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Applications of MXene (Ti3C2Tx) in photocatalysis:

a review
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Cite this: Mater. Adv., 2021,

2, 1570 Xing Li, a Yang Bai,*a Xian Shi,b Na Su,a Gongzhe Nie,a Rumeng Zhang,c
Hongbo Niead and Liqun Ye *ae

MXenes are two-dimensional nanomaterials, which can be constructed from different elements. The
rich interlayer groups, surface groups, and the flexible layer spacing of MXenes make them ideal
catalysts. Among these, Ti3C2Tx has gained particular attention as a photocatalyst for photocatalytic CO2
reduction reactions (CO2RR), hydrogen evolution reactions (HER), and photocatalytic degradation
reactions. The structure of Ti3C2Tx, hydrophilic surface functional groups, and the Gibbs free energy for
hydrogen adsorption lead to the excellent photocatalytic HER performance of this material. Numerous
Received 30th November 2020, surface defects on Ti3C2Tx also provide plentiful CO2 adsorption sites for CO2RR. It is the structure of
Accepted 27th January 2021 two-dimensional nanomaterials and their high-speed electron transport channels that enable their
DOI: 10.1039/d0ma00938e excellent catalytic oxidation activity. However, at present, there are still challenges that limit their further
application, the most significant of which is the material stability. In order to overcome this, the
rsc.li/materials-advances synthetic routes to prepare these photocatalysts need to be adapted.

1 Introduction Photocatalytic nanomaterials have an extensive number of

potential applications. When their particle size is below a
Photocatalysis is an environment-friendly technology developed certain value, the Fermi level of the electronic energy levels
in the 20th century. When light is absorbed by some special morphs from continuous to discrete levels and the energy gap
semiconductors, namely ‘‘photocatalysts’’, electrons (e ) originally grows wider. These semiconductors are, therefore, more suscep-
in the valence band (VB) are excited to the conduction band (CB) tible to photon excitation, which improves their photocatalytic
and holes (h+) are formed in the initial position. Free electrons activity.1
with strong reducibility can reduce the valence state of some Nanomaterials can be divided into four categories, according
elements in compounds (such as carbon in CO2 and nitrogen in to the dimensions of their structural scale: (1) zero-dimensional
N2) when regular methods are not useful or cost too much. Thus materials, e.g., groups of nanostructure clusters; (2) one-
far, photocatalysis has shown its huge application prospects in dimensional nanomaterials, e.g., fibrous nanotubes, nanowires,
clean energy, environmental remediation, and many other fields; nanoribbons, or other related structures; (3) two-dimensional
currently, researchers are heading towards new photocatalyst nanomaterials, e.g., layered nanomaterials, quantum wells,
development and reaction mechanisms. Photocatalytic hydrogen superlattices, and other structures; (4) three-dimensional nano-
evolution reaction (HER), CO2 reduction reaction (CO2RR), and materials, e.g., composite structures consisting of one or more
photocatalytic degradation reaction represent the three main zero-dimensional, one-dimensional, or two-dimensional nano-
aspects of photocatalysis. materials. The first three are collectively known as low Vannami
materials. In low Vannami materials, two-dimensional nano-
a
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, School of materials show significant changes in the surface, electron
Oil & Natural Gas Engineering, Southwest Petroleum University, Chengdu, energy levels, state density, and other aspects compared with
610500, China. E-mail: baiyanghyq@foxmail.com
b
three-dimensional materials. This due to the fact that their
Institute of Fundamental and Frontier Sciences, University of Electronic Science
and Technology of China, Chengdu, 610054, China
thickness is greatly reduced compared to other two-dimensional
c
Key Laboratory of Ecological Security for Water Source Region of Mid-line Project materials; thus, these possess unique optical and electronic
of South-to-North Water Diversion of Henan Province, College of Chemistry and characteristics, which make them a hot topic in catalysis.2,3
Pharmaceutical Engineering, Nanyang Normal University, Nanyang, 473061, MXenes are two-dimensional nanomaterials and have a general
China
d
material formula of Mn+1XnTx. In this formula, M represents
CNOOC (China) Co., LTD. Tianjing Branch, Tianjing, 300452, China
e
College of Materials and Chemical Engineering, Key Laboratory of Inorganic
nitrogen or carbon, X is generally a transition metal element,
Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges and T represents the functional groups. MXenes typically consist
University, Yichang, 443002, China. E-mail: lqye@ctgu.edu.cn of transition metal carbides, nitrides, or carbides that are several

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atomic layers thick. It was first reported in 20114 that MXene a few or single layers, mechanical or chemical intercalation
materials have comparable conductivity towards transition metal dissection is required. However, when chemical intercalation is
carbides due to the presence of hydroxy groups or terminal oxygen used for stripping, some organic molecules may occupy the
species on their surfaces. The most important feature of this range active sites exposed on the surface, which is unfavorable for
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of materials is that, unlike conventional battery materials, they photocatalytic reactions.

provide more channels for ions to move through, thus dramatically Etching is a slow process, as shown in Fig. 1(a). In this
increasing their speed. process, Al layers are gradually peeled off, while the Ti–C
Ti3C2Tx was the first discovered MXene material and is also the skeleton layers are not damaged because of their strong ionic
most widely used MXene material in the field of photocatalysis.5–7 bonding.12 Free groups such as –OH and some H2O molecules
It was first obtained by etching the Al layer of Ti3AlC2 with enter into the framework of Ti–C and become inter-connected
Open Access Article. Published on 28 January 2021. Downloaded on 8/10/2023 12:33:37 PM.

