343

12

Active Materials for Photocatalytic Reduction

of Carbon Dioxide
Balasubramanian Viswanathan
National Centre for Catalysis Research, Indian Institute of Technology‐Madras, Chennai, India

12.1 ­Introduction
Solar reforming of hydrocarbons from the photocatalytic reduction of carbon
dioxide is receiving considerable attention worldwide due to both the simplic-
ity of the process and the easy manageability of the system. Carbon dioxide, a
so‐called greenhouse gas, was considered as a waste material until recently, but
nowadays it is regarded as a good C1 source material and thus has become to
be considered to be valuable [1]. The methods of reducing carbon dioxide can
be electrochemical, photochemical, photocatalytic, photoelectrochemical, and
biochemical. Studies on methods for recycling carbon dioxide into useful
products, such as CO, methanol, methane, formic acid, formate, and ethane,
particularly using semiconductors in aqueous suspension systems, have
received considerable attention in recent times. There have been many
attempts to employ various means of activation to reduce carbon dioxide.
These are briefly summarized in Table 12.1.
Among the various activation procedures, only a few have been vigorously
pursued in view of the possibility of commercializing the developed process.
Among these very few possibilities, photocatalytic or photoelectrochemical
processes assume prominence.
It is known that every year, billions of metric tonnes of carbon dioxide (CO2)
are released into the atmosphere. But what if one could recycle all that CO2 and
turn it into something useful, making value‐added chemicals? This desire
mimics how nature converts carbon dioxide into carbohydrate by photosyn-
thesis. Scientific pursuits often try to mimic nature, and carbon dioxide reduc-
tion is another such attempt.

Photocatalytic Functional Materials for Environmental Remediation, First Edition.

Edited by Alagarsamy Pandikumar and Kandasamy Jothivenkatachalam.
© 2019 John Wiley & Sons, Inc. Published 2019 by John Wiley & Sons, Inc.
344 Photocatalytic Functional Materials for Environmental Remediation

Table 12.1  The processes employed to reduce carbon dioxide to useful chemicals [53].

Process Equation

gamma irradiation
1. Radiochemical CO2 HCOOH, HCHO

2. Chemical reduction 2Mg + CO2 → 2MgO + 2C

Sn + 2CO2 → SnO2 + 2CO
2Na + 2CO2 → Na2C2O4

Ce 4 ; T 900 C
3. Thermochemical CO2 CO 1 / 2O2
h
4. Photochemical CO2 CO, HCOOH, HCHO

5. Electrochemical CO2 xe xH eV
CO, HCOOH, COOH 2

bacteria
6. Biochemical CO2 4 H2 CH 4 2H2O

h
7. Biophotochemical CO2 oxoglutaric acid isocitric acid
hv
8. Photoelectrochemical CO2 2e 2H eV , semiconductor
CO H2O

enzyme , eV
9. Bioelectrochemical CO2 oxoglutaric acid methyl viologen
isocitric acid

h , enzyme p InP
10. Biophotoelectrochemical CO2 eV , methyl viologen
HCOOH

By combining electricity, water, and a variety of catalysts, scientists have

showed that they can reduce CO2 into short molecules such as carbon monox-
ide and methane, which they can then combine to form more complex hydro-
carbon fuels such as butane. Researchers think that we could now be on the
cusp of a CO2 recycling revolution, which would capture CO2 from power
plants – and maybe even directly from the atmosphere – and convert it into
value‐added fuels and chemicals. Strictly speaking, the photocatalytic reduc-
tion of carbon dioxide is not a catalytic process. It is an “uphill” process in that
the reaction involves an energy input which may be provided by incident radia-
tion. However, this inconsistency is often ignored and the process is still termed
as “photocatalytic” and is considered as an example of artificial photosynthesis.
In a broader sense, “photocatalytic” may not be very precise from a chemical
point of view, but in this chapter this term is used as we look at the majority of
publications in this area.
In view of the realization that photocatalytic reduction of carbon dioxide is
similar to photosynthesis, even after intense research on the reduction of
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 345

carbon dioxide into value‐added chemicals or fuels, the conversion levels still
remain small (less than millimolar quantities) and thus not are amenable for
commercial exploitation [2–4]. To utilize solar energy, the photosensitizer
should absorb irradiation in the visible or ultraviolet range. Even though this
process has environmental interest, the low turnover rates of the available cur-
rent procedures have prevented wide‐scale industrial adaptation. Lehn and
Ziessel [5], in the 1980s, were the first to initiate the study of catalytic carbon
dioxide reduction using visible light. They observed that Co(I) species pro-
duced in solutions containing CoCl2, 2,2′‐bipyridine (bpy), a tertiary amine,
and a Ru(bpy)3Cl2 photosensitizer was responsible for the reduction of carbon
dioxide. Subsequent to these studies, several catalysts have been reported with
rhodium bipyridyl photosensitizer.
One of the issues for the low yield in the reduction of carbon dioxide is asso-
ciated with the high value of the reduction potential for the initial electron
transfer from the catalyst surface. That is, for the following reduction reaction

CO2 aq e CO2 aq

the reduction potential value is −2.14 V versus the saturated calomel electrode
(SCE) [2], even though the subsequent electron transfers may be favorable, i.e.
have a more negative or positive value reduction potential with respect to the
conduction band minimum of most of the semiconductor materials, a situation
favorable for the feasibility of the reaction. Rapid reduction thus requires an
over‐potential of up to 0.6 V due to the kinetic restrictions imposed in convert-
ing the linear neutral molecule to the bent anion moiety.
The question to be answered at this stage is how this thermodynamic limita-
tion is overcome in the product formation in photocatalytic reduction of car-
bon dioxide? An answer may be that photon‐assisted multi‐electron transfer is
possible under photocatalytic reduction of carbon dioxide in aqueous solu-
tions. However, as this complex process has to involve various reactions and
each of the steps involved depends on the preference of the product to be
obtained, the reduction of carbon dioxide is governed by the reduction poten-
tial values for all of these steps. A listing of reduction potential values for the
photocatalytic reduction of carbon dioxide to various products in aqueous
media is given in Table 12.2 [6]. This listing shows how to tune the ultimate
product obtained in the photocatalytic reduction of carbon dioxide.

12.2 ­CO2 Photoreduction – Essentials
The carbon dioxide photoreduction reaction in aqueous media was first reported
by Inoue et al. in 1979 [7], where CO2 was photo‐reduced into organic materials,
such as formaldehyde (HCHO), formic acid (HCOOH), methanol (CH3OH),
346 Photocatalytic Functional Materials for Environmental Remediation

Table 12.2  Reduction potential values for carbon dioxide. The value for hydrogen

production from water is included for comparative purposes and its relevance in CO2
reduction.

