APL Materials RESEARCH UPDATE scitation.

org/journal/apm

Photocatalysis over MXene-based hybrids:

Synthesis, surface chemistry, and interfacial
charge kinetics
Cite as: APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711
Submitted: 1 May 2021 • Accepted: 1 July 2021 •
Published Online: 20 July 2021

Chao Peng,1,a) Tao Zhou,1 Ping Wei,1 Wenkang Xu,2 Hui Pan,3 Feng Peng,4 Jianbo Jia,1 Kun Zhang,1
and Hao Yu2,a)

AFFILIATIONS
1
School of Biotechnology and Health Sciences, Wuyi University, Jiangmen 529020, People’s Republic of China
2
School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology,
South China University of Technology, Guangzhou 510640, People’s Republic of China
3
Joint Key Laboratory of the Ministry of Education, Institute of Applied Physics and Materials Engineering, University of Macau,
Macao SAR, People’s Republic of China
4
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, People’s Republic of China

a)
Authors to whom correspondence should be addressed: [email protected] and [email protected]

ABSTRACT
Two-dimensional (2D) transition metal carbides and/or nitrides (MXenes) are a family of graphene-like 2D materials, with unique layered
structures, high mechanical strength, excellent carrier mobility, and outstanding physical and chemical properties. In particular, the work
function (Φ) of MXenes and Gibbs free energy of the adsorbed intermediate, such as H∗ (∣△GH∗ ∣), can be regulated by their surface adsorp-
tion groups (–OH, –O, and –F), enabling the applications in the field of photocatalysis. This article systematically summarizes the recent
advances of synthetic routes of MXene-based photocatalysts and discusses the interfacial charge kinetics and photogenerated charge transfer
mechanism of MXene-based photocatalysts. Furthermore, major challenges and further research trends of MXene-based photocatalysts are
also presented.
© 2021 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0055711

I. INTRODUCTION form a large family of ternary ceramic materials with the general for-
mula Mn+1 AXn , where n = 1–3, M is an early transition metal, A is
Two-dimensional (2D) materials, such as graphene, hexagonal an A-group element (mostly IIIA and IVA), and X is C,10 N,11,12 or
boron nitride, transition metal dichalcogenides (TMDs), and black B13,14 ] as the precursor. Typically, the metal A layers are etched away,
phosphorus (BP), have attracted extensive attention due to their out- leaving MX layers. After exfoliation, single-layered carbides/nitrides
standing features, including ultrahigh specific surface areas, tunable with the structure and morphology similar to graphene can be
electronic properties, excellent ionic conductivity, and high Young’s obtained, which are named as MXenes.9 MXenes may offer excel-
moduli.1 In addition to those newly emerged properties due to the lent mechanical properties and high carrier mobility and thus
atomic thickness, 2D materials achieve grain boundary-free assem- have been attracting wide interest from researchers in recent
bly and amplification.2 Recently, more and more 2D materials have years.15–17
been used to fabricate novel and efficient photocatalysts,3,4 such as Notably, MXenes also show their prominence in the field of
MoS2 ,5 VS2 ,6 WC1−x ,7 and WXy (X = C, N, S).8 photocatalysis because (i) the excellent metallic conductivity of the
MXenes, a type of 2D transition metal carbides/nitrides, were MXene assures efficient charge–carrier transfer;18,19 (ii) the elec-
first reported in 2011 by Naguib et al.9 They are usually derived trons and holes in MXenes have high anisotropy, which is benefi-
from the MAX phase of ternary ceramic materials [the MAX phases cial to their migration and separation;20,21 and (iii) as a compound