hydrofluoric acid. In this paper, the application of Ti3C2Tx as a by hydrogen bonds, which expands the layer spacing of Ti3C2Tx.
photocatalyst and approaches to improve its catalytic performance This permits ions with a large radius to enter the layer
are summarized. spacing,13 providing an operating space for the ion intercala-
tion method to peel-off few layers of Ti3C2Tx. The number of
–OH groups and H2O molecules within the interlayer space
2 MXene
accounts for the large electrical capacity of Ti3C2Tx.
2.1 From MAX to MXene. MXenes are a type of two- Ti3C2Tx obtained by direct etching with hydrofluoric acid
dimensional nanomaterials with covalent bonds formed possesses a different morphology to Ti3C2Tx obtained by etching
between the early transition elements and nitrogen or carbon with LiF/HCl. Furthermore, NMR spectroscopy revealed a greater
elements. This furnishes an intramolecular skeleton in which number of –OH and –F functional groups on the surface of
the layers are connected by hydrogen bonds. Since the first Ti3C2Tx etched by hydrofluoric acid, while LiF/HCl etching
Mxene, Ti3C2Tx, was discovered in 2011, more than 20 kinds of furnished a material with predominantly –O functional groups.
MXene materials including M2X, M3X2, and M4X3 have been
successively prepared.7,8 Due to their unique structure and
properties, MXenes have been widely favored for use in battery 2.2 Structure and properties of Ti3C2Tx
applications. 2.2.1 Structure of Ti3C2Tx. As shown in Fig. 2(a), the
The preparation of MXenes can be divided into two structure of Ti3C2Tx is comprised of three parts: the intralayer
approaches, namely, bottom-up and top-down. Presently, the skeleton region, the interlayer region, and the surface termi-
top-down etching method is commonly employed. This is due nating groups. In the intramolecular skeleton region, Ti atoms
to the MAX phase9,10 (commonly, M means early transition and C atoms are stacked alternately to form ionic bonds, and
metal elements such as Ti and Nb; A represents the Al or Si the skeleton of the entire main structure is formed on this
layer; X represents C or N elements) as M is mainly composed of basis. In the interlayer region, it was found through neutron
metallic bonds between the atoms, which are connected to A. diffraction that the interaction between the layers is established
The chemical properties are largely dictated by A. By using through hydrogen bonding between either O or F atoms on the
certain concentrations of hydrofluoric acid or LiF/HCl11 to etch surface and van der Waals forces between these atoms. The
the MAX phase of Ti3AlC2, ternary carbides within the titanium strength of interlayer hydrogen bonding depends not only on
carbon layers become closer to each other. In this process, the the orientation of –OH relative to the entire sheet but also on
Al layer is etched away gradually, resulting in a greater carbon– the number and distribution of the –OH groups. When there is
titanium interlayer spacing in the Ti3C2Tx product. In order to water between the layers, it can also participate in hydrogen
obtain Ti3AlC2 with a graphene-like structure consisting of only bonding. In addition, a large number of terminal groups are

Fig. 1 The process of etching Ti3AlC2 to yield Ti3C2.

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Fig. 3 Oxidation process of Ti3C2Tx.

atmosphere of N2, Ar, or other inert gases, the number of –F

groups on the surface of Ti3C2Tx is reduced, after which the
electrical capacity is greatly increased.
Fig. 2 Schematic diagram showing the crystal structure of Ti3C2 (a)19 and Ti3C2Tx shows an excellent absorption of light between
its monolayer with (b) top and (c) side view. The large blue balls represent 300 nm and 500 nm.27 Recently, researchers have even found
Ti atoms and the small brown balls represent C atoms. The highlighted unit that the absorption can be broadened to the near-infrared (NIR)
cell indicates the high symmetry A, B, and C adatom sites.20
region. According to a further study, this may be related to its
surface plasmon resonance (SPR), and the thinner the material,
the stronger the SPR.28 Such a peculiarity makes Ti3C2Tx an
randomly distributed on the surface of the Ti3C2Tx main ideal photothermal co-catalyst.
structure. These surface groups are directly bonded to the 2.2.3 Instability of Ti3C2Tx. MXenes typically have poor
exposed surface and Ti3C2Tx is obtained by top-down etching, stability. Ti3C2Tx is rapidly oxidized when heated under CO2, air,
which mainly includes surface groups such as –O, –OH, and –F. and other environments, and when the surface groups are all –O,
After a period of placement, the –F groups can be replaced by Ti3C2O2 exhibits metallic properties.29,30 Ti3C2Tx is also slowly
–O groups. The surface groups have a great influence on the oxidized when exposed to air under atmospheric conditions. After
properties of the Ti3C2Tx formed, which can be analyzed by oxidation, Ti3C2Tx is called oxidized MXene (denoted as MO).
electron energy loss spectroscopy (TEM),14,15 neutron scattering,16
and NMR techniques.17,18 These experiments confirm that the
surface functional groups of Ti3C2Tx are randomly distributed
with –O, –OH, and –F all directly bonded to the surface of the
exposed MXene plane. Furthermore, there are no adjacent –OH
functional groups found between the layers. The presence of
cations between the layers causes the MXene lamellae to slide
easily relative to each other, changing their rheological properties
and resulting in their clay-like properties.
2.2.2 Properties of Ti3C2Tx. The structure of Ti3C2Tx deter-
mines the electric storage performance. As Ti3C2Tx has a wide
spacing between the layers, the ions can travel through the
layers at a high speed, whilst the hydroxyl or terminal oxygen
groups on the surface furnish a material with excellent con-
ductivity. Both factors are important for the use of these MXene
materials in batteries.20–25
Various surface groups (such as –O, –F, and –OH) have
supplied abundant anchored sites for the base photocatalyst
to form efficient heterojunction structures, which are ideal for
photocatalytic activities.26 There is also a large number of
exposed metal sites on the surface, which can be used as active
sites for reactions.
The surface chemical state of MXene materials has a large Fig. 4 HAADF-STEM images from single-layer Ti3C2Tx MXene flakes prepared
influence on the regulation of its physical properties. When –F using etchants with different HF concentrations: (a) 2.7 wt% HF, (b) 5.3 wt% HF,
and (c) 7 wt% HF. Single VTi vacancies are indicated by the red circles, while
on the surface is replaced by an –O group, the electrochemical
vacancy clusters VC
Ti are shown by the blue circles. (d) Scatter plot of the defect
performance is improved. For example, when Ti3C2Tx is treated concentration from the images acquired from samples produced using differ-
with a KOH and CH3OOK solution, the –O groups on the ent HF concentrations. The red line shows the error plot with the average and
surface increase, along with the electric capacity. Under an standard deviation for different HF concentrations.33

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Table 1 Comparison of photocatalysts including Ti3C2Tx in HER

Review

H2 production
(mmol h 1 Activity improvement Monolayer or
Name gcatalyst 1) AQY (%) factor Sacrificial reagent Preparation methods multilayer Light source Morphology Year Ref.
CdS/Ti3C2Tx 14 342 40.1% (420 nm) 135.59 times Lactic acid One-step Ti3C2Tx NPs 300 W Xe lamp Cauliflower- 2017 30
(17.6%) hydrothermal method (l 4 420 nm) structure by
self-assembly of
many NPs
2D-Layered Carbon/TiO2 480.8 1.98% (400 nm) TEOA (10%) Ti3C2Tx oxidation Multilayer 300 W Xe lamp Nanosheets 2017 44
(l 4 400 nm)
Ti3C2Tx/rutile TiO2 17.8 0.3% Approximately 4 times Methanol (25%) Hydrothermal method Monolayer 200 W Hg lamp 2D sheetswith TiO2 2016 45
(l 4 400 nm) attached on the
surfaces and
between the sheets
Ti3C2/Pt/g-C3N4 5000 3.1% (420 nm) 15 times than pristine TEOA (10%) Hydrothermal and Monolayer 300 W Xe lamp Nanosheets with 2018 46
g-C3N4 photodeposition porous
method nanoparticles
Sulfur-doped Carbon/ 333 7.36% Methanol (10%) Ti3C2Tx oxidation Multilayer 300 W Xe lamp Nanosheets 2018 47
TiO2 (l 4 400 nm)
Ti3C2Tx/TiO2 783.11 5.86 (350 nm) 6 times Methanol (20%) Hydrothermal and Multilayer 300 W Xe lamp Nanoflowers 2018 48
nanoflowers calcination
Zn2In2S5/Ti3C2Tx 2596.76 8.96% (420 nm) 1.97 times 0.25 M Na2SO3/ Hydrothermal Multilayer 300 W Xe lamp Flower-like 2018 49
0.35 M Na2S/ (l 4 420 nm) microspheres

