberle, M. Felderhoff and F. Schüth, Angew. Chem. Int. Ed.,
Somorjai, H. Bluhm and M. Salmeron, Small, 2015, 11, 3045-
2009, 48, 6608-6630.
3053.
55. S.-i. Orimo, Y. Nakamori, J. R. Eliseo, A. Züttel and C. M.
26. A. B. Vysakh, C. L. Babu and C. P. Vinod, J. Phys. Chem. C, 2015,
Jensen, Chem. Rev., 2007, 107, 4111-4132.
119, 8138-8146.
56. N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M.
27. J. Xiang, P. Li, H. Chong, L. Feng, F. Fu, Z. Wang, S. Zhang and
O'Keeffe and O. M. Yaghi, Science, 2003, 300, 1127-1129.
M. Zhu, Nano Res., 2014, 7, 1337-1343.
57. D. Pakhare and J. Spivey, Chem. Soc. Rev., 2014, 43, 7813-
28. B. T. Sneed, A. P. Young, D. Jalalpoor, M. C. Golden, S. Mao, Y.
7837.
Jiang, Y. Wang and C.-K. Tsung, ACS Nano, 2014, 8, 7239-7250.

View Article Online
DOI: 10.1039/C6EE02002J
58. P. Makowski, A. Thomas, P. Kuhn and F. Goettmann, Energy 89. A. Horváth, G. Stefler, O. Geszti, A. Kienneman, A. Pietraszek
Environ. Sci., 2009, 2, 480-490. and L. Guczi, Catal. Today, 2011, 169, 102-111.
59. M. Yadav and Q. Xu, Energy Environ. Sci., 2012, 5, 9698-9725. 90. M. Ocsachoque, F. Pompeo and G. Gonzalez, Catal. Today,
60. Z. Wei, J. Sun, Y. Li, A. K. Datye and Y. Wang, Chem. Soc. Rev., 2011, 172, 226-231.

2012, 41, 7994-8008. 91. Z. Rui, D. Feng, H. Chen and H. Ji, Int. J. Hydrogen Energy,
61. V. Dal Santo, A. Gallo, A. Naldoni, M. Guidotti and R. Psaro, 2014, 39, 16252-16261.
Catal. Today, 2012, 197, 190-205. 92. V. L. Dagle, R. Dagle, L. Kovarik, A. Genc, Y.-G. Wang, M.
62. C. Song, Catal. Today, 2002, 77, 17-49. Bowden, H. Wan, M. Flake, V.-A. Glezakou, D. L. King and R.
63. J. H. Sinfelt and D. J. C. Yates, J. Catal., 1967, 8, 82-90. Rousseau, Appl. Catal., B, 2016, 184, 142-152.
64. N. Bion, D. Duprez and F. Epron, ChemSusChem, 2012, 5, 76- 93. F. Besenbacher, I. Chorkendorff, B. S. Clausen, B. Hammer, A.
84. M. Molenbroek, J. K. Nørskov and I. Stensgaard, Science, 1998,