Reaction Eredox (eV)

CO2 + e− → CO2− ≥−1.9

+ −
CO2 + 2H  + 2e  → HCOOH −0.61
CO2 + 2H2O + 2e− → HCOOH_ + OH− −1.491
CO2 + 2H+ + 2e− → CO + H2O −0.53
CO2 + 2H2O + 2e− → CO + 2OH− −1.347
+ −
2CO2 + 2H  + 2e  → H2C2O4 −0.913
2CO2 + 2e− → C2O42− −1.003
+ −
CO2 + 4H  + 4e  → C + 2H2O −0.20
CO2 + 4H+ + 4e− → HCHO + H2O −0.48
CO2 + 3H2O + 4e− → HCHO + 4OH− −1.311
CO2 + 2H2O + 4e− → C + 4OH− −1.040
+ −
CO2 + 6H  + 6e  → CH3OH + H2O −0.38
CO2 + 5H2O + 4e− → CH3OH + 6H2O −1.225
+ −
CO2 + 8H  + 8e  → CH4 + 2H2O −0.24
CO2 + 6H2O + 8e− → CH4 + 8OH− −1.072
+ −
2CO2 + 12H  + 12e  → C2H4 + 4H2O −0.349
2CO2 + 8H2O + 12e− → C2H4 + 12OH− −1.177
2CO2 + 12H+ +12e− → C2H5OH + 3H2O −0.329
2CO2 + 9H2O + 12e− → C2H5OH + 12 OH− −1.157
2CO2 + 14H+ + 14e− → C2H6 + 4H2O −0.270
3CO2 + 18H+ + 18e− → C3H7OH + H2O −0.310
2H+ + 2e− → H2 −0.42
3CO2 + 18H+ + 18e− → CH3CH(OH)CH3 + 5H2O −0.30
+ −
2CO2 + 10H  + 10e  → CH3CHO + 3H2O −0.36
3CO2 + 16H+ + 16e− → CH3CH2CHO + 5H2O −0.32
+ −
3CO2 + 16H  + 16e  → CH3COCH3 + 5H2O −0.31
2CO2 + 8H+ + 8e− → CH3COOH + 2H2O −0.31

Source: Values collected from Ref. [6].

and hydrocarbons (such as methane, CH4, and ethane, C2H6) by using semicon-
ductor photocatalysts. When the semiconductor is exposed to irradiation, it
absorbs appropriate photon energy (hν) corresponding to the bandgap or higher.
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 347

Then, if the absorbed photon energy is sufficient to overcome the bandgap of the
semiconductor (the forbidden or void energy region that extends from the top of
the filled valance band to the bottom of the vacant conduction band) the elec-
trons (e−) in the valence band (VB) can be excited and transferred to the conduc-
tion band (CB), leaving positively charged holes (h+) in the VB. These
photo‐generated electron and hole pairs (e−/h+) may move to the surface of the
semiconductor and react with the adsorbed species (e.g. CO2, H2O) to initiate
the CO2 photoreduction.
It should be realized that the photogeneration of electron and hole pairs is a
reversible process, and these electron and hole pairs may undergo bulk or sur-
face recombination, emitting photon and heat energy. Such a recombination
process can inhibit electron and hole pairs participating in surface reactions
for CO2 photoreduction. Therefore, a decrease of the electron and hole recom-
bination rate can increase the lifetime of these charge carriers and significantly
improve the efficiency of CO2 photoreduction. A pictorial representation of
the photocatalytic process is shown in Figure 12.1.
It can be seen that CO2 photoreduction with water requires both multi‐­
electron transfer reactions and water oxidation and they have to occur simul-
taneously. The band‐edge energy positions of the VB and CB of the

CB –
hν
on
ce n ati hν
rfa bi VB +
Su com – + +
re

3
– + D+
2

+ Oxidation
1 4 3
4
D

–++
n

–++
tio
ina

A– – Volume
co ce
mb

recombination
re urfa
S

Reduction
A

Figure 12.1  Schematic diagram of photoexcitation and electron‐transfer processes in a

semiconductor. Source: Adapted and reproduced from Refs. [21, 74]. The numbers 1, 2, 3,
and 4 inside circles denote the migration of charge carriers inside the semiconductor.
348 Photocatalytic Functional Materials for Environmental Remediation

semiconductor are critical to determine whether these reactions can be initi-

ated. The band‐edge position of the VB must be sufficiently positive to allow
the photo‐generated hole to initiate the necessary oxidation (e.g. more positive
than the redox potential of H2O decomposition). Meanwhile, the band‐edge
position of the CB must be sufficiently negative to allow the photo‐generated
electron to participate in the reduction reactions (e.g. more negative than the
redox potential of CO2, for example reduction into CH4, −0.24 V). Moreover,
based on the redox potentials, CO2 photoreduction may be more favorable to
be a multi‐electronic process which yields the final products, such as methane,
methanol, formaldehyde, formic acid, carbon monoide or others, through dif-
ferent intermediates. The various reduction processes that can take place
through the photocatalytic reduction of carbon dioxide are already listed in
Table 12.2. Depending on the nature of the semiconductor, a specific reduction
product can be selectively formed on a given semiconductor.
Although low yields in the photocatalytic reduction of carbon dioxide are
observed, encouraging laboratory experimental results have been obtained in
both gas and liquid phases. Semiconductor‐based systems, metal–organic
frameworks (MOFs), and composites involving C3N4 and MoS2 have been
examined for the photocatalytic reduction of carbon dioxide. Semiconductor
heterostructures, containing bimetallic alloys and chemical modification of
oxides with anion substitution (N3− and F− in place of O2−), have also been tried
as possible catalytic candidates.

12.3 ­Heterogeneous Photocatalytic Reduction

of Carbon Dioxide with Water
In the photocatalytic reduction of carbon dioxide with water, both the photore-
duction of carbon dioxide and the photooxidation of water take place simulta-
neously under sunlight irradiation, employing a photocatalyst. Since a variety of
reaction conditions affect the reaction, predicting the product distribution on a
catalyst system is often a difficult proposition, though it is feasible [6].
Photocatalytic reduction of carbon dioxide is one of the pathways involved in
the carbon dioxide conversion process and has been receiving considerable
attention from the scientific community in the last few decades. The mecha-
nism of carbon dioxide reduction is not still clear and the information available
is not sufficient for developing it into large‐scale commercially viable applica-
tions, possibly because of the innumerable hurdles associated with the reduc-
tion process. The reductive photocatalytic conversion of CO2 involves all the
redox reactions occurring at the interface of the semiconductor, such as water
splitting, hydrogen evolution, oxygen evolution, photooxidation reactions, and
reactions of radical intermediates. The overall product yield is highly depend-
ent on the extent of these competing reactions [8].
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 349