2021 The Author(s). Published by the Royal Society of Chemistry

H2PtCl6
d-Ti3C2/TiO2/g-C3N4 1620 4.16% (420 nm) 12.15 times than pure TEOA (10%) Calcination Monolayer 300 W Xe lamp 2D–2D 2018 50
g-C3N4 (l 4 420 nm) heterostructure
ZnS/Ti3C2 502.6 4 times Lactic acid (20%) Hydrothermal Multilayer 300 W Xe lamp Sphere-like 2019 51
structure
1D CdS nanorod/2D 2407 35.6% (429 nm) 6.68 times Lactic acid (10%) Electrostatic Monolayer 300 W Xe lamp 1D/2D nanosheets 2019 52
Ti3C2 MXene nanosheet self-assembly (l 4 420 nm)
TiO2 nanofibers/MXene 6979 3.8 times than TiO2 Methanol (10%) Electrostatic Monolayer 300 W Xe lamp Nanofibers/ 2019 53
Ti3C2 nanofibers self-assembly nanosheets
technique
TiO2 nanoparticale/ 2650 15.8% (305 nm) 2.88 times than TiO2 Methanol (25%) Electrostatic Monolayer 200 W Hg lamp Nanosheets 2019 54
monolayer Ti3C2 nanoparticles/multilayer self-assembly (285–325 nm)
Ti3C2 technique
MoS2/Ti3C2 6144.7 2.33 times Methanol (30%) Hydrothermal Multilayer 300 W Xe lamp Spheres-like 2019 55
(l 4 400 nm) structure
Ti3C2 MXene/O-doped g- 25124 17.59% 1.8 times than O-doped TEOA Electrostatic Multilayer 300 W Xe lamp 2D nanosheets 2019 56
C3N4 (405 nm) g-C3N4 self-assembly structure
technique
CdLa2S4/Ti3C2 11182.4 15.60% 13.4 times 0.25 M Na2SO3 Hydrothermal Monolayer 300 W Xe lamp Particle-like 2019 57
(420 nm) and (l 4 420 nm)
0.35 M Na2S
Ti3C2 MXene quantum 5111.8 3.654% 25.97 times TEOA (15%) Deposition Ti3C2 MXene 300 W Xe lamp Nanosheets 2019 58
dots/g-C3N4 quantum dots
MoxS@TiO2@Ti3C2 10505.8 7.535% 5.99 times than TEOA In situ growth and Multilayer 300 W Xe lamp Nanosheets 2019 59
Mo2S@TiO2@Ti3C2 hydrothermal
Ti3C2/porous MOFs 204 Approximately 8 times 0.1 M Na2S and Hydrothermal Monolayer 350 W Xe lamp 3D structure 2019 60
(UiO-66-NH2) 0.1 M Na2SO3
C-TiO2/g-C3N4 1409 8 times than C-TiO2 TEOA (10%) Calcination Multilayer 300 W Xe lamp Smooth sheet-like 2019 32
(l 4 420 nm) structure
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Table 1 (continued)

H2 production
(mmol h 1 Activity improvement Monolayer or
Name gcatalyst 1) AQY (%) factor Sacrificial reagent Preparation methods multilayer Light source Morphology Year Ref.
CdS@Ti3C2@CoO 134.46 1.75 times than CdS@CoO Calcination Monolayer 300 W Xe lamp Spheres-like 2019 61
(l 4 420 nm) structure
TiO2–Ti3C2–CoSx 950 5.8 times than TiO2 Methanol (20%) Hydrothermal Multilayer 300 W Xe lamp Smooth round block 2019 62
Materials Advances

morphology
Ti3C2(TiO2)@CdS/MoS2 8470 3.76 times than CdS/MoS2 lactic acid (20%) Hydrothermal Multilayer 300 W Xe lamp Nanospheres 2019 63
(l 4 420 nm)
Ti3C2 MXene/MoS2 6425.297 4.61% 7.15 times than TiO2/Ti3C2 TEOA Ti3C2Tx oxidation Multilayer 300 W Xe lamp Ti3C2 nanosheets 2019 64
nanosheets/TiO2 with MoS2

1574 | Mater. Adv., 2021, 2, 1570 1594

nanosheets nanoparticales
2D/3D g-C3N4/Ti3C2 116.2 6.64 times TEOA (10%) Calcination Multilayer 300 W Xe lamp Nanosheets 2020 65
(MXene) heterojunction (l 4 420 nm)
Au/MoS2/Ti3C2 12000 Methanol (30%) Electrostatic self- Multilayer Nanosphere-like 2020 66
assembly technique
2D/2D Ti3C2/g-C3N4 72.3 0.81% (400 nm) 10.18 times than pure TEOA (10%) Electrostatic self- Monolayer 200 W Hg lamp Flat irregularly 2019 67
g-C3N4 assembly approach shaped nanosheets
of 2D/2D structures
MXene@Au@CdS 17070.43 1.85 times than pure CdS 0.35 mol L 1 Na2S Hydrothermal Monolayer 300 W Xe lamp Nanosheets 2020 68
and 0.25 mol L 1 (l 4 420 nm)
Na2SO3 solution
Black phosphorus 684.5 11.35 times TEOA (25%) Solvent-heatmethod Multilayer 300 W Xe lamp Nanosheets 2020 69
quantum dots/ (l 4 420 nm)
Ti3C2@TiO2
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Fig. 5 TEM images of (a–c) CdS, (d–f) exfoliated Ti3C2 MXene nanosheets, (g–i) the composite CM-20, (j) the corresponding elemental mapping results
of CM-20, and (k) the oxidation process of Ti3C2Tx.52

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Fig. 6 (a and b) Photocatalytic H2 evolution performance of different samples, (c) the recycled photocatalytic H2 evolution experiments of CM-20,
(d) AQY values and the wavelength dependence of photocatalytic H2 evolution in the composite CM-20.52

When Ti3C2Tx is oxidized, it is only the Ti atoms that are oxidized defect configurations.34,35 As shown in Fig. 4, widespread Ti
into the corresponding oxide (TiO2), while the C atoms remain defects were directly detected through the HAADF-STEM imaging
unchanged. In other words, MO comprises a sandwich structure of the single-layer Ti3C2Tx flakes. Single-layered Ti3C2Tx obtained
of layered carbon layers and titanium oxide.31 Fig. 3 shows the by HF etching was observed through HAADF-STEM images in
structural evolution of Ti3C2Tx oxidation to MXene (MO). As can Fig. 4(a)–(c). Fig. 4(d) was obtained by calculating tens of such
be seen from Fig. 3, MO maintains a layered structure, whilst the images, and it reveals that the relationship between HF concen-
TiO2 nanoparticles formed by oxidation are coated within the tration and defect formation. It was found that vacancy clusters
carbon layer structure. Due to the photoresponse capacity of TiO2, are rarely observed after etching with 2.7 wt% HF concentration
this resulting structure is photocatalytically active. An example of but are relatively common after etching with 7 wt% HF.33
this is MO/g-C3N4, which can photocatalytically split water with a Generally speaking, the average concentration of VTi (Ti vacan-
relatively high efficiency.32 cies) is positively related to that of HF.
The crystal structure of Ti3C2Tx contains Ti defects, which
appear to contribute significantly to the instability of this 3. Application in photocatalysis
material.14,33 High angle annular dark field (HAADF)-STEM
imaging is an important tool in 2D materials’ characterization Due to the excellent structural properties of Ti3C2Tx, there are
and is used to unambiguously resolve the crystal structure and many cases in which Ti3C2Tx is used as a co-catalyst in