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-1

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

of metal and carbon, MXenes afford a natural platform to con- 1. Top-down routes
struct composites of metal oxide and carbonaceous materials.22,23
More importantly, the work function and carrier transport prop- The top-down route was currently the main preparation
erties of MXenes could be manipulated by their surface terminated method of MXenes. Pioneered by Naguib et al., the thin-layered
groups (–F, –OH, –O),24,25 allowing for tunable electronic properties MXenes [Fig. 1(a)] can be prepared through two steps: (i) treat-
by adjusting their surface chemistry, which provides the possibility ing the MAX phase precursor in high concentration HF acid to
to construct MXene-based composite catalysts and further control break the M–A bonds and etch away the A layers and (ii) swelling
their photocatalytic performance.26 the multilayer MXenes with isopropanol or other reagents and then
This article discusses the recent research update of photo- ultrasonically exfoliating them to obtain 2D MXenes.15
catalysis based on MXenes. First, we briefly introduce the types, The above two-stepped approach has been substantially
preparation methods, and physiochemical properties of MXenes. improved by modifying the etching and exfoliation stages since
Second, the effects of surface functional groups on their electronic 2014. Both Ti3 AlC2 15 and Ti3 SiC2 44 MAX phases have been suc-
properties are discussed. Next, several material synthesis strate- cessfully used for etching hydrofluoric acid to prepare the Ti3 C2 T x
gies of MXene-based photocatalysts are summarized. The interfacial MXene. To avoid the usage of high-concentration HF as the etch-
charge kinetics of MXene-based photocatalysts are analyzed based ing agent, which results in highly toxic and corrosive waste liquid,
on the structure–property relationship. Finally, challenges and the mixtures of fluoride salt and acid instead of HF as etchants have
potential opportunities to develop MXene-based photocatalysts in been proposed to replace HF. Halim et al. first demonstrated that
practical applications are discussed. NH4 HF2 could be used to etch Ti3 AlC2 films prepared through the
This article is complementary to other reviews on epitaxial growth method, in which NH4 + was dispersed between
MXenes,17,27–36 from the synthesis of MXenes27–29 to the preparation Ti3 C2 T x layers to improve the exfoliation of Ti3 C2 T x .45 Further-
and application of MXene-based photocatalysts.17,30,31,33–36 More more, the Ti3 AlC2 powder has been treated by a variety of bifluo-
importantly, this article does not simply summarize the preparation rides to synthesize the Ti3 C2 T x MXene. The etching reaction mecha-
and performance of MXene-based photocatalysts but build a bridge nism and the thermal stability of the as-prepared MXenes have been
between their surface chemistry and photocatalytic applications to clearly elucidated by Feng et al.46,47 The mixture of monofluoride
discuss their surface termination with the influence on their phys- (LiF, NaF, KF, and NH4 F) and concentrated hydrochloric acid has
iochemical properties and further elucidate the interfacial charge been employed to prepare Ti3 C2 T x MXene.19,48,49 Ghidiu et al.19 and
transfer kinetics of MXene-based photocatalysts. It is expected to Wang et al.50 applied the LiF/HCl and FeF3 /HCl to synthesize 2D
provide a valuable reference for researchers in the field of MXene Ti3 C2 T x MXene, respectively. Li cations in the LiF + HCl etchant
interface and catalysis. mixture migrate and intercalate into the interlayer space, while the
A layers are etched and removed as AlF3 . When concentrations of Li
ions are high enough, the resulting multilayered MXene “clay” spon-
II. SYNTHESIS AND PROPERTIES OF MXenes taneously delaminates and could be further exfoliated into single- or
A. MAX phase and types of MXenes few-layered MXenes by gentle agitation [Fig. 1(b)].19
The MAX phase is a kind of abundant ternary carbides,10 Recently, a hydrothermal route has also been developed to pre-
nitrides,11,12 or borides.13,14 The metal M layer might exist in three pare multilayer MXenes. Peng et al. exploited a new hydrothermal
different forms: single metal, disordered bimetal solid solution, and route with low-toxicity etching agents (NaBF4 and HCl) to syn-
ordered bimetal. So far, there have been more than 70 MAX phases thesize Ti3 C2 T x and Nb2 CT x MXenes.51 Wang et al. developed a
reported.10,37 hydrothermal process to synthesize Ti3 C2 T x using NH4 F as the etch-
As the M–A bond was much more active than the M–X ing agent.52 Despite the expanded scope of the preparation method
bond, the alumina layer can be selectively removed from the of MXenes, these endeavors still formed in situ hydrogen fluoride
MAX phase precursor. According to the stoichiometry of the MAX solution during the etching reaction.
phase precursor, MXenes could be classified into three categories: Alternative HF-free etching methods are highly desirable to
“M2 X1 ,” “M3 X2 ,” and “M4 X3 .” According to the composition of the prepare MXenes. Li et al. reported a fluorine-free synthesis of
metal M layer, it could be divided into the following types: single high purity Ti3 C2 T x (T = –OH, –O) via high-temperature alkali
metal element MXenes (e.g., Ti2 CT x , Ti3 C2 T x , and Nb4 C3 T x ), solid treatment.53 Sun et al. successfully etched Al from porous Ti2 AlC
solution MXenes [e.g., (Ti,V)3 C2 T x and (Ti,Nb)4 C3 T x ], ordered electrodes in dilute hydrochloric acid to form a layer of Ti2 CT x
bimetal MXenes [including out-of-plane ordered bimetal MXene, MXene via electrochemical etching.54 Huang’s group developed a
Mo2 TiC2 T x and Mo2 Ti2 C3 T x ,38 and in-plane ordered bimetal novel molten-salt etching approach to synthesizing -Cl terminated
MXene, (Mo2/3 Y1/3 )2 CT x 39 and Mo1.33 CT x 40 ], and multi-metal MXenes originated from the replacement reaction between a series
high-entropy 2D carbide MXenes41 derived from high-entropy of Zn-based MAX phases and the late transition-metal halides.55
MAX phases.42 In addition, Xu et al. reported the synthesis of Natu et al. etched and dispersed Ti3 C2 T x MXenes in several water-
a 2D nitride Ti4 N3 T x ,43 which further enriched the types of free polar organic solvents by using ammonium bifluoride as the
MXenes. etchant.56 These methods not only enriched the preparation route
of MXenes but also, more importantly, opened up the possibil-
ity for preparation of MXenes in a fluorine-free53 or water-free
B. Preparation of MXenes environment56 with controllable terminated groups on the surface.
Similar to other traditional 2D nanomaterials, MXenes can be On the other hand, many researchers have tried to swell
prepared via top-down or bottom-up strategies. the multilayer MXene with various organic solvents. Mashtalir