The work by Lehn et  al. showed the selective CO2 reduction into CO by
using Re(I) diimine complexes [5, 9]. Subsequently, metal complexes in photo-
catalysis have been studied for both CO2 reduction [10–13] and H2O oxidation
[14–16]. CO2 is reduced to form CO with homogeneous photocatalysts, such
as Re complexes; however, efficiency of the process increased in the presence
of electron donors, such as triethanolamine [17, 18]. However, CO2 reduction
and H2O oxidation processes require distinct and possibly separate reaction
conditions. As a result, carrying out these reactions simultaneously using a
metal complex catalyst in a single system is a difficult task. Reverse oxidation
of organic products generated from the reduction of CO2 and the reverse
reduction of O2 generated from the oxidation of H2O may terminate the conti-
nuity of the reaction. Catalysis by metal complexes will not be further consid-
ered here, as the scope of this chapter is only to examine the heterogeneous
photocatalytic reduction of carbon dioxide by semiconducting materials. It
could be questioned as to why one should restrict consideration only to semi-
conducting materials, especially for a globally important reaction such as car-
bon dioxide reduction. A limited answer to this point is that the literature is
vast if one were to consider all the information, and also there appears to be
vast choice of materials among the literature. Any successful direction in the
literature will go a long way in attempting to commercialize this process.
The reduction potentials for the proton‐coupled electron transfer (PCET)
reactions of carbon dioxide are within the range of −0.7 to −0.2 V (see
Table 12.2) and are close to the reduction potential of water (−0.414 V at pH 7).
Gas phase carbon dioxide is a linear molecule; when it is adsorbed on the cata-
lyst surface the bond angle is reduced from 180° and thus becomes susceptible
for reduction. The values of the reduction potentials of carbon dioxide are
given in Table 12.2 and generally refer to multi‐electron/proton transfer reac-
tions as compared to water decomposition. Water decomposition is a two‐
electron transfer reaction and hence in the liquid phase hydrogen generation
from water can be facile compared to the reduction of carbon dioxide. This
may account for the low yields obtained in the experiments on the reduction of
carbon dioxide in the presence of water decomposition. However, the solubil-
ity of carbon dioxide in water is small, being of the order of ~5.4–6 × 10−4 mol
fraction of carbon dioxide [19] in liquid phase at around atmospheric pressure.
The solubility of CO2 in water can be improved by the addition of substances
such as NaOH, NaHCO3, or Na2CO3.
It is normal to use sacrificial reagents to consume the generated holes. The
addition of a sacrificial reagent to the reaction mixture enhances photocata-
lytic reduction. For example, methanol is used as a sacrificial hole scavenger.
This implies that some of the CO2 reduction products are formed through the
action of holes and not the action of electrons. The presence of organic adsor-
bents (CH3CO2H, CH3OH, HCO2H) on the surface of the photocatalyst plays
an important role in the photoreduction of CO2. The presence of acetic acid on
350 Photocatalytic Functional Materials for Environmental Remediation

the photocatalyst surface leads to the formation of CH4. This can occur by the
conversion of acetic acid to CH4 via the photo‐Kolbe reaction.
It has been already stated that the deviation of the bond angle from 180° is
essential in activating carbon dioxide and facilitates its reduction. This implies
that the adsorption sites should be such that the bond angle of linear carbon
dioxide is reduced from the value of 180°. One such visualization has been
made in the literature and is shown in Figure  12.2. This type of site may be
present on stepped surfaces of semiconductors. Other geometrical arrange-
ments are possible for the adsorption and activation of carbon dioxide [20].
Fujishima, Honda, and their co‐workers reported the photocatalytic reduc-
tion of CO2 to organic compounds, such as HCOOH, CH4, CH3OH, and
HCHO, in the presence of semiconductor photocatalysts such as TiO2, ZnO,
CdS, SiC, and WO3 [7]. Heterogeneous semiconductor compounds, including
metal oxides, oxynitrides, sulfides, and phosphides, had been investigated for
this purpose [21, 22].
The photocatalytic CO2 reduction is a useful method since no additional
energy is needed and there is little negative effect on the environment. The use
of cheap and abundant sunlight to convert a greenhouse gas into other carbon‐
containing products is also an ideal approach. Some of the typical semiconduc-
tors employed for the study of this reaction are assembled in Table 12.3.

12.4 ­Nanomaterials and New Combinations

of Materials for Carbon Dioxide Reduction
In this section, a brief description of nanomaterials is given and we look at how
useful they are for the photocatalytic reduction of carbon dioxide. One‐­
dimensional (1D) nanomaterials with different morphologies and high surface
areas have been shown to facilitate electron transport and also to minimize the
loss of charge carriers [23]. Among the 1D nanostructures, highly ordered

Bent CO2+
CO

HCHO
Fuels
CH3OH

Figure 12.2  One adsorption geometry for carbon dioxide that facilitates its reduction.
Source: Reproduced from Ref. [75].
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 351

Table 12.3  Typical semiconductors used for the photoreduction of carbon dioxide.

Bandgap
Semiconductor (eV) Description Ref.

TiO2 3.2 UV, λ = 365 nm, λ = 254 nm, methane, CO, and [54–58]

other products
Graphene‐TiO2 methanol and formic acid, under light of 365 nm, [59]
can reach 160 and 150 μmol g−1
ZnO 3.44 CO formation rate (3.814 μmol g−1h−1) in [60, 61]
comparison with ZnO microspheres and ZnO
microflowers (3.357 and 1.627 Μ mol g−1 h−1,
respectively)
CdS 2.42 methanol nearly 40 μmol g−1 h−1; CdS on MMT, the [61, 62]
product yield H2 > CH4 > CO
Bi2O3 2.8 methanol nearly 60 μmol g−1h−1 [62]
SiC 3.0 HCOOH, HCHO, and CH3OH are the main [7]
products
u–g–C3N4 2.75 better performance in photocatalytic carbon [61, 63]
(Cu loaded) dioxide reduction, methane is major product
ZrO2 5.0 rates of gas evolutions were 19.5 μmol h−1 of H2, [64, 65]
10.8 μmol h−1 of O2, and 2.5 μmol h−1 of CO
Ta2O5‐rG high methanol yields [61]
ZnS 3.91 CO2 reduced to HCOOH, ZnS–MMT [8, 61,
(montmorillonite) nanocomposite exhibited 66]
5–6‐fold higher efficiency of photocatalytic CO2
reduction
GaN 3.4 the reduction of CO2 to CO dominates on as‐grown [65]
GaN nanowires under ultraviolet light irradiation
GaP 2.16 HCOOH, HCHO, and CH3OH are the reported [8]
products
GaAs 1.43 spontaneously produce CH3OH, even under [67]
conditions of no net current
PbS 0.37 The PbS QDs enhance CO2 photoreduction rates [68]
with TiO2 by a factor of ~5 in comparison to
unsensitized photocatalysts
SrTiO3 3.3 7 μmol h−1 methanol and less than 1 μmol h−1 [69]
formaldehye
LiNbO3 4.0 lithium niobate achieved unexpectedly high [70]
conversion of CO2 to products despite the low
levels of bandgap light available.
(Continued)
352 Photocatalytic Functional Materials for Environmental Remediation

Table 12.3  (Continued)

Bandgap
Semiconductor (eV) Description Ref.