Fig. 7 (a) Photocurrent density curves and (b) EIS Nyquist plots of CdS and CM-20.52

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photocatalytic systems or is directly involved in photocatalytic

reaction systems. This paper summarizes the application of
Ti3C2Tx in the field of photocatalysis from three aspects:
photocatalytic hydrogen evolution reactions (HER), photocatalytic
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CO2 reduction reactions (CO2RR), and photocatalytic degradation

reactions.

3.1 Application in HER

Ti3C2Tx is the most widely used photocatalytic agent in hydrogen
evolution reactions36–39 (HER). Ti3C2Tx has the following advan-
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tages that make it ideal for use in photolysis: (a) hydrophilic

surface functional groups are conducive for the adsorption of
water molecules and promote the reaction; and (b) the Gibbs free
energy of Ti3C2Tx adsorption on hydrogen approaches zero
infinitely, which is conducive for the reduction of H+. Scheme 1 Formation of Schottky barrier at the MXene/TiO2 interface.45
There are three important steps in the HER process, which
are:30,40,41 (a) initial h+ + e formation; (b) generation of H* (the
intermediate adsorption state); and (c) formation of the 1/2 H2 (2407 mmol h 1 gcatalyst 1), producing 6.68 times as much H2
product. The adsorption state of H* in process (b) directly affects as pure CdS (Fig. 6).
the final hydrogen evolution efficiency and is an extremely Theoretically, the surface negative value (zeta potential
important factor, which can be represented by the Gibbs adsorp- value: B18 mV) of Ti3C2Tx is sufficient to adsorb positively
tion free energy |DGH*|. Through simulation calculations, it was charged Cd2+. Ti3C2Tx treated with DMSO forms a low-layered
found that when all the Ti3C2Tx surface groups are –F, DGH* = structure, on which Cd2+ can be anchored and one-dimensional
0.927 eV, and the adsorption is too strong. When all the surface CdS nanorods can be grown. As shown in Fig. 5, due to the
groups are –O, |DGH*| is 0.003 eV, which is even better than the constraint effect of Ti3C2Tx, the length of 1D CdS nanorods in
commonly used catalyst Pt (DGH* E 0.090 eV).42,43 Therefore, the 1D CdS nanorods/2D Ti3C2Tx heterojunctions is smaller
Ti3C2Tx is a good HER co-catalyst. Examples of Ti3C2Tx used for than that of the 1D CdS nanorods alone.
photolysis in recent years are summarized below (Table 1). CdS equipped with Ti3C2Tx displays excellent electrochemical
Ti3C2Tx plays a significant role in HER, whether as a properties. As shown in Fig. 7, the photocurrent of 1D CdS
co-catalyst or as a part of the overall catalyst, as it greatly improves nanorods/2D Ti3C2Tx was significantly better than that of one-
the performance of the base catalyst. As shown in Table 1, the dimensional CdS nanorods and the optical resistance was
presence of Ti3C2Tx increases the yield of H2 compared to solely significantly lower than that of one-dimensional CdS nanorods.
the base catalyst by more than 2 times. The quantum efficiency is ESR tests show that the hydroxyl radical and superoxide radical
also significantly improved to 40.1%, whilst the maximum value of signals of 1D CdS nanorods/2D Ti3C2Tx were significantly
hydrogen production is 14.34 mmol g 1 h 1. enhanced after the addition of Ti3C2Tx. In conclusion, under the
Monolayer Ti3C2Tx or quantum dot Ti3C2Tx displays better same illumination conditions, 1D CdS nanorods/2D Ti3C2Tx gen-
activity in HER. However, the use of monolayer Ti3C2Tx as a erate more photogenic carriers. These produce oxygen-containing
photocatalyst has several disadvantages: (a) the preparation of
monolayer Ti3C2Tx is complex; (b) the structural stability is low
and the catalyst is easily oxidized in water; (c) manipulation of
the mono-layer or few-layer structures is not easy to carry out.
Few-layer structures are presently prepared by electrostatic self-
assembly or by in situ growth. The stability of the composite
catalyst obtained by in situ growth is significantly greater than
that obtained by electrostatic self-assembly.
Due to the surface hydrophilic groups,70 suitable Gibbs
adsorption free energies |DGH*|, and excellent electron transfer
efficiency, Ti3C2Tx not only plays an important role in the three-
step process of HER but can participate in electron hole
separation.
Xiao et al. successfully synthesized the Schottky junction of
1D CdS nanorod/2D Ti3C2 MXene nanosheet in 2019.52 As
shown in Fig. 5, Xiao et al. anchored Cd2+ using the deficiency
of Ti on the Ti3C2 surface and the electrostatic interaction of free
Cd2+ to prepare the 1D CdS nanorods. The composite material Fig. 8 SEM images of (a) TiO2 (50 wt%), (d) Ti3C2Tx, (b) TiO2/Ti3C2Tx
demonstrated excellent hydrogen production performance (5 wt%), and (c) TiO2/Ti3C2Tx.45

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Fig. 9 (a) Photocatalytic hydrogen production rates and (b) recycling studies over the TiO2/Ti3C2Tx (5 wt%) sample.45

groups with oxidizing reductivity, which can participate in photo-

catalytic hydrogenation reactions.
1D CdS nanorods/2D Ti3C2Tx typically exhibit better visible
light response, electron hole separation efficiency, and more
effective carrier transport efficiency after the formation of
multi-dimensional heterojunctions. This accounts for their
excellent photocatalytic hydrogen evolution capability.
Using Ti3C2Tx as the co-catalyst, Wang et al. synthesized a
TiO2/Ti3C2Tx complex photocatalyst,45 which was 4 times more
efficient than pure phase TiO2 in photohydrolyzing aquatic
hydrogen. This is attributed to the Schottky barrier formed
between TiO2 and Ti3C2Tx, which effectively improves the
separation efficiency of the electron holes. As shown in
Scheme 1, excited electrons can be wired to Ti3C2Tx from the
conduction band of TiO2 owing to the close contact between
Ti3C2Tx and TiO2; thus, negative charge is accumulated in
Ti3C2Tx and a depletion layer formed at the metal–semicon- Fig. 11 CO2RR process.
ductor interface, which is the Schottky barrier.45
In this work, Wang et al. treated Ti3C2Tx with DMSO to form
low-layer structures. Amorphous TiO2 was formed from TiCl4 a low-layered structure (Fig. 8). After water heat treatment, the
hydrolysis and then on the surface of Ti3C2Tx, amorphous TiO2 whole structure forms into a brittle cake structure (Fig. 9).
was coated. After hydrothermal treatment, anatase TiO2/Ti3C2Tx The TiO2/Ti3C2Tx material displays excellent photocatalytic hydro-
material was formed, as shown in Fig. 8. Amorphous TiO2 is gen evolution capability with good cycling stability. The hydrogen
micro-spherical and is coated on the surface of Ti3C2Tx, displaying production efficiency of TiO2/Ti3C2Tx-5% is about 4 times as high as