65. J. Sehested, Catal. Today, 2006, 111, 103-110. 279, 1913-1915.
66. H. S. Bengaard, J. K. Nørskov, J. Sehested, B. S. Clausen, L. P. 94. A. M. Molenbroek, J. K. Nørskov and B. S. Clausen, J. Phys.
Nielsen, A. M. Molenbroek and J. R. Rostrup-Nielsen, J. Catal., Chem. B, 2001, 105, 5450-5458.
2002, 209, 365-384. 95. Y.-H. Chin, D. L. King, H.-S. Roh, Y. Wang and S. M. Heald, J.
67. D. L. Trimm, Catal. Today, 1997, 37, 233-238. Catal., 2006, 244, 153-162.
68. Y.-g. Chen, K. Tomishige, K. Yokoyama and K. Fujimoto, Appl. 96. I. Gavrielatos, V. Drakopoulos and S. G. Neophytides, J. Catal.,
Catal. A: Gen., 1997, 165, 335-347. 2008, 259, 75-84.
69. K. Tomishige, S. Kanazawa, M. Sato, K. Ikushima and K. 97. L. Guczi, G. Stefler, O. Geszti, I. Sajó, Z. Pászti, A. Tompos and
Kunimori, Catal. Lett., 2002, 84, 69-74. Z. Schay, Appl. Catal., A, 2010, 375, 236-246.
70. S. Wang, G. Q. Lu and G. J. Millar, Energy & Fuels, 1996, 10, 98. N. V. Parizotto, K. O. Rocha, S. Damyanova, F. B. Passos, D.
896-904. Zanchet, C. M. P. Marques and J. M. C. Bueno, Appl. Catal., A,
71. Y. H. Hu and E. Ruckenstein, in Advances in Catalysis, 2007, 330, 12-22.
Academic Press, 2004, vol. 48, pp. 297-345. 99. H. Jeong and M. Kang, Appl. Catal., B, 2010, 95, 446-455.
72. Z. Hou, P. Chen, H. Fang, X. Zheng and T. Yashima, Int. J. 100. Y. Xu, C. Fan, Y.-A. Zhu, P. Li, X.-G. Zhou, D. Chen and W.-K.
Hydrogen Energy, 2006, 31, 555-561. Yuan, Catal. Today, 2012, 186, 54-62.
73. J. R. Rostrup-Nielsen, Catal. Today, 2000, 63, 159-164. 101. D. Li, T. Shishido, Y. Oumi, T. Sano and K. Takehira, Appl.
74. B. Steinhauer, M. R. Kasireddy, J. Radnik and A. Martin, Appl. Catal., A, 2007, 332, 98-109.
Catal. A: Gen., 2009, 366, 333-341. 102. K. Tomishige, Journal of the Japan Petroleum Institute, 2007,
75. N. V. Parizotto, D. Zanchet, K. O. Rocha, C. M. P. Marques and 50, 287-298.
J. M. C. Bueno, Appl. Catal., A, 2009, 366, 122-129. 103. H. Wu, V. La Parola, G. Pantaleo, F. Puleo, A. Venezia and L.
76. M. García-Diéguez, E. Finocchio, M. Á. Larrubia, L. J. Alemany Liotta, Catalysts, 2013, 3, 563.
and G. Busca, J. Catal., 2010, 274, 11-20. 104. L. Pleth Nielsen, F. Besenbacher, I. Stensgaard, E.
77. M. García-Diéguez, I. S. Pieta, M. C. Herrera, M. A. Larrubia and Laegsgaard, C. Engdahl, P. Stoltze, K. W. Jacobsen and J. K.
L. J. Alemany, J. Catal., 2010, 270, 136-145. Nørskov, Phys. Rev. Lett., 1993, 71, 754-757.
78. M. García-Diéguez, I. S. Pieta, M. C. Herrera, M. A. Larrubia and 105. M. Rangan, M. M. Yung and J. W. Medlin, J. Catal., 2011,
L. J. Alemany, Appl. Catal., A, 2010, 377, 191-199. 282, 249-257.
79. S. R. de Miguel, I. M. J. Vilella, S. P. Maina, D. San José-Alonso, 106. C. Xie, Y. Chen, Y. Li, X. Wang and C. Song, Appl. Catal. A:
M. C. Román-Martínez and M. J. Illán-Gómez, Appl. Catal., A, Gen., 2010, 390, 210-218.
2012, 435–436, 10-18. 107. S. A. Theofanidis, V. V. Galvita, H. Poelman and G. B. Marin,
80. X. Yu, F. Zhang, N. Wang, S. Hao and W. Chu, Catal. Lett., 2013, ACS Catal., 2015, 5, 3028-3039.
144, 293-300. 108. P. Djinović, I. G. Osojnik Črnivec, B. Erjavec and A. Pintar,
81. L. Li, L. Zhou, S. Ould-Chikh, D. H. Anjum, M. B. Kanoun, J. Appl. Catal., B, 2012, 125, 259-270.
Scaranto, M. N. Hedhili, S. Khalid, P. V. Laveille, L. D'Souza, A. 109. V. M. Gonzalez-delaCruz, R. Pereñiguez, F. Ternero, J. P.
Clo and J.-M. Basset, ChemCatChem, 2015, 7, 819-829. Holgado and A. Caballero, J. Phys. Chem. C, 2012, 116, 2919-
82. C. Dai, S. Zhang, A. Zhang, C. Song, C. Shi and X. Guo, J. Mater. 2926.
Chem. A, 2015, 3, 16461-16468. 110. H. Ay and D. Üner, Appl. Catal., B, 2015, 179, 128-138.
83. N. H. Elsayed, N. R. M. Roberts, B. Joseph and J. N. Kuhn, Appl. 111. W. An, X. C. Zeng and C. H. Turner, J. Chem. Phys., 2009,
Catal., B, 2015, 179, 213-219. 131, 174702.
84. V. S. Guggilla, J. Akyurtlu, A. Akyurtlu and I. Blankson, 112. S. M. Sidik, S. Triwahyono, A. A. Jalil, Z. A. Majid, N.
Industrial & Engineering Chemistry Research, 2010, 49, 8164- Salamun, N. B. Talib and T. A. T. Abdullah, Chem. Eng. J., 2016,
8173. 295, 1-10.
85. V. S. Guggilla, V. P. S. Mangalampalli, J. F. Akyurtlu and A. 113. H. Arbag, S. Yasyerli, N. Yasyerli, G. Dogu and T. Dogu, Appl.
Akyurtlu, Industrial & Engineering Chemistry Research, 2013, Catal., B, 2016, 198, 254-265.
52, 338-345. 114. X. Zhang, C. Yang, Y. Zhang, Y. Xu, S. Shang and Y. Yin, Int. J.
86. M. Nowosielska, W. K. Jozwiak and J. Rynkowski, Catal. Lett., Hydrogen Energy, 2015, 40, 16115-16126.
2008, 128, 83-93. 115. M. Abdollahifar, M. Haghighi, A. A. Babaluo and S. K.
87. H. Arbag, S. Yasyerli, N. Yasyerli and G. Dogu, Int. J. Hydrogen Talkhoncheh, Ultrason. Sonochem., 2016, 31, 173-183.
Energy, 2010, 35, 2296-2304. 116. L. De Rogatis, T. Montini, B. Lorenzut and P. Fornasiero,
88. M. Ferrandon, A. J. Kropf and T. Krause, Appl. Catal. A: Gen., Energy Environ. Sci., 2008, 1, 501-509.
2010, 379, 121-128. 117. A. Le Valant, N. Bion, F. Can, D. Duprez and F. Epron, Appl.
Catal. B: Environ., 2010, 97, 72-81.

Please
View Article Online
DOI: 10.1039/C6EE02002J
118. G. Zhou, L. Barrio, S. Agnoli, S. D. Senanayake, J. Evans, A. 146. M. Shiraga, D. Li, I. Atake, T. Shishido, Y. Oumi, T. Sano and
Kubacka, M. Estrella, J. C. Hanson, A. Martínez-Arias, M. K. Takehira, Appl. Catal., A, 2007, 318, 143-154.
Fernández-García and J. A. Rodriguez, Angew. Chem. Int. Ed., 147. D. Li, M. Shiraga, I. Atake, T. Shishido, Y. Oumi, T. Sano and
2010, 49, 9680-9684. K. Takehira, Appl. Catal. A: Gen., 2007, 321, 155-164.

119. M. M. Rahman, T. L. Church, M. F. Variava, A. T. Harris and 148. J. A. Velasco, C. Fernandez, L. Lopez, S. Cabrera, M.
A. I. Minett, RSC Adv., 2014, 4, 18951-18960. Boutonnet and S. Järås, Fuel, 2015, 153, 192-201.
120. R. M. Navarro, R. Guil-Lopez, A. A. Ismail, S. A. Al-Sayari and 149. H. E. Figen and S. Z. Baykara, Int. J. Hydrogen Energy, 2015,
J. L. G. Fierro, Catal. Today, 2015, 242, Part A, 60-70. 40, 7439-7451.
121. D. Zanchet, J. B. O. Santos, S. Damyanova, J. M. R. Gallo and 150. P. Benito, V. Dal Santo, V. De Grandi, M. Marelli, G.
J. M. C. Bueno, ACS Catal., 2015, 5, 3841-3863. Fornasari, R. Psaro and A. Vaccari, Appl. Catal., B, 2015, 179,
122. P. Mierczynski, K. Vasilev, A. Mierczynska, W. Maniukiewicz, 150-159.