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-2

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

FIG. 1. (a) Schematic diagram of the preparation process of MXenes. Reproduced with permission from Naguib et al., Adv. Mater. 26(7), 992–1005 (2014). Copyright 2014
Wiley. (b) Schematic of MXene clay synthesis and electrode preparation. Reproduced with permission from Ghidiu et al., Nature 516(7529), 78–81 (2014). Copyright 2014
Nature Publishing Group. (c) Schematic for the MXene delamination process by reacting MXenes with an organic base that causes multilayered MXene powder (pictured
in bottom left) to swell significantly. Reproduced with permission from Naguib et al., Dalton Trans. 44, 9253–9358 (2015). Copyright 2015 Royal Society of Chemistry. (d)
Images of the 1 l MXene reactor and the 3D model of the synthesis setup. The system has an internal jacket coupled with a cooling tank. This allows the temperature to
be kept constant throughout the entire reaction. There is a screw feeder with an attached gas inlet to dry and apply downward pressure to the system to allow for uniform
addition of the MAX powder; the mixer and thermocouple jacket are fabricated from Teflon to protect the reactor parts from being dissolved during HF-reactions. The agitator
was designed to promote more homogeneous mixing of the reaction media. (e) Images of the precursor Ti3 AlC2 MAX used in the synthesis of the 1 and 50 g Ti3 C2 T x batch
sizes. A 1 l solution of delaminated Ti3 C2 T x solution (10 mg ml−1 ) is also shown. The large-batch synthesis can produce up to 5 l of this MXene solution. Reproduced with
permission from Shuck et al., Adv. Eng. Mater. 22(3), 1901241 (2020). Copyright 2020 Wiley.