Fig. 10 (a) PL spectra and (b) DRS spectra of TiO2, TiO2/Ti3C2Tx (5 wt%), TiO2/Ti3C2Tx (10 wt%), and TiO2/Ti3C2Tx (50 wt%).45

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surface, the redox reaction is carried out on the surface of

the catalyst. The product then de-attaches, which completes
the entire photocatalytic CO2 reduction reaction.
Ti3C2Tx is also widely used in the photocatalytic CO2
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reduction reaction. However, due to its own carbon source

and instability, further research is needed to understand the
mechanism of photocatalytic CO2 reduction of Ti3C2Tx.
Fig. 12 Two pathways in CO2RR.
In 2017, Zhang et al. summarized the CO2 reduction capacity
of three MXene materials with surface groups, which terminate
that of pure phase TiO2, reaching 17.8 mmol h 1 gcatalyst 1. The with –O through theoretical calculations.75 Among the three
Open Access Article. Published on 28 January 2021. Downloaded on 8/10/2023 12:33:37 PM.

hydrogen production efficiency of the 10% and 50% samples materials, Ti2CO2, V2CO2, and Ti3C2O2, Ti2CO2 showed the best
decreased slightly, which may be related to light energy absorp- photocatalytic CO2 reduction capacity. Of the two reduction
tion, as shown in Fig. 10(a). With the increase in Ti3C2Tx paths76–78 shown in Fig. 12, the pathway of ‘‘CO2–HCOO–
addition, the light absorption capacity of the samples in the HCOOH’’ has a favorable energy barrier of about 0.53 eV.
250–380 nm region is gradually decreased. This significant Through DFT calculations, it was revealed that in the first
improvement in the hydrogen production efficiency is closely step reaction of CO2 adsorption in CO2RR, the O atom of the
related to the smooth carriage of Ti3C2Tx. As shown in Fig. 10(b), CO2 molecule occupies an O defect position on the MXene. This
after the formation of the Schottky barrier, the carrier separa- mode in adsorption requires the lowest energy. The adsorption
tion efficiency is improved, thus improving its photocatalytic energies of the three materials were Ti3C2O2 ( 0.73 eV), Ti2CO2
capacity. ( 0.67 eV), and V2CO2 ( 0.35 eV). Ti2CO2 has a lower adsorp-
Thus, in conclusion, after loading with Ti3C2Tx, H2 produc- tion energy compared to V2CO2 as the Ti atoms are more likely
tion increased at least twice. Such an amazing promotion is to lose electrons than the V atoms.
mainly related with 3 aspects of Ti3C2Tx: (a) it supplies a high If the reaction proceeds via pathway 1 (Fig. 11), one of the
throughput channel as a co-catalyst for the excited electrons oxygen atoms of the CO2 molecule is captured by the oxygen
while the holes cannot pass the boundaries; (b) its hydrophil- defect. This results in the breaking of the C–O bond, while CO
city; and (c) the Gibbs free energy of Ti3C2Tx adsorption on is produced. In this step, Ti3C2O2 would lower the energy
hydrogen approaches zero infinitely. barrier of the C–O bond to about 0.86 eV. Pathway 2 (Fig. 11)
has an energy barrier greater than 1 eV. In this pathway, the
3.2 Application in CO2RR CO2 molecules are captured by an oxygen defect on the surface
The photocatalytic CO2 reduction reaction (CO2RR) consists of of MXene and are hydrogenated to form COOH. This is further
five steps:71–74 light absorption, charge separation, CO2 adsorp- hydrogenated and converted into the products CO and H2O.
tion, surface redox reaction, and product desorption. As shown CO, which is produced, can further react to form HCOOH,
in Fig. 11, when the CB of the photocatalyst is greater than the HCOH, CH2OH, CH4, and other products.
redox potential of CO2, and charge separation occurs whilst the Studies into the application of Ti3C2Tx in CO2RR is summarized
electrons and holes recombine. Several complex factors dictate in Table 2.
which of these two competing processes predominantly occurs. In 2018, Cao et al. prepared a 2D/2D heterogeneous junction
After the adsorption of CO2 and the migration of photogenerated of Ti3C2Tx/Bi2WO6 and the composite showed excellent photo-
electrons and holes from the inside of the crystal structure to the catalytic CO2 reduction performance.82 As shown in Fig. 13,

Table 2 Comparison of photocatalysts including Ti3C2Tx in CO2RR

Activity
Products and yield improvement Reaction Preparation Monolayer
Photocatalyst (mmol g 1 h 1) factor conditions Light source method Morphology or Multilayer Year Ref.
2D/2D Ti3C2 CO (5.19) 8.37 (CO) 20 mg 300 W Xe Calcination 2D/2D Monolayer 2020 79
MXene/g-C3N4 CH4 (0.044) 2.09 (CH4) catalyst gas–solid lamp under N2 nanosheets
nanosheet (l 4 420 nm) atmosphere
Alklinized Ti3C2/ CO (11.21 mmol g 1) 5.96 (CO) 40 mg catalyst 300 W Xe Alkali etching 3D Multilayer 2019 80
decorating g-C3N4 gas–solid lamp
CH4 (0.044 mmol g 1) 5.6 (CH4) (l 4 420 nm)
TiO2/Ti3C2 CO — 50 mg 300 W Xe Calcination Nanoparticles Multilayer 2018 81
CH4 (0.22) catalyst liquid– lamp
solid
2D/2D ultrathin CO 4.34 (CH4) 100 mg Xe lamp Hydrothermal Flat shape 2D Monolayer 2018 82
Ti3C2/Bi2WO6 CH4 (1.78) 6.28 (CH3OH) catalyst liquid– structure
solid
CH3OH (0.44)
2D/2D/0D TiO2/ CO (4.39) 1.39 (CO) 30 mg catalyst 300 W Xe Electrostatic 2D/2D Ti3C2 quan- 2020 83
C3N4/Ti3C2 (than TiO2/C3N4) liquid–solid lamp self-assembly structure tum dots
CH4 (1.20)