M. I. Szynkowska and T. P. Maniecki, Appl. Catal., B, 2016, 185, 151. K. Nakagawa, N. Ikenaga, Y. Teng, T. Kobayashi and T.
281-294. Suzuki, Appl. Catal., A, 1999, 180, 183-193.
123. L. V. Mattos, G. Jacobs, B. H. Davis and F. B. Noronha, Chem. 152. A. C. W. Koh, L. Chen, W. Kee Leong, B. F. G. Johnson, T.
Rev., 2012, 112, 4094-4123. Khimyak and J. Lin, Int. J. Hydrogen Energy, 2007, 32, 725-730.
124. K. O. Christensen, D. Chen, R. Lødeng and A. Holmen, Appl. 153. L. Li, P. Lu, Y. Yao and W. Ji, Catal. Commun., 2012, 26, 72-
Catal., A, 2006, 314, 9-22. 77.
125. C. Zhang, P. Zhang, S. Li, G. Wu, X. Ma and J. Gong, PCCP, 154. L. De Rogatis, T. Montini, A. Cognigni, L. Olivi and P.
2012, 14, 3295-3298. Fornasiero, Catal. Today, 2009, 145, 176-185.
126. R. I. Masel, Principles of Adsorption and Reaction on Solid 155. A. C. Ferreira, A. M. Ferraria, A. M. B. do Rego, A. P.
Surfaces, Wiley-IEEE, New York, 1996. Gonçalves, M. R. Correia, T. A. Gasche and J. B. Branco, J.
127. T. S. Moraes, R. C. Rabelo Neto, M. C. Ribeiro, L. V. Mattos, Alloys Compd., 2010, 489, 316-323.
M. Kourtelesis, S. Ladas, X. Verykios and F. B. Noronha, Appl. 156. A. C. Ferreira, A. P. Gonçalves, T. A. Gasche, A. M. Ferraria,
Catal., B, 2016, 181, 754-768. A. M. B. d. Rego, M. R. Correia, A. M. Bola and J. B. Branco, J.
128. M. C. Sanchez-Sanchez, R. M. Navarro Yerga, D. I. Alloys Compd., 2010, 497, 249-258.
Kondarides, X. E. Verykios and J. L. G. Fierro, The Journal of 157. S. K. Singh and Q. Xu, Catal. Sci. Technol., 2013, 3, 1889-
Physical Chemistry A, 2010, 114, 3873-3882. 1900.
129. S. A. Tupy, A. M. Karim, C. Bagia, W. Deng, Y. Huang, D. G. 158. A. Klerke, C. H. Christensen, J. K. Norskov and T. Vegge, J.
Vlachos and J. G. Chen, ACS Catal., 2012, 2, 2290-2296. Mater. Chem., 2008, 18, 2304-2310.
130. M. C. Sanchez-Sanchez, R. M. Navarro, I. Espartero, A. A. 159. C. J. H. Jacobsen, S. Dahl, B. S. Clausen, S. Bahn, A.
Ismail, S. A. Al-Sayari and J. L. G. Fierro, Top. Catal., 2013, 56, Logadottir and J. K. Nørskov, J. Am. Chem. Soc., 2001, 123,
1672-1685. 8404-8405.
131. R. M. Navarro, R. Guil-Lopez, J. M. Gonzalez-Carballo, A. 160. A. Boisen, S. Dahl, J. K. Nørskov and C. H. Christensen, J.
Cubero, A. A. Ismail, S. A. Al-Sayari and J. L. G. Fierro, Appl. Catal., 2005, 230, 309-312.
Catal., A, 2014, 474, 168-177. 161. S.-F. Yin, Q.-H. Zhang, B.-Q. Xu, W.-X. Zhu, C.-F. Ng and C.-T.
132. C. He, J. Zheng, K. Wang, H. Lin, J.-Y. Wang and Y. Yang, Au, J. Catal., 2004, 224, 384-396.
Appl. Catal., B, 2015, 162, 401-411. 162. D. A. Hansgen, D. G. Vlachos and J. G. Chen, Nat Chem,
133. T. S. Moraes, R. C. R. Neto, M. C. Ribeiro, L. V. Mattos, M. 2010, 2, 484-489.
Kourtelesis, S. Ladas, X. Verykios and F. Bellot Noronha, Catal. 163. W. Guo, M. Stamatakis and D. G. Vlachos, ACS Catal., 2013,
Today, 2015, 242, Part A, 35-49. 3, 2248-2255.
134. R. Pérez-Hernández, G. Mondragón Galicia, D. Mendoza 164. W. Guo and D. G. Vlachos, Nat Commun, 2015, 6.
Anaya, J. Palacios, C. Angeles-Chavez and J. Arenas-Alatorre, 165. H. Dietrich, K. Jacobi and G. Ertl, J. Chem. Phys., 1996, 105,
Int. J. Hydrogen Energy, 2008, 33, 4569-4576. 8944-8950.
135. P. K. Sharma, N. Saxena, A. Bhatt, C. Rajagopal and P. K. Roy, 166. S. B. Simonsen, D. Chakraborty, I. Chorkendorff and S. Dahl,
Catal. Sci. Technol., 2013, 3, 1017-1026. Appl. Catal., A, 2012, 447–448, 22-31.
136. M. M. Rahman, Int. J. Hydrogen Energy, 2015, 40, 14833- 167. L.-F. Zhang, M. Li, T.-Z. Ren, X. Liu and Z.-Y. Yuan, Int. J.
14844. Hydrogen Energy, 2015, 40, 2648-2656.
137. A. J. Vizcaíno, A. Carrero and J. A. Calles, Int. J. Hydrogen 168. S. Wang, D. Zhang, Y. Ma, H. Zhang, J. Gao, Y. Nie and X.
Energy, 2007, 32, 1450-1461. Sun, ACS Appl. Mater. Interfaces, 2014, 6, 12429-12435.
138. A. Carrero, J. A. Calles and A. J. Vizcaíno, Appl. Catal., A, 169. G. Chen, S. Desinan, R. Rosei, F. Rosei and D. Ma, Chem. Eur.
2007, 327, 82-94. J., 2012, 18, 7925-7930.
139. P. Biswas and D. Kunzru, Catal. Lett., 2007, 118, 36-49. 170. G. P. Rachiero, U. B. Demirci and P. Miele, Int. J. Hydrogen
140. J. A. Calles, A. Carrero and A. J. Vizcaíno, Microporous Energy, 2011, 36, 7051-7065.
Mesoporous Mater., 2009, 119, 200-207. 171. N. Cao, J. Su, W. Luo and G. Cheng, Int. J. Hydrogen Energy,
141. F. Wang, Y. Li, W. Cai, E. Zhan, X. Mu and W. Shen, Catal. 2014, 39, 426-435.
Today, 2009, 146, 31-36. 172. H.-L. Jiang, T. Umegaki, T. Akita, X.-B. Zhang, M. Haruta and
142. L.-C. Chen and S. D. Lin, Appl. Catal., B, 2011, 106, 639-649. Q. Xu, Chem. Eur. J., 2010, 16, 3132-3137.
143. B. Christian Enger, R. Lødeng and A. Holmen, Appl. Catal., A, 173. F. Qiu, G. Liu, L. Li, Y. Wang, C. Xu, C. An, C. Chen, Y. Xu, Y.
2008, 346, 1-27. Huang, Y. Wang, L. Jiao and H. Yuan, Chem. Eur. J., 2014, 20,
144. S. A. Al-Sayari, The Open Catalysis Journal, 2013, 6, 17-28. 505-509.
145. P. Corbo and F. Migliardini, Int. J. Hydrogen Energy, 2007, 174. K. Mori, T. Taga and H. Yamashita, ChemCatChem, 2015, 7,
32, 55-66. 1285-1291.