MoS2 1.23 compared with the pristine Bi2S3 or MoS2, the [71]
as‐synthesized D‐Bi2S3@MoS2 composite has
exhibited much higher adsorption behavior and
photocatalytic activity under visible light irradiation
BaLa4Ti4O15q ~4 and 5 H2: 10 μmol h−1, O2: 7 μmol h−1, CO: 4.3 μmol h−1, [68]
HCOOH: 0.3 μmol h−1
KTaO3 ~3.5 reduce CO2 to CO and oxidize water to O2 [72]
−1
WO3 and 2.8 around 5 μmol h methanol [61, 69]
graphene‐WO3

vertical TiO2 nanotube arrays (NTAs) have shown significant photocatalytic

activity of CO2 reduction [24, 25]. However, maintaining the long‐time stabil-
ity and high activity of the catalyst, especially the co‐catalyst, is still a great
challenge. Noble metal Pt nanoparticles (NPs) are easily poisoned by CO dur-
ing the catalytic process [26] and for non‐noble metal NPs, changes in the
surface states [27] are the main reason for the co‐catalyst deactivation.
Efficient photocatalytic conversion of CO2 into CO and hydrocarbons by
hydrous hydrazine (N2H4·2H2O) is shown on SrTiO3/TiO2 coaxial NTAs
loaded with Au/Cu bimetallic alloy. The synergetic catalytic effect of the Au/
Cu alloy nanoparticles and the facile electron transfer in the SrTiO3/TiO2
coaxial nanoarchitecture are the reasons for the efficiency. The reduction
products are identified by IR spectroscopy [28]. By varying the fraction of one
component in this bimetallic alloy system, a Au3Cu@STO3/TiO2 NTA has
been found that is the most reactive photocatalyst in this family to generate
hydrocarbons from diluted CO2 with N2H4·2H2O acting as the hydrogen source
and electron donor and also providing a reductive atmosphere for maintaining
the alloying system.
Plasmonic photocatalysts have become popular in recent times [29–31].
This is because nano metals such as Au, Ag, and Pt exhibit strong absorption
in the UV‐vis region due to their surface plasmon resonance (SPR) [32]. SPR
means the collective oscillations of conduction band electrons in a metal par-
ticle and it is driven by the electromagnetic field of incident light [33, 34].
Dispersing metal nanoparticles (10–100 nm) on a semiconductor photocata-
lyst shows significant enhancement in photocatalytic activity under UV and
visible light irradiation due to SPR.
The surface plasmonic resonance frequency can be tuned by manipulating
the size, shape, and material of the nanoparticles. Noble metal nanoparticles
are a combination of surface area and active sites. In the photocatalytic CO2
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 353

reduction with water, it has been reported that depositing Au nanoparticles on

TiO2 results in plasmonic enhancement (532 nm) of a 24‐fold enhanced photo-
catalytic activity. The synthesis, characteristics, and application of plasmonic
photocatalysts in CO2 reduction with H2O, where CH4 and CO are produced
under visible light irradiation (>400 nm wavelength) has also been reported.
The comparative photocatalytic activities toward the CO2 reduction of a dif-
ferent photocatalyst in the presence of water under visible light were evaluated
by the quantity of carbon‐containing products. The results show the increas-
ing amount of CH4 and CO formation with time under visible light.
There are various ways, as shown above, that carbon dioxide can be reduced
to value‐added chemicals and fuels. In all these attempts, it is the selection of
materials to promote the reaction in the desired direction that appears to be
both critical and challenging [35]. Many developments have been carried out in
the photocatalytic reduction of carbon dioxide. Recently, it has been shown that
even infrared radiation can be effectively utilized, using an oxygen‐­deficient
WO3 system to reduce CO2 [36]. The pictorial representation of this process
that has been proposed [36] is reproduced in Figure 12.3. These developments
show that though the conversion levels of carbon dioxide is low at present, it is
certain that, in the near future, the conversion of carbon dioxide into value‐
added chemicals and fuels will become a commercially viable process. However,
this exploitation requires that some fundamental principles are fully understood
and the material selection is made on a rational basis.
Only a few of the variations in the choice of materials or combinations will be
considered in this section. In a recent publication [37], the photosynthetic

–1.0 CB
Potential vs. NHE (V) at pH = 0

0.0 CO/CO2

IB
1.0
O2/H2O

2.0

VB
3.0
Oxygen-deficient
4.0 WO3 atomic layers
WO3 atomic layers

Figure 12.3  Energy level diagram of layers and oxygen‐deficient WO3 atomic layers which
can be used with the infrared radiation of solar radiation for the photocatalytic reduction of
carbon dioxide. Source: Reproduced from Ref. [36].
354 Photocatalytic Functional Materials for Environmental Remediation

conversion of carbon dioxide to hydrocarbons (methane and other higher hydro-

carbons) on Pd/TiO2 in conjunction with Nafion has been reported. The conver-
sion efficiency of this process is, as usual, not high. Since the one‐electron
reduction of CO2 (the initial step in the reduction process) requires high poten-
tials of the order of 2 V (as pointed out earlier in this chapter), a favorable path-
way is to reduce CO2 though PCETs. The role of the Nafion layer is to enhance
the local proton activity within the layer to facilitate PCET reactions, to stabilize
intermediates, and to inhibit the re‐oxidation of the CO2 reduction products. It
is observed that Nf/Pd–TiO2 is more active than Pd–TiO2 for the photoproduc-
tion of hydrocarbons (e.g. methane, ethane, and propane). The conceptual design
of the catalyst system employed in this study is shown in Figure 12.4 [37].
In the light of these results, the following points are presented for conceptual
analysis and possible adaptation.

i) Is a direct proton source desirable (rather than the protons coming from
the decomposition of water), so that the reduction of CO2 is facilitated?
ii) It is essential that the species employed as a proton source should not
undergo any electrochemical reaction within the potential range for the
CO2 reduction reaction.
iii) The reactivity of the proton should be as high as that in Nafion (very nearly
a bare proton), where the proton is in a highly electronegative environment
of fluorine atoms.
iv) The available protons should be capable of reacting with carbon dioxide
directly, promoted by the light absorbed by semiconductors (TiO2), and
the reduction reaction should be carried out on some reactive metal sites.
This possibly means the photon absorption and reactive sites may be
distinguishable.

CH4
Nafion layer CO2

H+ H+ F2 F2
C C
CO2 C x CF y
H+ CH4 F2 F2 O
O CF2 O C S
Pd H+ CF z C
F2 OH
H2O O
H+ CF3

e– O2
h+
TiO2 H+

Figure 12.4  Pd/TiO2 on Nafion catalyst system for the photochemical reduction of carbon
dioxide. Source: Reproduced from Ref. [37] with permission from the Royal Society of
Chemistry.
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 355

Considering these aspects, and also based on argumentative considerations,

it is possible that alternative PCET catalyst support systems that may sustain
more acidic protons can be tried, such as heteropoly acids or super acids (such
as sulfated zirconia).
Another opinion in material selection in recent times is the hybrid perovs-
kites (CH3NH3PbI3) as a possible alternative for solar cell and photocatalytic
applications. These materials have been shown to be nearly two times more
active (24%) as compared to kesterite (Cu2ZnSn(S,Se)4) materials [38], while
the number of publications about hybrid perovskites is nearly three times the
number of those on kesterite. It may be presumed that kesterite may become
one of the possible alternative materials for the photocatalytic reduction of
carbon dioxide in the near future. In the next decade, there is the possibility
that the efficiency of these materials may improve and thus pave the way for
the commercialization of this process.
Many more variations are being tried to increase the useful photon energy
range into the visible and near infrared, as well as to increase the efficiency of
the process. These attempts are continuing exercises in research, and will con-
tinue to be, until a viable and efficient system has been identified.