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Fig. 13 (a–c) Typical FESEM, AFM images, and height cutaway view of Bi2WO6, (d–f) Ti3C2 nanosheets, (g–i) TB2 (Ti3C2Tx/Bi2WO6), and (j) schematic
illustration of the synthetic process.82

multi-layer structure Ti3C2Tx was tested with DMSO. After the formed. The concurrent addition of CTAB furthermore ensures
formation of low-layer structure Ti3C2Tx, the oxygen-rich surface the ultrathin structure of both Bi2WO685 and Ti3C2Tx.86
was negatively charged, which permitted Bi3+ to be adsorbed The successful preparation of heterojunctions greatly
from hydrolyzed Bi(NO3)355H2O.84 After the addition of a tung- enhances the ability of Bi2WO6 to reduce CO2. The CH4
sten source, a 2D/2D Ti3C2Tx/Bi2WO6 heterojunction was production of the sample TB2 reached 1.78 mmol h 1 g 1, while

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Fig. 14 (a) Photocatalytic activity of TB0 to TB5; (b) GC-MS spectra over TB2 after irradiation for several hours with different carbon sources; (c) GC-MS
analysis of the reaction products with 12C and 13C as carbon sources.82

Fig. 15 (a) UV-Vis DRS of all the as-prepared samples; (b) TRPL spectra of TB0 and TB2; (c) EIS plots and (d) transient photocurrent of the prepared samples.82

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the yield of CH3OH reached 0.44 mmol h 1 g 1. The isotopic Yang et al. prepared 2D/2D Ti3C2 MXene/g-C3N4 heterojunc-
spectra of Fig. 14(b) and (c) indicates that the produced CH4 and tions in 2020.79 As shown in Fig. 16(g), Ti3AlC2 was successfully
CH3OH are formed from the photocatalytic reduction of CO2. etched to form Ti3C2, as indicated by the XRD patterns.87,88 2D
As shown in Fig. 15(a), Ti3C2Tx exhibits excellent light g-C3N4 was found to grow on the surface of Ti3C2 under an
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absorption performance between 200–800 nm. The light atmosphere of N2. The formed 2D/2D Ti3C2 MXene/g-C3N4
absorption capacity of Bi2WO6 was also significantly improved demonstrated excellent photocatalytic CO2 reduction capability.
by carrying Ti3C2Tx. To be noted, as shown in Fig. 14(b), the As shown in Fig. 17, the photocatalytic performance of pure phase
fluorescence lifetime decreased after loading with Ti3C2Tx. This g-C3N4 for the production of CO and CH4 is only 0.62 mmol h 1 g 1
is because TC supplies a more efficient non-radiative decay and 0.021 mmol h 1 g 1, respectively, in contrast to Ti3C2,
pathway. In electrochemical tests, the photocurrent photoelectric wherein the production of CO and CH4 is 5.19 mmol h 1 g 1,
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impedance spectrum further revealed that the carriage of Ti3C2Tx 0.044 mmol h 1 g 1, respectively. The isotopic experiments
greatly promoted the carrier strength of Bi2WO6. This further confirm that the product is produced by the photocatalytic
confirmed the successful construction of the Ti3C2Tx/Bi2WO6 reduction of CO2.
heterojunction. The tests of PL and TRPL showed that the composite rate of
electron holes45,89 decreased significantly after carrying Ti3C2.
As shown in Fig. 18(b), the fitted pure phase C3N4 had a lifetime
of only 4.14 ns, while 10TC had a lifetime of 4.51 ns, which
represents a significant increase in the lifetime of the carriers.
This is closely related to the smooth carrying of Ti3C2. An
excellent ‘‘storage capacitor’’ is produced when Ti3C2 forms a
heterojunction with g-C3N4. When the electrons are transmitted
to the semiconductor surface, they transfer to Ti3C2 quickly while
the holes cannot. This greatly reduces the electron hole compo-
site and improves the photocatalytic performance of the material.
On the other hand, abundant defects on the Ti3C2 surface provide
excellent sites for CO2 adsorption.
In conclusion, the application of Ti3C2Tx in CO2RR is
relatively less than that of photocatalytic water splitting. This
is because of its instability and its own carbon resources, which
can cause interferences during the photocatalytic CO2
reduction reaction. As shown in Table 2, among limited reports,
Ti3C2Tx with both single-layered structures and multi-layered
structures shows an obvious production promotion. It is to be
noted that there are no new products (such as C2 products,
formaldehyde, and methyl ether) after loading with Ti3C2Tx
compared to the base photocatalyst. This phenomenon confirms
that Ti3C2Tx cannot change the energy barrier of the base
photocatalyst for CO2 reduction. Thus, in general, the obvious
promotion during CO2RR may be related to the two features of
Ti3C2Tx: (a) abundant surface vacancies for CO2 adsorption and
(b) promoting the separation of carriers.

3.3 Applications in degradation

The main principle of photocatalytic degradation by photo-
catalytic semiconductor materials is that light stimulates the
generation of oxidizing holes.90–93 These can oxidize dissolved
oxygen into efficient oxygen-active species such as superoxide
radicals ( O2 ), singlet oxygen ( O), and hydroxyl radicals
( OH). These species can directly oxidize the substrate.94–96
Ti3C2 has a wealth of surface groups and active sites, which
are conducive for the adsorption of substrates. Accordingly,
Ti3C2 has been of particular interest as a photoactive degrada-
Fig. 16 FESEM images of UCN (a) and 10TC (b) samples, AFM images and
tion catalyst. A summary of the previous studies investigating
the corresponding height profiles of UCN (c and e), 10TC (d and f) samples, the application of Ti3C2 in photocatalytic degradation reactions
and (g) schematic illustration for the fabrication process.79 is shown in Table 3.

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Fig. 17 Photocatalytic CO2 reduction performance of the as-prepared samples (a); cycling tests over the 10TC sample (b); GC-MS analysis of the
products from the photoreduction of CO2 over 10TC using labelled 12CO2 and 13CO2 as the carbon sources (c and d).79