View Article Online
DOI: 10.1039/C6EE02002J
175. J.-M. Yan, X.-B. Zhang, S. Han, H. Shioyama and Q. Xu, J. 206. Ç. Çakanyıldırım, U. B. Demirci, T. Şener, Q. Xu and P. Miele,
Power Sources, 2009, 194, 478-481. Int. J. Hydrogen Energy, 2012, 37, 9722-9729.
176. H.-L. Jiang, T. Akita and Q. Xu, Chem. Commun., 2011, 47, 207. Q.-L. Zhu, D.-C. Zhong, U. B. Demirci and Q. Xu, ACS Catal.,
10999-11001. 2014, 4, 4261-4268.

177. A. Yousef, N. A. M. Barakat, M. El-Newehy and H. Y. Kim, Int. 208. X. Xiong, L. Zhou, G. Yu, K. Yang, M. Ye and Q. Xia, Int. J.
J. Hydrogen Energy, 2012, 37, 17715-17723. Hydrogen Energy, 2015, 40, 15521-15528.
178. S. Cho, J. Lee, Y. Lee and D. Kim, Catal. Lett., 2006, 109, 181- 209. L. Zhang, L. Zhou, K. Yang, D. Gao, C. Huang, Y. Chen, F.
186. Zhang, X. Xiong, L. Li and Q. Xia, J. Alloys Compd., 2016, 677,
179. S. K. Singh, X.-B. Zhang and Q. Xu, J. Am. Chem. Soc., 2009, 87-95.
131, 9894-9895. 210. C. V. Ovesen, B. S. Clausen, B. S. Hammershøi, G. Steffensen,
180. S. K. Singh and Q. Xu, Chem. Commun., 2010, 46, 6545- T. Askgaard, I. Chorkendorff, J. K. Nørskov, P. B. Rasmussen, P.
6547. Stoltze and P. Taylor, J. Catal., 1996, 158, 170-180.
181. L. He, Y. Huang, X. Y. Liu, L. Li, A. Wang, X. Wang, C.-Y. Mou 211. A. A. Gokhale, J. A. Dumesic and M. Mavrikakis, J. Am.
and T. Zhang, Appl. Catal., B, 2014, 147, 779-788. Chem. Soc., 2008, 130, 1402-1414.
182. A. K. Singh, M. Yadav, K. Aranishi and Q. Xu, Int. J. Hydrogen 212. N. Schumacher, A. Boisen, S. Dahl, A. A. Gokhale, S. Kandoi,
Energy, 2012, 37, 18915-18919. L. C. Grabow, J. A. Dumesic, M. Mavrikakis and I. Chorkendorff,
183. J. Wang, X.-B. Zhang, Z.-L. Wang, L.-M. Wang and Y. Zhang, J. Catal., 2005, 229, 265-275.
Energy Environ. Sci., 2012, 5, 6885-6888. 213. C. A. Callaghan, S. A. Vilekar, I. Fishtik and R. Datta, Appl.
184. J. B. Yoo, H. S. Kim, S. H. Kang, B. Lee and N. H. Hur, J. Catal., A, 2008, 345, 213-232.
Mater. Chem. A, 2014, 2, 18929-18937. 214. S.-C. Huang, C.-H. Lin and J. H. Wang, J. Phys. Chem. C, 2010,
185. B. Xia, N. Cao, H. Dai, J. Su, X. Wu, W. Luo and G. Cheng, 114, 9826-9834.
ChemCatChem, 2014, 6, 2549-2552. 215. L.-Y. Gan, R.-Y. Tian, X.-B. Yang, H.-D. Lu and Y.-J. Zhao, J.
186. J. Wang, W. Li, Y. Wen, L. Gu and Y. Zhang, Advanced Energy Phys. Chem. C, 2012, 116, 745-752.
Materials, 2015, 5, n/a-n/a. 216. J.-H. Lin and V. V. Guliants, Appl. Catal., A, 2012, 445–446,
187. J. Chen, Q. Yao, J. Zhu, X. Chen and Z.-H. Lu, Int. J. Hydrogen 187-194.
Energy, 2016, 41, 3946-3954. 217. V. M. Shinde and G. Madras, Appl. Catal., B, 2012, 123–124,
188. S. K. Singh and Q. Xu, Inorg. Chem., 2010, 49, 6148-6152. 367-378.
189. L. He, Y. Huang, A. Wang, Y. Liu, X. Liu, X. Chen, J. J. Delgado, 218. J.-H. Lin and V. V. Guliants, ChemCatChem, 2012, 4, 1611-
X. Wang and T. Zhang, J. Catal., 2013, 298, 1-9. 1621.
190. Y. Jiang, Q. Kang, J. Zhang, H.-B. Dai and P. Wang, J. Power 219. A. R. S. Rad, M. B. Khoshgouei, S. Rezvani and A. R. Rezvani,
Sources, 2015, 273, 554-560. Fuel Process. Technol., 2012, 96, 9-15.