et al. used urea, dimethyl sulfoxide, hydrazine hydrate, and synthesis bottlenecks whereby few have been produced in large vol-
N,N-dimethylformamide/hydrazine hydrate mixture to treat umes. Shuck et al.60 developed a synthesis route of Ti3 C2 T x MXene
Ti3 C2 T x and found that swelling with dimethyl sulfoxide could in two batch sizes, 1 and 50 g [Figs. 1(d) and 1(e)], and deter-
obtain lamellar Ti3 C2 T x .57 Naguib et al. reported that Ti3 CNT x and mined that MXenes experience no change in structures or properties
V2 CT x can be swelled with a variety of organic bases (tetrabuty- when scaling synthesis, making them viable for further scale-up and
lammonium hydroxide, hydroxyethyl trimethylamine hydroxide, commercialization.
n-butylamine), and after simple centrifugal filtration to remove the
2. Bottom-up routes
precipitate, the dispersions of MXenes were obtained [Fig. 1(c)].58
After simple soaking of Ti3 AlC2 with HF, Xuan et al. further used Compared with the top-down approaches, bottom-up routes
tetramethylammonium hydroxide (TMAOH) to swell and etch it may produce 2D materials with fewer structural defects and cleaner
and successfully prepared Ti3 C2 T x nanosheets.59 surfaces.
Furthermore, scaling the production of synthetic MXene mate- Xu et al. have prepared 2D single-layer Mo2 C crystals via a
rials to industrial quantities has faced significant challenges due to chemical vapor deposition (CVD) method.43 Moreover, they also

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-3

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

showed that other ultrathin carbide crystals, such as tungsten and prepared by HF etching had a large number of surface defects,
tantalum carbides, could be grown by CVD with a high crystallinity which would affect the adsorption groups on the surface.64 They
and very low defect concentrations.43 This “bottom-up” strategy depicted Ti point defects including single Ti vacancy [Fig. 2(a)] and
affords materials with fewer defects and chemical adsorption groups, Ti vacancy clusters [Figs. 2(b)–2(e)]. The –O and –OH groups are
which enables the further understanding of the intrinsic properties prone to be terminated on the titanium defect site and non-defect
of MXenes. site, respectively.64
Xie et al. combined density functional theory (DFT) calcula-
III. SURFACE CHEMISTRY OF MXenes tions and experiments to shed light on the relation between sur-
face structure and preparation conditions.65 The surface of MXenes
A. Surface groups on MXenes (Ti3 C2 T x and Nb2 CT x ) from a wet chemical etching route could
Currently, high-concentration hydrofluoric acid or fluoride has be initially covered with a large amount of –OH groups and a
been used to etch the MAX phase to prepare MXene. When the MAX small fraction of –F. Then, –OH would be partially removed by the
phase was treated by the wet chemical method to etch the atoms in dehydration to form –O groups after annealed under vacuum at
the A layer, it would be positively charged on the M metal of the high temperatures (above 673 K).65 Similar conclusions were also
outer layer. As a result, functional groups are needed to achieve the obtained on Ti2 CT x . Lai et al. demonstrated that a large amount
charge balance via adsorption.61 Khazaei et al. showed through the of –OH and a small amount of –F adsorbed on Ti2 CT x from the
first-principles calculations that MXenes have a negative generation hydrofluoric acid etching method, denoted as Ti2 C(OH)x Fy ; after
energy due to the adsorbed groups on the surface. A further com- annealing, it was transformed to Ti2 COx .66 Persson et al.67 com-
parison showed that the MXene with surface adsorbed functional bined atomically resolved in situ heating in a scanning transmission
groups is thermodynamically favorable.62 Therefore, the surface of electron microscope (STEM) and simulations with temperature pro-
MXene prepared in the solution phase is not naked, but termi- grammed x-ray photoelectron spectroscopy (TP-XPS) in the room
nated by the corresponding groups adsorbed. To describe the surface temperature to 750 ○ C range to clarify the surface terminations of
groups, Ti3 C2 T x is applied to express its chemical formula, in which MXene changes with annealing temperature. As the temperature
T might be –OH, –F, and –O [Fig. 3(a)].9 increases, the F 1s spectra show that the –F desorption occurs with
Karlsson et al. found that the coverage of O-based surface heat treatment [Fig. 2(f)], while O1s spectra show gradual intensity
groups terminated on Ti3 C2 T x MXene sheets is non-uniform at the redistribution from 531.9 to 529.9 eV [Fig. 2(g)]. Through TP-XPS,
atomic level evidenced by aberration corrected STEM-EELS.63 Sang it was shown that the functional groups consist of F and O occupy-
et al. further demonstrated that the Ti3 C2 T x MXene nanosheets ing well-defied sites on the Ti3 C2 T x surfaces. F and O coordinates to