In 2018, Cai et al. produced a Ag3PO4/Ti3C2 composite of carriers; (ii) the strong redox reactivity of the surface Ti sites,
photocatalyst, which possessed excellent photocatalytic degra- which promote multiple electron reduction reactions to induce
dation performance.87 more  OH production; and (iii) a Schottky junction formed at the
As shown in Fig. 19, after DMSO and sonication treatment, Ag3PO4/Ti3C2 interface enabling efficient transfer electrons to the
Ti3C2 with a low-layer structure was formed. After the addition Ti3C2 surface. This inhibits the photocossion of Ag3PO4 caused
of silver nitrate, Ag+ was adsorbed due to the negative charge on by photogeneration electrons.
the surface of Ti3C2. Ag3PO4 nanoparticles were grown in situ, Under high temperature conditions, Ti in the Ti3C2 skeleton
forming a heterojunction between the Ag3PO4 nanoparticles layer is oxidized into TiO2, while C still exists in the form of a
and the Ti3C2 nanosheets. graphene-like layer. Therefore, under high temperature condi-
As shown in Fig. 20, the heterojunction of the Ag3PO4 tions, Ti3C2 can be converted into amorphous TiO2 anchored
nanoparticles/Ti3C2 nanosheets shows a photocatalytic degra- within the graphene-like layer. In 2020, Wu et al. took advan-
dation stage rate K of 0.094, 0.005, 0.32, and 0.0042 min 1 for tage of this material, which displayed excellent photocatalytic
methyl orange (MO), 2,4-dinitrophenol (2,4-DNP), tetracycline degradation performance.105
(TC–H), thiamphenicol (TPL), and chloramphenicol (CPL), As shown in Fig. 22(e) and (f), high temperature treated
respectively. According to EPR analysis, the hydroxyl radical Ti3C2 still retains its morphology and a 3D block-shaped
( OH) plays an important role in the oxidation system, as morphology is formed after carrying g-C3N4 (Fig. 23).
shown in Fig. 20(f). This may be related to abundant Ti defects Graphene layers anchored to TiO2/g-C3N4 show first-order
on the Ti3C2 surface. Ti sites exposed on the surface of Ti3C2 kinetic constants for the degradation of rhodamine B (RhB),
have strong redox reactivity, which promotes multiple electron tetracycline (TC), ciprofloxacin (CIP), and bisphenol A (BPA) of
reduction reactions (O2 - H2O2 -  OH). 0.0559, 0.0244, 0.0168, and 0.0194 min 1, respectively. Accord-
As shown in Fig. 21, PL, TRPL, and the electrochemical ing to the EPR test results (Fig. 24(a)–(d)), the oxygen active
characterization spectra indicate that the carrier separation species that play a role in the oxidation process mainly include

efficiency of the material is significantly improved after carrying O2 and  OH. Furthermore, signals corresponding to the holes
Ti3C2. This may be attributed to (i) the abundant surface hydro- (h+) were also detected. The contribution to the degradation of
philic functional groups of the Ti3C2 construct, which have these test molecules appears to be in the order of  O2 4 h+ 4

strong interfacial contact with Ag3PO4, facilitating the separation OH.

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Fig. 18 PL spectra, EIS, and TPR plots of UCN, Ti3C2, and 10TC samples (a, c, and d); TR-PL spectra of UCN and 10TC (b).79

High-temperature treated Ti3C2 has a greatly enhanced light is complex. Despite this, Ti3C2Tx has an excellent optical
absorption capacity, whilst the carrier separation efficiency and response ability and displays broad catalytic activity.
transmission efficiency are also improved. The improvement of
the photocurrent (Fig. 24(e) and (f)) also verified that the
graphene layers anchoring TiO2 lead to the formation of a 5. Summary and outlook
heterogeneous junction. This is due to the change in the 5.1 Summary
electric field between g-C3N4.
In conclusion, as a co-catalyst, the application of Ti3C2Tx in In recent years, Ti3C2Tx has attracted wide interest as a photo-
photocatalytic degradation is mainly due to its three character- catalytic material due to its rich surface space and surface
istics: (a) in a liquid–solid phase reaction, its hydrophilicity defects, hydrophilic properties, large interlayer spacing, and
makes it easy for the adsorption or contact between the pollutants excellent microwave absorbing properties. Ti3C2Tx-based
and photocatalysts; (b) high throughput electron transfer makes it photocatalysts are widely used in hydrogen evolution reactions
easier to generate concentrated holes (h+); and (c) Ti sites (HER), CO2 reduction reactions (CO2RR), photocatalytic degra-
exposed on the surface of Ti3C2 have strong redox reactivity, dation reactions, and show excellent catalytic performance. The
which promotes multiple electron reduction reactions, such as application of Ti3C2Tx in photocatalysis still warrants further
the reaction of activating molecular oxygen (O2-H2O2- OH). investigation.
The further application of Ti3C2Tx in photocatalysis depends
4. Challenges on the development of the material itself. Methods to improve
The application of Ti3C2Tx in photocatalysis is worthy of further the stability of the Ti3C2Tx structure need to be explored, starting
investigation, despite the many problems that need to be from synthetic methods. In addition, the rich groups on the
solved. The main issue lies in the instability of the composite surface of Ti3C2Tx and its hydrophilicity should be further
material, resulting in unstable photocatalytic performance. explored, particularly in photocatalytic liquid phase reactions.
This contributes to the difficulty in determining the photo-
catalytic process mechanisms of Ti3C2Tx-based photocatalysts. 5.2 Outlook
Many of the existing solutions use either few- or single-layer 5.2.1 Mechanism. During the photocatalytic reaction, espe-
structured materials. However, the preparation process of these cially the reaction including liquid phase, the mechanism

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Table 3 Application of Ti3C2Tx in photocatalytic degradation reactions

Removal rate (%)/rate Light Oxygenic Monolayer

Review

Photocatalyst Substrate of degradation constants (min 1) Reaction conditions source species Morphology or multilayer Year Ref.
Ag3PO4/Ti3C2 Methyl orange (MO) (rate constants) 0.094 20 mg catalyst + 50 300 W Xe h+ (main) 2D Ti3C2/Ag3PO4 particles Monolayer 2018 87
(MO) mL 20 mg L 1 sub- lamp (l 4
strate, 30 min dark 420 nm)
adsorption

2,4-Dinitrophenol (2,4-DNP) 2,4-DNP (0.005) OH
Tetracycline hydrochloride TC–H (0.32)
(TC–H)
Thiamphenicol (TPL) TPL (0.0042)
Chloramphenicol (CPL) CPL (0.025)

Ti3C2/SrTiO3 composites UO22+ (Removal rate) 20 mg catalyst + 60 300 W Xe OH 2D Ti3C2/SrTiO3 particles Multilayer 2019 97
mL 50 ppm sub- lamp (l =
strate, 8 hours dark 320–
adsorption 2500 nm)
77% in 180 min
Ti3C2–OH/Bi2WO6 composites Rhodamine B (Rate constants) 0.0596 10 mg catalyst + 50 mL 2  10 5 300 W Xe lamp (l = h+ Porous spherical structure Ti3C2–OH 2019 98
mol L 1 substrate, 30 min dark 400–2500 nm)
adsorption
MoS2@Ti3C2 Nanohybrid Liquid paraf- (Rate constants) 0.0476 A certain amount of sample + 1000 W high- MoS2 nanosheets/Ti3C2 sheets Multilayer 2019 99
fin (LP) 2.0 g of deionized water and pressure mercury
1.0 g of LP + 10 mL dichlor- lamp