191. Y. Du, J. Su, W. Luo and G. Cheng, ACS Appl. Mater. 220. E. T. Saw, U. Oemar, X. R. Tan, Y. Du, A. Borgna, K. Hidajat
Interfaces, 2015, 7, 1031-1034. and S. Kawi, J. Catal., 2014, 314, 32-46.
192. Y.-Y. Jiang, H.-B. Dai, Y.-J. Zhong, D.-M. Chen and P. Wang, 221. Y. C. Huang, T. Zhou, H. Liu, C. Ling, S. Wang and J. Y. Du,
Chem. Eur. J., 2015, 21, 15439-15445. ChemPhysChem, 2014, 15, 2490-2496.
193. L. Wen, X. Du, J. Su, W. Luo, P. Cai and G. Cheng, Dalton 222. E. T. Saw, U. Oemar, M. L. Ang, K. Hidajat and S. Kawi,
Trans., 2015, 44, 6212-6218. ChemCatChem, 2015, 7, 3358-3367.
194. N. Cao, L. Yang, H. Dai, T. Liu, J. Su, X. Wu, W. Luo and G. 223. O. Arbeláez, T. R. Reina, S. Ivanova, F. Bustamante, A. L.
Cheng, Inorg. Chem., 2014, 53, 10122-10128. Villa, M. A. Centeno and J. A. Odriozola, Appl. Catal., A, 2015,
195. N. Cao, J. Su, W. Luo and G. Cheng, Int. J. Hydrogen Energy, 497, 1-9.
2014, 39, 9726-9734. 224. GreeleyJ, I. E. L. Stephens, A. S. Bondarenko, T. P.
196. A. K. Singh and Q. Xu, Int. J. Hydrogen Energy, 2014, 39, Johansson, H. A. Hansen, T. F. Jaramillo, RossmeislJ,
9128-9134. ChorkendorffI and J. K. Nørskov, Nat Chem, 2009, 1, 552-556.
197. N. Cao, L. Yang, C. Du, J. Su, W. Luo and G. Cheng, J. Mater. 225. J. R. Greer, Science, 2014, 343, 1319-1320.
Chem. A, 2014, 2, 14344-14347. 226. D. Strmcnik, M. Uchimura, C. Wang, R. Subbaraman, N.
198. S. K. Singh, Y. Iizuka and Q. Xu, Int. J. Hydrogen Energy, Danilovic, V. van der, A. P. Paulikas, V. R. Stamenkovic and N.
2011, 36, 11794-11801. M. Markovic, Nat Chem, 2013, 5, 300-306.
199. D. Bhattacharjee, K. Mandal and S. Dasgupta, J. Power 227. T. Reier, M. Oezaslan and P. Strasser, ACS Catal., 2012, 2,
Sources, 2015, 287, 96-99. 1765-1772.
200. S.-H. Wu and D.-H. Chen, J. Colloid Interface Sci., 2003, 259, 228. E. Ortel, T. Reier, P. Strasser and R. Kraehnert, Chem.
282-286. Mater., 2011, 23, 3201-3209.
201. D. G. Tong, X. L. Zeng, W. Chu, D. Wang and P. Wu, Mater. 229. T. Reier, Z. Pawolek, S. Cherevko, M. Bruns, T. Jones, D.
Res. Bull., 2010, 45, 442-447. Teschner, S. Selve, A. Bergmann, H. N. Nong, R. Schlögl, K. J. J.
202. D. G. Tong, D. M. Tang, W. Chu, G. F. Gu and P. Wu, J. Mayrhofer and P. Strasser, J. Am. Chem. Soc., 2015, 137,
Mater. Chem. A, 2013, 1, 6425-6432. 13031-13040.
203. W. Gao, C. Li, H. Chen, M. Wu, S. He, M. Wei, D. G. Evans 230. W.-F. Chen, K. Sasaki, C. Ma, A. I. Frenkel, N. Marinkovic, J.
and X. Duan, Green Chem., 2014, 16, 1560-1568. T. Muckerman, Y. Zhu and R. R. Adzic, Angew. Chem. Int. Ed.,
204. K. V. Manukyan, A. Cross, S. Rouvimov, J. Miller, A. S. 2012, 51, 6131-6135.
Mukasyan and E. E. Wolf, Appl. Catal., A, 2014, 476, 47-53. 231. W. Ma, R. Ma, C. Wang, J. Liang, X. Liu, K. Zhou and T.
205. J. Hannauer, O. Akdim, U. B. Demirci, C. Geantet, J.-M. Sasaki, ACS Nano, 2015, 9, 1977-1984.
Herrmann, P. Miele and Q. Xu, Energy Environ. Sci., 2011, 4, 232. H. Chen, X. Huang, L.-J. Zhou, G.-D. Li, M. Fan and X. Zou,
3355-3358. ChemCatChem, 2016, 8, 992-1000.