12.5 ­Selection of Materials
It is realized that in any successful attempt to make this process viable com-
mercially, the selection of photocatalytic material is an important requirement.
There have been various attempts in this direction in the past based on various
methodologies. However, even today, the search continues to identify a mate-
rial which will be able to provide the efficiency required. In this connection it
has been pointed out earlier that the positions of the conduction band mini-
mum and valence band maximum of the semiconductor represent the reduc-
tion and oxidation ability of the system. A compilation of the known
semiconductors and their characteristics is attempted in Table 12.4. The data
presented in this table may be useful in order to select a semiconductor mate-
rial based on the logistics of the process instead of on a trial and error basis.
This is an important aspect, since the selection of suitable materials is the
immediate need for making this process commercially viable and environmen-
tally acceptable. Note that in the two “Band edge” columns in Table 12.4, the
figures in brackets are the pH value at which the band edges values are reported
if this isn’t pH 7. The values given in Table 12.4 can be used to identify appro-
priate and suitable semiconductor materials for the simultaneous photocata-
lytic reduction of carbon dioxide and photodecomposition of water.
356 Photocatalytic Functional Materials for Environmental Remediation

Table 12.4  List of semiconductors with data on bandgap, valence band maximum,

and conduction band minimum.

Eg CB edge at VB edge at
Name Formula (eV) pH = 7 (eV) pH = 7 (eV) λ (nm)

aluminum oxide Al2O3 7.1 −3.6 3.5 175

antimony oxide Sb2O3 3.00 0.32 3.32 413
antimony sulfide Sb2S3 1.72 0.22 1.94
arsenic sulfide As2S3 2.50 0.08 2.58 496
barium titanate BaTiO3 3.30 0.08 3.38 376
barium titanate BaTiO3 3.30 −3.4 0.1 376
bismuth niobium Bi4NbO8Cl 2.39 −2.11 0.28 519
oxychloride
bismuth oxide Bi2O3 2.80 0.33 3.13 443
bismuth oxychloride BiOCl 3.42 −1.5 1.92 363
bismuth vanadate BiVO4 2.4 −0.3 2.1 517
boron carbon nitride h‐BCN 2.82 −1.59 1.23 440
cadmium ferrite CdFe2O4 2.30 0.18 2.48 539
cadmium oxide CdO 2.20 0.11 2.31 564
cadmium selenide CdSe 2.0 1.2 3.2 620
cadmium sulfide CdS 2.4 −0.6 1.8 517
cadmium sulfide CdS 2.40 −0.52 1.88 517
cerium oxide Ce2O3 2.40 −0.50 1.9 517
chromium oxide Cr2O3 3.50 −0.57 2.93 354
cobalt oxide CoO 2.01 −0.11 1.9 617
cobalt titanate CoTiO3 2.25 0.14 2.39 551
copper iron sulfide CuFeS2 0.35 0.47 0.82 —
copper oxide CuO 1.70 0.46 2.16 729
copper(II) oxide CuO 1.35 4.07 5.42 1032
copper titanate CuTiO3 3.0 −0.18 2.81 413
copper titanate CuTiO3 2.99 −0.18 2.81 415
cuprous oxide Cu2O 1.9 −1.30 0.60 620
cuprous oxide Cu2O 2.20 −0.28 1.92 564
FAPbI3 FAPbI3 1.5 −5.42 −3.92 827
ferric oxide Fe2O3 2.2 0.13 2.33 560
ferric oxide Fe2O3 2.20 0.28 2.48 564
ferrous ferric oxide Fe3O4 0.10 1.23 1.33 —
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 357

Table 12.4  (Continued)

Eg CB edge at VB edge at
Name Formula (eV) pH = 7 (eV) pH = 7 (eV) λ (nm)

ferrous sulfide FeS 0.10 0.47 0.57 —

gallium oxide Ga2O3 4.80 −1.54 3.26 258
indium oxide In2O3 2.9 −3.88 (at pH −0.98 428
8.64)
indium oxide In2O3 2.80 −0.62 2.18 443
indium sulfide In2S3 2.00 −0.80 1.20 620
indium tantalum oxide InTaO4 2.6 −0.75 1.85 477
iron disulfide FeS2 0.95 0.42 1.37 —
iron titanate FeTiO3 2.80 −0.21 2.59 443
iron(II) oxide FeO 2.40 −0.17 2.23 517
lanthanum oxide La2O3 5.50 −1.97 3.53 227
lead copper antimony PbCuSbS3 1.50 0.11 1.61
sulfide
lead oxide PbO 2.80 −0.48 2.32 443
lead sulfide PbS 0.37 0.24 0.61
lead titanate PbTiO3 2.75 −2.75 0.0 451
lithium niobate LiNbO3 3.50 −0.73 2.77 354
lithium tantalate LiTaO3 4.00 −0.95 3.05 310
magnesium oxide MgO 7.3 −3.0 4.3 159
magnesium titanate MgTiO3 3.70 −0.75 2.95 335
manganese dioxide MnO2 0.25 1.33 1.58
manganese disulfide MnS2 0.50 0.49 0.99 —
manganese oxide MnO 3.60 −1.01 2.59 344
manganese(II) oxide MnO 3.6 −3.49 0.11 345
(at pH 8.61)
manganese sulfide MnS 3.00 −1.19 1.81 413
manganese titanate MnTiO3 3.10 −0.46 2.64 400
mercury oxide HgO 1.90 0.63 2.53 653
methyl lead bromide MaPbBr3 2.3 −5.68 −3.38 539
methyl lead chloride MAPbCl3 3.09 −2.54 0.55 400
methyl lead iodide MAPbI3 1.55 −5.43 −3.88 800
methyl tin iodide MASnI3 1.3 −5.47 −4.17 954
molybdenum sulfide MoS2 1.17 0.23 1.40
(Continued)
358 Photocatalytic Functional Materials for Environmental Remediation

Table 12.4  (Continued)