2021 The Author(s). Published by the Royal Society of Chemistry

omethane as the sacrifice
reagent, 30 min dark adsorption
0D/2D Bi3TaO7/Ti3C2 Methylene blue (Rate constants) 50 mg catalyst + 100 300 W Xe lamp  OH Bi3TaO7 nanoparticles/Ti3C2 Multilayer 2020 100
0.032 mL 10 mg L 1 (l 4 420 nm) nanosheets
Substrate, 60 min
dark adsorption
2D/2D Ti3C2/Porous g-C3N4 Phenol (Rate constants) 20 mg catalyst + 50 500 W Xe lamp 2D/2D Ti3C2/PCN nanocomposite Multilayer 2020 101
0.022 mL 10 mg L 1 (l 4 400 nm) with ultra-
sonication
Substrate, 30 min
dark adsorption
CdS@Ti3C2@TiO2 Sulfachloropyridazine (Removal rate) SCP 50 mg catalyst + 200 Light intensity  O2 CdS nanoparticles/Ti3C2@TiO2 Bulk 2019 102
(SCP) (about 95% in 60 mL 20 mg L 1 300 mW cm 2 (l bulk Ti3C2@TiO2
min) = 400–1050 nm)
Methylene blue (MB) MB (about 80% in
60 min)
Rhodamine B (RhB) RhB (about 99% in substrate, 30 min
60 min) dark adsorption
Phenol Phenol (about 50%
in 60 min)
(111) TiO2-x/Ti3C2 Mmethylene blue (MB) (Removal rate) MB 10 mg catalyst + 200 500 W Xe lamp  OH (main) TiO2 nanoparticles/Ti3C2 Multilayer 2017 103
(75% in 150 min) mL 20 mg L 1 (l 4 400 nm) nanosheets
(001) TiO2/Ti3C2 Methyl orange (MO) (Rate constants) 10 mg catalyst + 200 300 W Xe lamp  OH (main) TiO2 square nanosheets/Ti3C2 Multilayer 2016 104
0.018 mL 20 mg L 1 sub- nanosheets
strate, 60 min dark
adsorption
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Table 3 (continued)

Removal rate (%)/rate Light Oxygenic Monolayer

Photocatalyst Substrate of degradation constants (min 1) Reaction conditions source species Morphology or multilayer Year Ref.

Graphene layers anchored TiO2/ Rhodamine B (RhB) (Rate constants) 10 mg catalyst + 200 300 W Xe lamp OH 3D bulk Bulk 2020 105
g-C3N4 0.0559 (RhB) mL (RhB 20 mg L 1, (l 4 400 nm) Ti3C2@TiO2
TC 10 mg L 1, CIP 3
mg L 1, BPA 5 mg
Materials Advances

L 1), 60 min dark

adsorption

Tetracycline (TC) 0.0244 (TC) O2
Ciprofloxacin (CIP) 0.0168 (CIP) h+
Bisphenol A (BPA) 0.0194 (BPA)

1586 | Mater. Adv., 2021, 2, 1570 1594

2D/2D Ti3C2/MoS2 Methylene orange (Rate constants) 50 mg catalyst + 50 400 W metal h+ Flower-like nanosphere Multilayer 2020 106
(MO) 0.00836 mL 20, 30, 50 mg halide lamp
L 1 substrate, 30
min dark adsorp-
tion, 60 min dark
adsorption

OH

a-Fe2O3/ZnFe2O4@Ti3C2 Rhodamine B (RhB) (Rate constants) 20 mg catalyst + 100 300 W Xe lamp O2 a-Fe2O3/ZnFe2O4 nanoparticles/ Multilayer 2019 107
0.02686 (RhB) mL 10 mg L 1 sub- (l 4 400 nm) Ti3C2 nanosheets
(Removal rate) strate, 30 min dark
adsorption

Cr(VI) Cr(VI) OH
Light off: about h+
70% in 90 min
Light on: about
90% in 90 min
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Fig. 19 TEM images of (a) bulk Ti3C2, (b) single Ti3C2 sheet, (c) Ag3PO4/Ti3C2 composite. (d) EDX spectra of the Ag3PO4/Ti3C2 composite and (e) the
schematic representation of single 2D Ti3C2 sheets and Ag3PO4/Ti3C2 synthesis.87

needs to be explored. As is known to all, the structure of pure performance, isotope detection shows that some carbon
Ti3C2Tx is not stable in both air and water. In air, the fresh- resources come from CO2 molecular; thus, there are still some
etched surface groups (such as –OH and –F) can be replaced by ambiguities and other possibilities. For example, the valence
oxygen termination after being exposed to air for a period of state of ‘‘C’’ in Ti3C2Tx is mostly ‘‘ 4’’, which makes it
time; in water, Ti3C2Tx can even be oxidized after being replaced possible for CO2 to react with Ti3C2Tx in order to form the
for 21 days in room temperature.108 Thus, it needs to be explored CO as product; this pathway involves redox reaction rather
more whether the structure of Ti3C2Tx is changed during the than catalysis.
photocatalytic reaction and if it does, how it changes. This, in all, the mechanism needs to be explored more, both
During photocatalytic CO2RR, although both monolayer- during the photocatalytic reaction and the oxidation of Ti3C2Tx
structured and multilayer-structured Ti3C2Tx exhibit high itself.

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Fig. 20 Photocatalytic degradation of various pollutants by the as-prepared catalysts. (a) CPL, (b) TPL, and (c) TC-H degradation efficiency in the
presence of the as-prepared catalysts under visible light irradiation (l 4 420 nm). HPLC chromatogram of (d) CPL and (e) TPL under different
degradation times using the as-prepared catalysts. (f) UV-vis absorption spectra of TC–H under different degradation times using different
catalysts.87

Fig. 21 UV-vis diffuse reflectance spectra (a), PL spectra (b), time-resolved PL decay spectra (c), EIS Nyquist plots (d), transient photocurrent
responses (e) of the as-prepared catalysts, and DMPO spin-trapping ESR spectra for DMPO– OH in the Ag3PO4/Ti3C2 system in the presence or
absence of HA.87

5.2.2 Development direction. The application of Ti3C2Tx in new two-dimensional materials. For further applications, the
photocatalysis is meaningful not just because it obviously following directions are necessary: to explore new methods of
promotes the reaction but also due to its applications in other preparation to get structurally-stable Ti3C2Tx; to explore easier

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Fig. 22 SEM images of C3N4 (a and b), Ti3C2 (c and d), heated Ti3C2 (e and f), and graphene layers anchored TiO2/g-C3N4 (g and h).105

Fig. 23 The photocatalytic degradation performance of TC (a), CIP (b), BPA (c), and RhB (d) by photocatalysts under visible light irradiation.105

methods of preparation to get monolayered Ti3C2Tx; to explore Conflicts of interest

more effective combination between Ti3C2Tx and the base
photocatalyst; to explore methods of regulating the surface There are no conflicts to declare.
groups and interlayer groups; to explore other application in
the MXene family; to explore the mechanism.
Ti3C2Tx is the earliest material in the MXene family; thus,
Acknowledgements
the improvement of its application in photocatalysis repre- This work was supported by the National Natural Science
sents a great significance for the application of the whole Foundation of China (No. 51702270 and 51872147), the 111
family. Project (D20015), the Program for Innovative Research Team of

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Fig. 24 Trapping experiment for the photocatalytic degradation of TC over GTOCN3 (a); ESR spectra of CNTOC3 for (b) DMPO– O2 , (c) TEMPO–h+,
(d) DMPO– OH in the dark and under visible light irradiation, I–T curves under visible light irradiation (e) and the EIS response (f) of the samples.105

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