Please
View Article Online
DOI: 10.1039/C6EE02002J
233. B. M. Hunter, W. Hieringer, J. R. Winkler, H. B. Gray and A. 264. M. J. Climent, A. Corma and S. Iborra, Green Chem., 2014,
M. Muller, Energy Environ. Sci., 2016, 9, 1734-1743. 16, 516-547.
234. W. Wang, S. Wang, X. Ma and J. Gong, Chem. Soc. Rev., 265. S. De, B. Saha and R. Luque, Bioresour. Technol., 2015, 178,
2011, 40, 3703-3727. 108-118.

235. G. Centi, E. A. Quadrelli and S. Perathoner, Energy Environ. 266. E. E. Benson, C. P. Kubiak, A. J. Sathrum and J. M. Smieja,
Sci., 2013, 6, 1711-1731. Chem. Soc. Rev., 2009, 38, 89-99.
236. C. van der Giesen, R. Kleijn and G. J. Kramer, Environmental 267. D. M. Alonso, S. G. Wettstein and J. A. Dumesic, Chem. Soc.
Science & Technology, 2014, 48, 7111-7121. Rev., 2012, 41, 8075-8098.
237. Y. Xuecheng, G. Han, Y. Dongjiang, Q. Shilun and Y. 268. P. Gallezot, P. J. Cerino, B. Blanc, G. Flèche and P. Fuertes, J.
Xiangdong, Curr. Org. Chem., 2014, 18, 1335-1345. Catal., 1994, 146, 93-102.
238. X. Chang, T. Wang and J. Gong, Energy Environ. Sci., 2016, 269. A. Shrotri, A. Tanksale, J. N. Beltramini, H. Gurav and S. V.
DOI: 10.1039/C6EE00383D. Chilukuri, Catal. Sci. Technol., 2012, 2, 1852-1858.
239. T. Inui and T. Takeguchi, Catal. Today, 1991, 10, 95-106. 270. J. Pang, A. Wang, M. Zheng, Y. Zhang, Y. Huang, X. Chen and
240. M. A. A. Aziz, A. A. Jalil, S. Triwahyono and A. Ahmad, Green T. Zhang, Green Chem., 2012, 14, 614-617.
Chem., 2015, 17, 2647-2663. 271. G. Liang, L. He, M. Arai and F. Zhao, ChemSusChem, 2014, 7,
241. J. Gao, Q. Liu, F. Gu, B. Liu, Z. Zhong and F. Su, RSC Adv., 1415-1421.
2015, 5, 22759-22776. 272. M.-Y. Zheng, A.-Q. Wang, N. Ji, J.-F. Pang, X.-D. Wang and T.
242. S. Tada and R. Kikuchi, Catal. Sci. Technol., 2015, 5, 3061- Zhang, ChemSusChem, 2010, 3, 63-66.
3070. 273. K. Fabicovicova, O. Malter, M. Lucas and P. Claus, Green
243. M. A. Vannice, J. Catal., 1975, 37, 449-461. Chem., 2014, 16, 3580-3588.
244. M. A. Vannice, J. Catal., 1975, 37, 462-473. 274. A. A. Rosatella, S. P. Simeonov, R. F. M. Frade and C. A. M.
245. G. Zhi, X. Guo, Y. Wang, G. Jin and X. Guo, Catal. Commun., Afonso, Green Chem., 2011, 13, 754-793.
2011, 16, 56-59. 275. L. Hu, L. Lin and S. Liu, Industrial & Engineering Chemistry
246. H. Zhu, R. Razzaq, C. Li, Y. Muhmmad and S. Zhang, AIChE J., Research, 2014, 53, 9969-9978.
2013, 59, 2567-2576. 276. Y.-B. Huang, M.-Y. Chen, L. Yan, Q.-X. Guo and Y. Fu,
247. S. Hwang, U. G. Hong, J. Lee, J. H. Baik, D. J. Koh, H. Lim and ChemSusChem, 2014, 7, 1068-1072.
I. K. Song, Catal. Lett., 2012, 142, 860-868. 277. L. Yu, L. He, J. Chen, J. Zheng, L. Ye, H. Lin and Y. Yuan,
248. S.-H. Kang, J.-H. Ryu, J.-H. Kim, S.-J. Seo, Y.-D. Yoo, P. S. Sai ChemCatChem, 2015, 7, 1701-1707.
Prasad, H.-J. Lim and C.-D. Byun, Korean J. Chem. Eng., 2011, 278. S. Sitthisa, W. An and D. E. Resasco, J. Catal., 2011, 284, 90-
28, 2282-2286. 101.
249. S. Hwang, U. G. Hong, J. Lee, J. G. Seo, J. H. Baik, D. J. Koh, H. 279. Y. Yang, Z. Du, Y. Huang, F. Lu, F. Wang, J. Gao and J. Xu,
Lim and I. K. Song, Journal of Industrial and Engineering Green Chem., 2013, 15, 1932-1940.
Chemistry, 2013, 19, 2016-2021. 280. B. Chen, F. Li, Z. Huang and G. Yuan, Appl. Catal., A, 2015,
250. D. Pandey and G. Deo, J. Mol. Catal. A: Chem., 2014, 382, 500, 23-29.
23-30. 281. F. M. A. Geilen, B. Engendahl, A. Harwardt, W. Marquardt, J.
251. D. Pandey and G. Deo, Journal of Industrial and Engineering Klankermayer and W. Leitner, Angew. Chem. Int. Ed., 2010, 49,
Chemistry, 2016, 33, 99-107. 5510-5514.
252. D. Pandey and G. Deo, Chem. Eng. Commun., 2016, 203, 282. J. Q. Bond, D. M. Alonso, D. Wang, R. M. West and J. A.
372-380. Dumesic, Science, 2010, 327, 1110-1114.
253. J. Ren, X. Qin, J.-Z. Yang, Z.-F. Qin, H.-L. Guo, J.-Y. Lin and Z. 283. Y. Yang, G. Gao, X. Zhang and F. Li, ACS Catal., 2014, 4,
Li, Fuel Process. Technol., 2015, 137, 204-211. 1419-1425.
254. K. Zhao, Z. Li and L. Bian, Frontiers of Chemical Science and 284. I. Obregón, I. Gandarias, N. Miletić, A. Ocio and P. L. Arias,
Engineering, 2016, DOI: 10.1007/s11705-016-1563-5, 1-8. ChemSusChem, 2015, 8, 3483-3488.
255. F. Ocampo, B. Louis, L. Kiwi-Minsker and A.-C. Roger, Appl. 285. M. Saidi, F. Samimi, D. Karimipourfard, T.
Catal., A, 2011, 392, 36-44. Nimmanwudipong, B. C. Gates and M. R. Rahimpour, Energy
256. S. Hwang, J. Lee, U. G. Hong, J. H. Baik, D. J. Koh, H. Lim and Environ. Sci., 2014, 7, 103-129.
I. K. Song, Journal of Industrial and Engineering Chemistry, 286. S. Dutta, K. C. W. Wu and B. Saha, Catal. Sci. Technol., 2014,
2013, 19, 698-703. 4, 3785-3799.
257. W. Zhen, B. Li, G. Lu and J. Ma, RSC Adv., 2014, 4, 16472- 287. J. He, C. Zhao and J. A. Lercher, J. Am. Chem. Soc., 2012,
16479. 134, 20768-20775.
258. K. K. Ramasamy, M. Gray, H. Job and Y. Wang, Chem. Eng. 288. Q. Song, F. Wang and J. Xu, Chem. Commun., 2012, 48,
Sci., 2015, 135, 266-273. 7019-7021.
259. A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107, 289. J. Zhang, H. Asakura, J. van Rijn, J. Yang, P. Duchesne, B.
2411-2502. Zhang, X. Chen, P. Zhang, M. Saeys and N. Yan, Green Chem.,
260. P. Gallezot, Chem. Soc. Rev., 2012, 41, 1538-1558. 2014, 16, 2432-2437.
261. M. Besson, P. Gallezot and C. Pinel, Chem. Rev., 2014, 114, 290. J. Zhang, J. Teo, X. Chen, H. Asakura, T. Tanaka, K. Teramura
1827-1870. and N. Yan, ACS Catal., 2014, 4, 1574-1583.
262. G. W. Huber, S. Iborra and A. Corma, Chem. Rev., 2006, 106, 291. J. Zhang, M. Ibrahim, V. Collière, H. Asakura, T. Tanaka, K.
4044-4098. Teramura, K. Philippot and N. Yan, J. Mol. Catal. A: Chem.,
263. D. M. Alonso, J. Q. Bond and J. A. Dumesic, Green Chem., 2016, DOI: 10.1016/j.molcata.2016.01.014.
2010, 12, 1493-1513. 292. J. Zhang and N. Yan, Particle & Particle Systems
Characterization, 2016, DOI: 10.1002/ppsc.201600005.