Eg CB edge at VB edge at
Name Formula (eV) pH = 7 (eV) pH = 7 (eV) λ (nm)

nickel disulfide NiS2 0.30 0.89 1.19

nickel oxide NiO 4.3 −0.5 3.8 285
nickel oxide NiO 3.50 −0.50 3.0 413
nickel sulfide NiS 0.40 0.53 0.97
nickel titanate NiTiO3 2.18 0.20 2.38 569
nickel titanate NiTiO3 2.18 0.20 2.38 569
niobium oxide Nb2O5 3.40 0.09 3.49 365
niobium pentoxide Nb2O5 3.40 0.09 3.49 365
palladium oxide PdO 1.00 0.79 1.79 1240
platinum sulfide PtS2 0.95 1.03 1.98
potassium niobate KNbO3 3.30 −0.86 2.44 376
potassium tantalate KTaO3 3.50 −0.93 2.57 354
rhodium sulfide Rh2S3 1.50 0.11 1.61
ruthenium sulfide RuS2 1.38 0.39 1.77
silicon Si 1.1 −0.6 0.5 1125
silicon carbide SiC 3.0 −1.5 1.5 415
silver oxide Ag2O 1.20 0.19 1.49 1033
silver sulfide Ag2S 0.92 0.0 0.92 1348
strontium titanate SrTiO3 3.4 −3.24 0.16 364
(at pH 8.6)
strontium titanate SrTiO3 3.40 −1.26 2.14 365
tantalum oxide Ta2O3 4.00 −0.17 3.83 310
tin dioxide SnO2 3.50 0.0 3.5 354
tin oxide SnO2 3.5 −4.5 (at pH 4.3) −1.0 354
tin oxide SnO 4.20 −0.91 3.29 295
tin sulfide SnS 1.01 0.16 1.17
titanium oxide (anatase) TiO2 3.23 −0.29 2.94 384
titanium oxide (rutile) TiO2 3.02 −0.52 2.5 410
titanium sulfide TiS2 0.70 0.26 0.96
tungsten oxide WO3 2.6 0 2.5–2.8 495–
442
tungsten oxide WO3 2.70 0.74 3.44 459
tungsten selenide WSe2 1.4 −0.25 1.15 1032
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 359

Table 12.4  (Continued)

Eg CB edge at VB edge at
Name Formula (eV) pH = 7 (eV) pH = 7 (eV) λ (nm)

tungsten sulfide WS2 1.35 0.36 1.71

vanadium pentoxide V2O5 2.7 −4.7 (at pH −2.0 458
6.54)
vanadium pentoxide V2O5 2.80 0.20 3.0 443
zinc indium sulfide Zn3In2S6 2.81 −0.91 1.90 441
zinc oxide ZnO 3.2 −0.31 2.91 387
zinc oxide ZnO 3.20 −0.31 2.89 388
zinc sulfide ZnS 3.7 −3.46 (at pH 0.24 335
1.7)
zinc sulfide ZnS 3.60 −1.04 2.56 344
zinc titanate ZnTiO3 3.07 −0.23 2.84 404
zirconium dioxide ZrO2 5.00 −1.09 3.9 248
zirconium sulfide ZrS2 1.82 −0.21 1.61 681

Source: data collected from literature, especially from Refs. [4, 73], among others.

12.6 ­Material Modifications for Improving Efficiency

According to the given description of the mechanism of carbon dioxide photore-
duction, it can be stated that the selection of the semiconductor photocatalyst is
the key for the success of this process. The semiconductor photocatalyst suitable
for carbon dioxide photoreduction should not only provide appropriate valence
bands and conduction bands with suitable energy positions that can induce
water decomposition and carbon dioxide reduction reactions simultaneously,
but also have the properties of chemical stability and low cost [39]. According to
the research reported so far, all these factors have been found in only one mate-
rial, which is titanium dioxide (TiO2). This is the most widely used semiconduc-
tor, and it has been claimed to be one of the best options to act as a photocatalyst
for CO2 photoreduction [40, 41]. Two common crystalline structures of TiO2,
rutile and anatase, are commonly used in photocatalysis, with anatase showing a
higher photocatalytic activity. This may be because of the relatively larger band-
gap of anatase (3.2 eV) than that of rutile (3.0 eV), which allows anatase to pro-
vide more sufficiently negative and positive redox potentials in CB and VB
during photocatalysis. Hence, most of the reports on TiO2 have shown that the
anatase form successfully initiates CO2 photoreduction. However, there are
aspects of anatase which have to be improved before it can be exploited for use
in a commercial process for the conversion of carbon dioxide.
360 Photocatalytic Functional Materials for Environmental Remediation

However, there are still disadvantages hindering the use of TiO2 as an effec-
tive catalyst for CO2 photoreduction. Firstly, the efficiency of CO2 photoreduc-
tion using TiO2 is still too low for practical applications. It can be seen that
even the best work could only achieve a CO2 conversion rate at around
26 μmol g−1 h−1 [40]. Such reaction efficiency is obviously too low for practical
applications and, therefore, it is necessary to improve the activity of TiO2 or
find alternative materials for carbon dioxide photoreduction.
Yet another problem when using TiO2 is its relatively large bandgap (3.2 eV)
that can only be effectively excited by ultraviolet (UV) light. As only small frac-
tion of the solar spectrum is within the UV region (not higher than 3%), there
is a need to modify the light absorption range of TiO2 to efficiently utilize solar
energy for CO2 photoreduction. One of the most widely used methods to
improve the activity of TiO2 for CO2 photoreduction is by modifying TiO2 with
a metal. This is because the added metal is able to act as a trap of the photo‐
generated charge carriers in order to suppress the electron/hole recombination
rate and improve the activity of TiO2.
Metal loading on or in a semiconductor can either create alternate adsorption
sites or alter the electronic energy levels, thus facilitating the electron‐transfer
reactions. (Metal can be loaded on the surface and not incorporated into the
lattice, or it can be loaded in the lattice, in which case the doped metal can give
rise to additional allowed energy levels in the so‐called forbidden gap or can
alter the Fermi level of the semiconductor by charge injection into the host lat-
tice.) Thus, metal loading on to a semiconductor may function as electron traps,
thereby suppressing electron/hole recombination rate and thus promoting the
desired reaction. This process increases the possibility of these charge carriers
reacting with the adsorbed species on the metallic sites that are loaded on the
semiconductor photocatalyst. If the loaded metal undergoes oxidation due to
calcination, then what one gets is a coupled/composite semiconductor system
which also experiences Fermi‐level equalization due to intimate contact. When
the added metal is doped into the lattice of the semiconductor (TiO2), the dop-
ing can be either substitutional or interstitial. Both of these two types of doping
can affect the lattice spacing of TiO2. Incorporation in the substitutional posi-
tion or interstitial position is reflected in the variation of the lattice spacing of
the parent semiconductor. Additional allowed energy levels in the forbidden
gap of the semiconductor depends on their energy positions, can act as electron
or hole traps, and promotes the corresponding reduction or oxidation reactions
or facilitates the recombination of the charge carriers. Hence, the ratio of the
doped metal to that of the parent semiconductor must be carefully considered,
because the presence of the metal dopant can simultaneously suppress and
enhance the recombination of the photo‐generated electron and hole within the
semiconductor. It has been reported in the literature that incorporation of met-
als such as Cu, Pt, Pd, Rh, Fe, and Ag into TiO2 can improve the photocatalytic
reduction of carbon dioxide. All these studies can be generally understood by
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 361