FIG. 2. Atomic-scale HAADF-STEM images of defects in single-layer Ti3 C2 T x . Comparison between the experimental HAADF-STEM image, defect crystal structure deter-
mined from DFT, and simulated HAADF-STEM image of titanium defect site (VTi ) (a) and two adjacent VTi within the same sublayer (b). Experimental HAADF-STEM images
of vacancy clusters: two adjacent VTi forming within two different sublayers (c), three VTi within the same sublayer (d), and 17 VTi within the same sublayer (e). The scale
bars are 0.5 nm. Reproduced with permission from Sang et al., ACS Nano 10, 9193–9200 (2016). Copyright 2016 American Chemical Society. TP-XPS measurements
revealing the temperature dependent behavior of (a) F 1s and (b) O 1s. Reproduced with permission from Persson et al., 2D Mater. 5(1), 015002 (2018). Copyright 2018
IOP Publishing.

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-4

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

a single site and two sites, respectively. As the temperature increases, Ti3 C2 F2 and 0.05–0.07 eV for Ti3 C2 (OH)2 .76 Naguib et al. calculated
the functional F gradually desorbs and is essentially removed at the bandgaps of Ti3 C2 T x terminated by –F and –OH on the surface
750 ○ C. Upon F desorption, the O surface atoms that coordinate to as 0.05 and 0.1 eV, respectively,9 similar to the results from the work
the alternative site, which most likely is a bridge position, migrate of Tang et al.76
to the preferred coordination vacated by the desorbed F. Further Nevertheless, the continuous electronic states crossing the
investigation revealed that O terminations can reach supersatura- Fermi level for F- and O-terminated Ti3 C2 T x indicate that their
tion with x ≈ 3.5 while maintaining the structural integrity of the conductivities are excellent. Hence, Ti3 C2 T x retains the outstand-
Ti3 C2 T x MXene sheet.68 ing electrical conductivity, even after decorated with numerous
Actually, it is a challenging task to determine the actual com- functionalities, implying its exceptional capability to transport
position of the surface terminations. At present, the common tech- carriers.77
nology to characterize surface terminations of MXene is XPS.69–71 In
addition, Raman spectroscopy (Raman),72 multinuclear solid-state
NMR spectroscopy (NMR),73 and thermal gravimetric analysis with C. Effects of surface groups on the work function
mass spectrometry analysis (TA-MS)74 have also been applied to of MXenes
analyze the surface chemistry of MXenes. Despite the limited effect on the bandgap of MXenes, a deci-
Halim et al.70 reported the in-depth analysis of the XPS spectra sive effect of surface adsorption groups on the work function can be
of the core levels of several multilayered MXenes (Ti3 C2 T x , Ti2 CT x , expected.
Ti3 CNT x , Nb2 CT x , and Nb4 C3 T x ). The surface groups present Khazaei et al. studied in detail the effect of surface adsorp-
before and after sputter-cleaning were identified and quantified. In tion groups on the properties and work functions of MXenes
all the cases, the presence of three surface terminations –O, –OH, through first-principles calculations.24 Taking Tin+1 Cn T x as an
and –F, in addition to –OH groups, relatively strongly bonded to example, the value of n has almost no effect on the work function,
H2 O molecules. The surface chemistry of MXenes is closely related while the adsorbed groups significantly influence the work func-
by etching conditions. Benchakar et al.71 clearly demonstrated that tion [Fig. 3(b)]. Liu et al. performed first-principles calculations for
the etching agent (HF, LiF/HCl, or FeF3 /HCl) strongly modifies the the work functions of 21 MXenes. It was shown that the Fermi lev-
nature of surface terminal groups (F, OH, and/or O), oxidation sen- els/work functions of various MXenes had a similar dependence on
sitivity, delamination ability, and so on. Sarycheva and Gogotsi72 their surface groups [Fig. 3(c)].25 These results indicate that both