View Article Online
DOI: 10.1039/C6EE02002J
293. Y. Nakagawa and K. Tomishige, Catal. Commun., 2010, 12, 322. A. Iglesias-Juez, A. B. Hungría, A. Martínez-Arias, J. A.
154-156. Anderson and M. Fernández-García, Catal. Today, 2009, 143,
294. Y. Wang, S. Sang, W. Zhu, L. Gao and G. Xiao, Chem. Eng. J., 195-202.
2016, 299, 104-111. 323. A. B. Hungría, N. D. Browning, R. P. Erni, M. Fernández-

295. S. G. Jadhav, P. D. Vaidya, B. M. Bhanage and J. B. Joshi, García, J. C. Conesa, J. A. Pérez-Omil and A. Martínez-Arias, J.
Chem. Eng. Res. Des., 2014, 92, 2557-2567. Catal., 2005, 235, 251-261.
296. J. Nerlov and I. Chorkendorff, J. Catal., 1999, 181, 271-279. 324. A. B. Hungría, M. Fernández-García, J. A. Anderson and A.
297. F. Studt, F. Abild-Pedersen, Q. Wu, A. D. Jensen, B. Temel, J.- Martínez-Arias, J. Catal., 2005, 235, 262-271.
D. Grunwaldt and J. K. Nørskov, J. Catal., 2012, 293, 51-60. 325. A. B. Hungría, J. J. Calvino, J. A. Anderson and A. Martínez-
298. F. Zhao, M. Gong, Y. Zhang and J. Li, J. Porous Mater., 2016, Arias, Appl. Catal., B, 2006, 62, 359-368.
DOI: 10.1007/s10934-016-0128-9, 1-8. 326. S. E. Golunski and S. A. Roth, Catal. Today, 1991, 9, 105-112.
299. L. T. M. Nguyen, H. Park, M. Banu, J. Y. Kim, D. H. Youn, G. 327. S. Shan, V. Petkov, L. Yang, J. Luo, P. Joseph, D. Mayzel, B.
Magesh, W. Y. Kim and J. S. Lee, RSC Adv., 2015, 5, 105560- Prasai, L. Wang, M. Engelhard and C.-J. Zhong, J. Am. Chem.
105566. Soc., 2014, 136, 7140-7151.
300. D. Preti, C. Resta, S. Squarcialupi and G. Fachinetti, Angew. 328. Y. Hilli, N. M. Kinnunen, M. Suvanto, A. Savimäki, K. Kallinen
Chem. Int. Ed., 2011, 50, 12551-12554. and T. A. Pakkanen, Appl. Catal., A, 2015, 497, 85-95.
301. S. Wesselbaum, U. Hintermair and W. Leitner, Angew. 329. J. Shen, R. E. Hayes, X. Wu and N. Semagina, ACS Catal.,
Chem. Int. Ed., 2012, 51, 8585-8588. 2015, 5, 2916-2920.
302. L. Wang and R. T. Yang, Energy Environ. Sci., 2008, 1, 268- 330. R. Mu, Q. Fu, H. Xu, H. Zhang, Y. Huang, Z. Jiang, S. Zhang, D.
279. Tan and X. Bao, J. Am. Chem. Soc., 2011, 133, 1978-1986.
303. G. Peng, S. J. Sibener, G. C. Schatz, S. T. Ceyer and M. 331. B. D. Chandler, C. G. Long, J. D. Gilbertson, C. J. Pursell, G.
Mavrikakis, J. Phys. Chem. C, 2012, 116, 3001-3006. Vijayaraghavan and K. J. Stevenson, J. Phys. Chem. C, 2010,
304. G. Peng, S. J. Sibener, G. C. Schatz and M. Mavrikakis, Surf. 114, 11498-11508.
Sci., 2012, 606, 1050-1055. 332. D. Wang and Y. Li, J. Am. Chem. Soc., 2010, 132, 6280-6281.
305. V. R. Stamenkovic, B. S. Mun, M. Arenz, K. J. J. Mayrhofer, C. 333. J. P. Holgado, F. Ternero, V. M. Gonzalez-delaCruz and A.
A. Lucas, G. Wang, P. N. Ross and N. M. Markovic, Nat Mater, Caballero, ACS Catal., 2013, 3, 2169-2180.
2007, 6, 241-247. 334. P. Kratzer, B. Hammer and J. K. Norskov, J. Chem. Phys.,
306. M. K. Debe, Nature, 2012, 486, 43-51. 1996, 105, 5595-5604.
307. J. W. Hong, S. W. Kang, B.-S. Choi, D. Kim, S. B. Lee and S. W. 335. G. Chen, Y. Zhao, G. Fu, P. N. Duchesne, L. Gu, Y. Zheng, X.
Han, ACS Nano, 2012, 6, 2410-2419. Weng, M. Chen, P. Zhang, C.-W. Pao, J.-F. Lee and N. Zheng,
308. Y. Nie, L. Li and Z. Wei, Chem. Soc. Rev., 2015, 44, 2168- Science, 2014, 344, 495-499.
2201. 336. M. A. Keane, ChemCatChem, 2011, 3, 800-821.
309. M. Wang, W. Zhang, J. Wang, D. Wexler, S. D. Poynton, R. C. 337. V. I. Kovalchuk and J. L. d’Itri, Appl. Catal., A, 2004, 271, 13-
T. Slade, H. Liu, B. Winther-Jensen, R. Kerr, D. Shi and J. Chen, 25.
ACS Appl. Mater. Interfaces, 2013, 5, 12708-12715. 338. M. Martin-Martinez, L. M. Gómez-Sainero, M. A. Alvarez-
310. J. Wu, S. Shan, V. Petkov, B. Prasai, H. Cronk, P. Joseph, J. Montero, J. Bedia and J. J. Rodriguez, Appl. Catal., B, 2013,
Luo and C.-J. Zhong, ACS Catal., 2015, 5, 5317-5327. 132–133, 256-265.
311. S. Dresp, F. Luo, R. Schmack, S. Kuhl, M. Gliech and P. 339. N. Lingaiah, M. A. Uddin, A. Muto, T. Iwamoto, Y. Sakata and
Strasser, Energy Environ. Sci., 2016, DOI: 10.1039/C6EE01046F. Y. Kusano, J. Mol. Catal. A: Chem., 2000, 161, 157-162.
312. I. Danaee, M. Jafarian, A. Mirzapoor, F. Gobal and M. G. 340. K. V. Murthy, P. M. Patterson, G. Jacobs, B. H. Davis and M.
Mahjani, Electrochim. Acta, 2010, 55, 2093-2100. A. Keane, J. Catal., 2004, 223, 74-85.
313. N. A. M. Barakat and M. Motlak, Appl. Catal., B, 2014, 154– 341. V. Simagina, V. Likholobov, G. Bergeret, M. T. Gimenez and
155, 221-231. A. Renouprez, Appl. Catal. B: Environ., 2003, 40, 293-304.
314. N. A. M. Barakat, M. Motlak, B.-S. Kim, A. G. El-Deen, S. S. 342. A. Śrębowata, W. Juszczyk, Z. Kaszkur and Z. Karpiński,
Al-Deyab and A. M. Hamza, J. Mol. Catal. A: Chem., 2014, 394, Catal. Today, 2007, 124, 28-35.
177-187. 343. A. Śrębowata, M. Sadowska, W. Juszczyk, Z. Kaszkur, Z.
315. X. Cui, W. Guo, M. Zhou, Y. Yang, Y. Li, P. Xiao, Y. Zhang and Kowalczyk, M. Nowosielska and Z. Karpiński, Catal. Commun.,
X. Zhang, ACS Appl. Mater. Interfaces, 2015, 7, 493-503. 2007, 8, 11-15.
316. I. Danaee, M. Jafarian, F. Forouzandeh, F. Gobal and M. G. 344. G. Yuan, C. Louis, L. Delannoy and M. A. Keane, J. Catal.,
Mahjani, Int. J. Hydrogen Energy, 2008, 33, 4367-4376. 2007, 247, 256-268.
317. R. Ding, J. Liu, J. Jiang, F. Wu, J. Zhu and X. Huang, Catal. Sci. 345. Z. Wu, Z. Zhao and M. Zhang, ChemCatChem, 2010, 2, 1606-
Technol., 2011, 1, 1406-1411. 1614.
318. F. Gao, Y. Wang, Y. Cai and D. W. Goodman, J. Phys. Chem. 346. A. Śrębowata, I. Zielińska, R. Baran, G. Słowik and S. Dzwigaj,
C, 2009, 113, 174-181. Catal. Commun., 2015, 69, 154-160.
319. L. Liu, F. Zhou, L. Wang, X. Qi, F. Shi and Y. Deng, J. Catal., 347. Y. H. Choi and W. Y. Lee, J. Mol. Catal. A: Chem., 2001, 174,
2010, 274, 1-10. 193-204.
320. K. Liu, A. Wang and T. Zhang, ACS Catal., 2012, 2, 1165- 348. S. Mallick, S. Rana and K. Parida, Industrial & Engineering
1178. Chemistry Research, 2011, 50, 12439-12448.
321. K. Persson, A. Ersson, K. Jansson, N. Iverlund and S. Järås, J. 349. A. Śrębowata, R. Baran, S. Casale, I. I. Kamińska, D. Łomot,
Catal., 2005, 231, 139-150. D. Lisovytskiy and S. Dzwigaj, Appl. Catal., B, 2014, 152–153,
317-327.