the “metal‐modified TiO2” terminology instead of specifying them as either

doping or metal loading.
TiO2 has been chosen as a representative system. The modifications that have
been described, namely doping and coupling, are general in nature and applica-
ble to all the semiconductors that have been tried for this photocatalytic reac-
tion. These studies been attempted in many other semiconductor systems, as
shown in Table 12.4. In spite of the many variations that have been tried, the
efficiency of the resultant systems has not improved to the desired level and
thus the exercise to identify the selection of materials with optimum efficiency
is still continuing. These studies that covered the TiO2 system are equally appli-
cable to other systems as well and hence they are not covered in this chapter.
To summarize the reactions on semiconductor surfaces, the reduction
potentials for various reaction products in the photocatalytic reduction of car-
bon dioxide are shown in Figure 12.5. On the left‐hand side the potential scale
is with zero at vacuum and on the right‐hand side the electrochemical scale is
shown at pH = 0.

E vs Vacuum E vs NHE (pH 0)

–2.0 –2.5

–2.0
CO2/CO2•
SiC
–3 Cu2O
–1.5
GaP
CuFeO2 –1.0
Si GaAs CdS CO2/HCO2H
Inp
2.24 eV

CO2/CO
3.0 eV

–4 TiO2 –0.5
1.1 eV

CdTe ZnO WO3 WS2 CO2/HCOH

CdSe MoS2
0.0 H2O/H2
1.4 eV

1.95 eV
1.47 eV

CO2/CH3OH
2.4 eV

1.17 eV
2.4 eV

–5 0.5
1.35 eV
1.7 eV

CO2/CH4
1.0 O2/H2O
3.2 eV

3.2 eV

–6 1.5
2.7 eV

2.0

–7 2.5

3.0

Figure 12.5  Conduction band potentials (open squares) and valence band potentials (gray
squares) of some commonly used semiconductors, along with with the potentials of several
carbon dioxide/water redox couples at pH = 0.
362 Photocatalytic Functional Materials for Environmental Remediation

The efforts extended in making this process more efficient have not so far
yielded the desired results. This probably indicates that the basic choice of
materials has not been appropriate. In spite of the concerted efforts to modify
and redesign the available known materials, perhaps one now has to focus on
completely new materials for this reaction. It has been pointed out already that
the energetic position of the conduction band and the valence band controls
the reduction and oxidation reactions that can be promoted by these semicon-
ductors. These positions, as given in Table 12.4, are for the static state of the
semiconductor under a semiconductor/vacuum interface. These redox values
may be altered during the adsorption and activation of the reagents. This has
partly been taken care of in the concept of band bending when the interface is
changed to the reaction medium [42]. There is a possibility that the energy
level positions of the bands of the semiconductor may functionally change
depending on the reaction conditions employed. This aspect has not yet been
fully and explicitly dealt within the literature.
It was pointed out earlier that the adsorption of carbon dioxide should be
such that the band angle should reduce from 180° to a nearly tetrahedral angle.
There can be various modes of adsorption of carbon dioxide on the catalyst
surface, depending on the nature of the surface morphology. Essentially, the
possible structural modes of adsorption of carbon dioxide can be visualized as
shown in Figure 12.6 [3].
The modes shown in Figure 12.6 are the ideal configurations of the adsorp-
tion mode of carbon dioxide. Depending on the nature of the surface site and
the adsorption geometry of the substrate, the modes of adsorption of CO2 can
vary and one typical configuration was shown in Figure 12.2. As already stated,
the reduction of CO2 is limited kinetically since the lowest unoccupied molec-
ular orbital (LUMO) level is an antibonding orbital and hence the reduction
process has to be coupled with proton transfer. For this purpose the qualitative
molecular orbital energy diagram for carbon dioxide is as shown in Figure 12.7.
The reduction of carbon dioxide to hydrocarbons can be carried out on sur-
faces where proton and electron transfers are simultaneously possible. Thus
the search for catalyst systems should be carried out on such surfaces where
the transfer is facile for both these species.
Carbon dioxide is chemically inert, has a closed shell electronic configura-
tion, and is linear in structure. The addition of a single electron causes the
necessary bond angle reduction and bends the molecule structure due to the
repulsion between the added electron and the electron pairs on the oxygen
atoms. This repulsion contributes to the high energy of the LUMO level of the
carbon dioxide molecule and thus accounts for the low electron affinity of the
molecule. This situation makes it virtually certain that no semiconductor is
capable of transferring the single electron to a free CO2 molecule; the reduc-
tion potential is around −1.90 V as stated above. Though single electron reduc-
tion thus experiences a higher energy barrier, the situation is manageable with
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 363

Physisorbed CO2 and its vibrations

(Weakly) chemisorbed CO2 (C-down configuration) and its vibrations

O-Down configuration Mixed configuration Upright configuration

(Weakly) chemisorbed CO2 (O-down configuration)

Figure 12.6  Possible adsorption modes (physisorbed, chemisorbed with C or O down) of

carbon dioxide on surfaces. Source: Reproduced from Ref. [3].

proton‐assisted transfer of multiple electrons. This is clear from the values of

reduction potentials given in Table 12.2.

12.7 ­Perspectives in the Photocatalytic Reduction

of Carbon Dioxide
In essence, the search for suitable semiconductor materials has been focusing
on the following aspects:
1) Extending the photoresponse of the semiconductor to the visible region of
the solar spectrum.
2) Sensitizing the semiconductor (by the addition of molecular species or cou-
pling/modifying) to effectively utilize the excitons and improve the
efficiency.
364 Photocatalytic Functional Materials for Environmental Remediation

Carbon CO2 Oxygen

a1u combination
orbitals
a1g
e1u

(e1u)
2p
(a1u)
e1g e1g
Energy

e1u
a1u 2p(degenerate)
e1u a1g
2s (a1g) π

σ a1u

σ a1g

a1u
a1u
a1g 2s(degenerate)
a1g

Figure 12.7  Qualitative molecular orbital diagram for carbon dioxide. Source: Reproduced
from Ref. [3].