utilized Raman spectroscopy to determine the effects of the synthe- the value of n and the type of metal M have minor effects on the
sis method, state of the material (single flakes, colloidal solution, work function of MXenes, while the surface adsorption groups are
and stacked flakes), and intercalated species on the surface chem- the decisive influential factor determining the work function. In gen-
istry of MXene. Griffith et al.73 systematically studied the chem- eral, the work function of pure MXenes is about 3–4 eV. –F groups
istry of Nb-based MAX and MXene phases with their unique elec- have little effect on their work function. If MXenes are terminated
tronic and mechanical properties via solid-state nuclear magnetic by –O, the work function could be significantly increased to about
resonance (NMR) spectroscopy. Seredych et al.74 provided detailed 6 eV, even higher than the work function of metallic Pt, indicating
insight into the surface terminations of MXenes (Ti3 C2 T x , Mo2 CT x , that –O functionalized MXenes can be an excellent electron accep-
and Nb2 CT x ) via thermal gravimetric analysis with mass spectrom- tor. It is interesting that if MXenes are terminated by –OH groups,
etry analysis (TA-MS) technology, enabling probing surface termi- the work functions drastically reduced to about 2 eV. Tahini et al.
nations (–OH, –O–, –F) and intercalated species (structural water further demonstrated that the work function of MXenes is strongly
and salts). When studying the surface chemistry of MXene materials dependent on the terminating functional groups, which is induced
and its related effects on their properties, researchers should adopt by surface dipoles and Fermi level shifts.78 The work function dif-
as many analytical technologies and objective evaluation as possible ference relative to the bare MXene shows a linear relationship with
to avoid drawing farfetched conclusion. respect to the surface dipole moment [Fig. 3(d)]. These theoretical
The surface groups of MXenes depend not only on the post- results suggest that MXenes can be a highly tunable carrier trans-
heat treatment but also on how MXenes are dispersed. DFT calcu- mitter to fulfill the diverse design of electronic devices and novel
lations revealed that the structural stability of MXenes was closely materials involving carrier manipulation.
related to the pH value. Taking Ti3 C2 T x as an example, when the pH It is worth noting that the terminations on MXenes are known
value was 0, –O and –OH coexisted on the surface; as the pH value to be randomly distributed over the surfaces, with limited experi-
increased, –OH would be gradually removed and, finally, Ti3 C2 Ox mental control over their composition. Unfortunately, plenty of the-
would be formed.75 oretical investigations into MXene materials generally suffer from
modeling only one termination species at a time and/or with full
coverage so far. Caffrey addressed this issue with mixed termina-
B. Effects of surface groups on the bandgap tions or surface coverage to compare the structural and electronic
of MXenes properties of two common MXenes, namely, Ti3 C2 T 2 and V2 CT 2 ,
Although the bandgap of MXenes is close to zero, they can be with both uniform terminating groups and explicitly mixed termina-
tuned by their surface adsorption groups to some extent. The DFT tions.79 The work functions of the uniformly terminated structures,
calculation by Tang et al. showed that naked Ti3 C2 has a high elec- the average value of the mixed terminated structures, and the value
tron density close to the Fermi level, thus exhibiting metallic prop- found by taking a weighted average of the uniformly terminated
erties.76 When –F and –OH are adsorbed on the surface, the energy structures were calculated [Fig. 3(e)]. As expected, the values for the
band of Ti3 C2 T x changes to deliver a bandgap of 0.03–0.04 eV for uniformly terminated surfaces are in good agreement with previous