Please
View Article Online
DOI: 10.1039/C6EE02002J
350. R. Baran, A. Srebowata, S. Casale, D. Łomot and S. Dzwigaj,

Catal. Today, 2014, 226, 134-140.
351. S. L. Pirard, J. G. Mahy, J.-P. Pirard, B. Heinrichs, L. Raskinet
and S. D. Lambert, Microporous Mesoporous Mater., 2015,

209, 197-207.
352. J.-C. Chen, M.-Y. Wey, C.-L. Yeh and Y.-S. Liang, Appl. Catal.,
B, 2004, 48, 25-35.
353. F. Rahmaninejad, V. S. Gavaskar and J. Abbasian, Appl.
Catal., B, 2012, 119–120, 297-303.
354. R. Jin, Y. Liu, Y. Wang, W. Cen, Z. Wu, H. Wang and X. Weng,
Appl. Catal., B, 2014, 148–149, 582-588.

355. P. Gouy-Pailler and Y. Pauleau, Journal of Vacuum Science &
Technology A, 1993, 11, 96-102.
356. H. H. Hwu and J. G. Chen, Chem. Rev., 2005, 105, 185-212.
357. S. Carenco, D. Portehault, C. Boissière, N. Mézailles and C.
Sanchez, Chem. Rev., 2013, 113, 7981-8065.
358. R. Prins and M. E. Bussell, Catal. Lett., 2012, 142, 1413-
1436.
359. S. T. Hunt, M. Milina, A. C. Alba-Rubio, C. H. Hendon, J. A.
Dumesic and Y. Román-Leshkov, Science, 2016, 352, 974-978.
360. S. T. Hunt, T. Nimmanwudipong and Y. Román-Leshkov,
Angew. Chem. Int. Ed., 2014, 53, 5131-5136.

Energy & Environmental Science: Accepted Manuscript

Uploaded by

Copyright:

Available Formats

Energy & Environmental Science: Accepted Manuscript

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Energy & Environmental Science: Accepted Manuscript

Uploaded by

Copyright:

Available Formats

View Article Online

This is an Accepted Manuscript, which has been through the

Accepted Manuscripts are published online shortly after

You can find more information about Accepted Manuscripts in the

Please note that technical editing may introduce minor changes

Energy & Environmental Science Accepted Manuscript

Ni-based bimetallic heterogeneous catalysts for energy and

minimizing waste generation and energy requirements. Metal-

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

compared to conventional and/or presently reported systems.

2. Preparation of bimetallic Ni catalysts

Please do not adjust margins

with similar reduction potential are reduced simultaneously

Energy & Environmental Science Accepted Manuscript

reduce metals with different reduction potential resulting in an

Structural modification largely enhances the capability in

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

surface oxidized to form “SO-IrNi@IrOx” metal oxide core-shell

2.2 Alloyed structure

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

complex since it starts from atomic-level precursors and needs

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

Besides determining the relationship between Eseg and

particular case of bimetallic Ni–Pt system, the segregation of

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

the storage of H2 by both physical and chemical approaches. In

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

described by the Mars–van Krevelen mechanism, where CO2

Incorporation of noble metals such as Pt, Rh can

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

dodecane high reducibility of Ni

precipitation acetaldehyde decomposition and reforming over the

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

suggested that the formation of a uniform FeNi alloy structure

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

Development of noble-metal-free catalyst is of economic

Please do not adjust margins

Energy & Environmental Science Accepted Manuscript

(wt/wt) material sel. (%)

form smaller size

and Ni-Rh NPs and promotion effect of NaOH

effect and promotion effect of ZIF-8