3) Altering the valence band maximum in order to change the value of the
bandgap.
4) Altering the conduction band minimum to more reductive potential values
so as to facilitate hydrogen production.
5) To generate multiple photocatalytically active sites and also to alter the sur-
face area, new nanoscale morphologies have been employed.
In spite of these attempts, so far no realizable success in the reduction of
carbon dioxide seems to have been achieved. This may mean that the steps so
far attempted, though they may logically be in the correct direction, may only
marginally improve the efficiency; perhaps the search has to take an alterna-
tive, so far untrodden, path.
At present, the formation rates of products from the photocatalytic reduc-
tion of carbon dioxide on semiconductors rarely exceed tens of mmol g−1 h−1.
This means that the efficiency of the process is generally lower than in natural
photosynthesis or even less than that achieved in the photocatalytic generation
of hydrogen. However, this has not hampered the interest of scientists pursu-
ing this research field.
Recent developments are concentrated on the search for new photocatalytic
materials and new nanoscale configurations. New photocatalytic materials
could be novel materials of metals with d0 or d10 electronic configurations,
though this concept that systems with this electronic configuration will be
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 365

appropriate semiconductors for this reaction has not yet been fully established.
New nanoscale configurations could offer improved surface area, increased
charge separation, and vectorial electron transfers. The mechanism of the pro-
cess has been studied by both experimental and computational methods. These
studies are aimed to answer the unanswered questions concerning the chemi-
cal pathways of CO2 reduction. Of particular interest are the approaches to
overcome the barrier associated with the activation of a CO2 molecule toward
the first one‐electron reduction. This step is rate limiting, because of the highly
negative electrochemical reduction potential of CO2 to the anion radical with
respect to the conduction band levels of commonly employed semiconductors.
Other important aspects of the mechanism that are relevant for a deeper
understanding of the process include charge‐carrier dynamics within the semi-
conductors, the effect of the nanostructure of the photocatalyst, and the impact
of the choice of the catalytic metal on the photocatalytic reduction of carbon
dioxide. Most of the studies reported on this reaction employ TiO2 and its vari-
ations [43, 44], as it is considered a good model system for comparative study.
The situation regarding the results reported about this system does not allow
a direct comparison of the system as there is no standardized procedure
adopted or assigned to report the results. It may be worthwhile if standardiza-
tion could be achieved on the amount of the catalyst employed and also if there
was a proper measure of the photon intensity employed. Another aspect on
which there is no clarity or consistency is the counter reaction; this is the reac-
tion involving oxygen or hydrogen peroxide formation in relation to the reduc-
tion reaction carried out. Until this is achieved, there will be always doubt on
the sustainability of the reaction or long‐term use of the catalysts for commer-
cial exploitation. The system ultimately employed commercially should be
based on the cost of the material and also that it is abundantly available.
Since ultimately the products of reaction should be separable, photoelectro-
chemical cells will be advantageous for exploiting this reaction commercially.
The feverish attitude in studying this reaction and the consistent attempts to
identify the appropriate semiconductors for promoting this reaction can be
expected to move this process closer to success.
In the future, the direction of research may be to exploit the effects of mixed
crystal phase, defect disorders, and modifications in designing the chosen
catalyst systems. It is also necessary that the mechanistic details of the charge
transfer will have to be elucidated with respect to details of each and every step
at the interface.
Various configurations and various additives have been tried for the photo-
catalytic reduction of carbon dioxide. Varghese et al. [45] reported experiments
conducted in outdoor sunlight. The relative hydrocarbon production rate of
111 ppm cm−2  h−1, or ≈160 μl g−1  h−1 has been reported when the nanotube
array samples are loaded with both Cu and Pt nanoparticles. This rate of CO2
366 Photocatalytic Functional Materials for Environmental Remediation

SUN

CH4, H2,O2 CO-CATALYST CO2, H2O

Figure 12.8  Flow through nanotube array loaded with co‐catalyst for photocatalytic
conversion of carbon dioxide and water into hydrocarbons. Source: Reproduced from
Ref. [45].

to hydrocarbon production appears to be higher than what is so far reported.

The pictorial representation of their system is shown in Figure 12.8.
Osterloh, in a recent commentary on recent advances in solar fuels and pho-
tocatalysis, said that this area continues to attract interest in the scientific com-
munity [46]. Solar photon energy can be used to form fuels. However, harnessing
solar photons and utilizing their energy in technologically useful processes is
not an easy job. It requires materials that are strong light absorbers, that exhibit
long excited state lifetimes, and enable fast charge carrier processes.
As has been pointed out earlier, designing appropriate photocatalysts is
important as it determines the activity and selectivity of CO2 reduction.
Nanostructuring resulted in increasing surface area and an increase in the
number of active reaction sites, as pointed out earlier. In recent times interest
has been focused on various configurations of composite photocatalysts by
introducing metal and metal oxide co‐catalysts, as well as Z‐scheme systems
[47]. These systems are mainly aimed to improve the charge separation.
Additionally, Z‐scheme photocatalytic systems have shown a strong tendency
toward oxidation and reduction, while their narrow bandgap is beneficial to
utilize visible light. Although various photocatalysts have shown good perfor-
mance, the photocatalytic reduction of protons to hydrogen, a competitive
reaction in aqueous CO2 photoreduction, remains a major obstacle.
Significant improvements in catalyst and reactor design are needed for the
photocatalytic functionalization of CO2 to become a viable technology for the
production of energy and chemicals. Fundamental strategies for the rational
design of materials for effective transformations of CO2 to value‐added chemi-
cals have to be evolved [48].
 Active Materials for Photocatalytic Reduction of Carbon Dioxide 367

In recent times, a number of reviews and perspectives have been published

in the literature on the photocatalytic reduction of carbon dioxide [49–51]. In
spite of this spate of activity on this reaction, commercially viable processes are
yet to evolve. The various reasons for this have been outlined.
The reasons for this failure can be many; however, the foremost among them
is the choice of material. In the literature, various sensitization methods have
been focused toward exploiting the visible range of the solar spectrum.
However, even the utilization of the ultraviolet component of the solar spec-
trum (~3%) [52] alone may be enough to satisfy the energy needs of the Earth.
Under these circumstances, the search for photocatalysts active in the visible
spectrum has to be justified.
Secondly, the various sensitization methods employed in the fast five dec-
ades have not yielded the desired results. Hence, this may mean that the search
for the selection of suitable materials must be directed elsewhere.
In conclusion, in spite of the various tools (both experimental and theoreti-
cal) on hand and also having the facility to scan a number of samples at the
same time (high throughput analysis), the appropriate material for photocata-
lytic reduction of carbon dioxide or hydrogen generation from water has not
been achieved in the last five decades, though vigorous attempts have been
directed to do so. This may mean that nature still holds her secrets, as in pho-
tosynthesis. In our anxiety to mimic nature, we have not yet learnt the ways in
which nature performs her functions to satisfy all the needs of the humanity in
a satisfactory manner.

­Acknowledgement
The author’s grateful thanks are due to his colleagues and to the Department of
Science and Technology, Government of India, for the creation of the National
Center for Catalysis Research at the Indian Institute of Technology, Madras.

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3 Aulice Scibioh, M. and Viswanathan, B. (2018). Carbon Dioxide to Chemicals
and Fuels. Elsevier. ISBN: 9780444639967.
4 Wang, W.‐N., Soulis, J., Jeffrey Yang, Y., and Biswas, P. (2014). Comparison of
CO2 photoreduction systems: a review. Aerosol Air Qual. Res. 14: 533–549.
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5 Lehn, J.‐M. and Ziessel, R. (1982). Photochemical generation of carbon

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