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-5

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

FIG. 3. (a) Schematic of Ti3 C2 T x and surface terminated groups. Reproduced with permission from Shahzad et al., Science 353(6304), 1137–1140 (2016).176 Copyright 2016
American Association for the Advancement of Science, AAAS. (b) Work functions of bare and functionalized Tin+1 Cn T x with F, OH, and O chemical groups. Reproduced
with permission from Khazaei et al., Phys. Rev. B 92(7), 075411 (2015). Copyright 2015 American Physical Society. (c) Work functions of MXenes with a bare surface, –O,
–OH, and –F termination. For comparison, work functions of Sc and Pt metals are indicated by the dashed lines. Reproduced with permission from Liu et al., J. Am. Chem.
Soc. 138(49), 15853–15856 (2016). Copyright 2016 American Chemical Society. (d) Changes in the work function upon functionalization with respect to the surface dipole
moment. Reproduced with permission from Tahini et al., Nanoscale 9(21), 7016–7020 (2017). Copyright 2017 Royal Society of Chemistry. (e) Work functions of both uniformly
and mixed terminated Ti3 C2 T 2 (blue bars) and V2 CT 2 (orange bars). The error bars on the work function calculated for the mixed terminations represent the range of values
calculated for each individual structure. Note that the work functions of bare Ti3 C2 and V2 C monolayers are 3.91 and 4.60 eV, respectively. (f) Work function calculated for
each individual surface, Φ, for Ti3 C2 T 2 (blue circles) and V2 CT 2 (orange squares), compared to the value that would be found by taking the weighted average of the uniformly
covered surfaces, Φ− . The black dashed line corresponds to the case when Φ = Φ− , and the gray shaded area shows a region within ±1 eV of this line. Reproduced with
permission from N. M. Caffrey, Nanoscale 10, 13520–13530 (2018). Copyright 2018 Royal Society of Chemistry. (g) Secondary electron cutoff (SECO) spectra of Ti3 C2 T x
annealed at different temperatures. (h) Work function values determined from the SECOs in (g) as a function of annealing temperature. Work functions obtained from DFT for
different surface terminations, calculated by using the real surface stoichiometry obtained from XPS (blue) and obtained by averaging the work functions of purely terminated
Ti3 C2 O2 , Ti3 C2 F2 , Ti3 C2 (OH)2 , and Ti3 C2 surfaces, weighted by the experimentally determined stoichiometry (red). Reproduced with permission from Schultz et al., Chem.
Mater. 31(17), 6590–6597 (2019). Copyright 2019 American Chemical Society.

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-6

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

calculations: a very high work function for structures with a uni- indicating the very strong adsorption of H∗ , while the △GH∗ of
form –O termination and an ultra-low work function for structures Ti3 C2 F2 was 1.995 eV,77 suggesting the very weak H∗ adsorption.
terminated with uniform –OH groups,24,25 while the work function Surprisingly, the △GH∗ of Ti3 C2 O2 was 0.002 83 eV,77 even closer
of Ti3 C2 T 2 monolayers (MLs) with mixed terminations is 2.46 eV. to zero than the benchmark catalyst Pt (−0.09 eV)77,78 and MoS2
Individual surfaces had work functions ranging between 1.44 and (0.08 eV).77 Ling et al.87 investigated the ∣△GH∗ ∣ and HER cat-
3.68 eV. For the V2 CT 2 monolayers with mixed terminations, the alytic activity of 17 –O terminated MXenes, including ten mono-
average work function is 4.64 eV, with the work functions of indi- metal carbides and seven bimetal carbides. Ti2 CO2 and W2 CO2 were
vidual surfaces ranging between 2.5 and 5.6 eV. Figure 3(f) compares found as the potential active HER catalysts, with the smallest ∣△GH∗ ∣
the calculated work function of each individual surface, Φ, to the of 0.12 eV.
value that would be found by taking the weighted average of the Guo et al.20 highlighted the fully oxidized 2D Zr2 CO2 and
uniformly covered surface, Φ− . It is depicted that Φ− always over- Hf2 CO2 as the candidates of photocatalysts for possible high effi-
estimates the actual work function of the Ti3 C2 T 2 surface by ∼1 eV. ciency water splitting. The ∣△GH∗ ∣ of fully oxidized vanadium car-
The average error (Φ vs Φ− ) of Ti3 C2 T 2 and V2 CT 2 was 38% and 9%, bide (V2 CO– ) MXenes and transition metal (Fe, Co, and Ni) pro-
respectively. This calculation method with mixed terminations or moted V2 CO2 were also performed by Ling et al.88 It was depicted
surface coverage was also adopted into structure–activity correlation that the pure V2 CO2 was not an ideal catalyst for HER, while ≈16.7%
of MXenes for C–H activation by Niu et al.80,81 monolayer (ML) Fe-promoted, 16.7%–25% ML Co-promoted, and
Schultz et al.82 provided direct evidence of the effects of sur- ≈25% ML Ni-promoted systems were found to be the best catalysts
face termination on the work function and electronic band structure for the HER activity with optimal ∣△GH∗ ∣ ≈ 0 eV.
of Ti3 C2 T x MXenes using a combination of ultraviolet photoemis-
sion spectroscopy (UPS), x-ray photoelectron spectroscopy (XPS), IV. SYNTHESIS OF MXene-BASED PHOTOCATALYSTS
and inverse photoemission spectroscopy (IPES) measurements of Thanks to the unique electronic properties, MXenes and their
Ti3 C2 T x after different annealing temperatures with DFT calcula- derivates have been used in photocatalytic degradation of organic
tions. The in situ XPS indicated that F occupies the face centered pollutants, hydrogen production, CO2 reduction, nitrogen fixation,
cubic adsorption site and O initially occupies the bridge site and methane dry reforming, organic synthesis, and so on. Because of
the hexagonal close-packed site, followed by a rearrangement to the the very narrow bandgap of the MXene, it cannot be directly used
face-centered cubic site after fluorine desorption at high annealing as photocatalysts. The lower thermodynamic stability of carbides
temperatures. Upon heating in vacuum, the sample work function allows for the synthesis of composites of oxides and carbon from
increases from 3.9 to 4.8 eV [Fig. 3(g)], most probably due to desorp- MXenes as precursors. Herein, we categorize these materials as
tion of water, carbon-dominated contaminations, and OH species, MXene-derived and MXene-based photocatalysts.
and decreases again at higher temperatures to 4.1 eV due to fluorine The former refers to the powder photocatalyst derivatized from
desorption. The measured work function cannot be obtained by sim- MXenes and without MXenes as ingredients of the final photocat-
ply averaging the work function values of purely terminated MXene alyst. So far, a variety of MXene derivates have been employed as
surfaces, but it can be better reproduced by modeling the real sur- photocatalysts. Ti3 C2 T x MXenes have been demonstrated as precur-
face mixed termination to account for local dipole effects [Fig. 3(h)]. sors to synthesize hybrids of TiO2 and carbon. Yuan et al.89 fabri-
This further demonstrates that theoretical calculations considering cated 2D-Layered carbon/TiO2 hybrids derived from Ti3 C2 MXenes
the mixed terminations or surface coverage will be in line with the for photocatalytic hydrogen evolution. The carbon layers provided
experimental results. electron transport channels and improved the hole–electron sep-
As a successful application, Agresti et al. recently used Ti3 C2 T x aration efficiency. Huang et al.90 prepared N-doped TiO2 @C via
MXenes with different termination groups (T x ) to adjust the per- heating ultrathin Ti3 C2 T x MXenes in the presence of nitrogen-
ovskite absorber and the TiO2 electron transport layer (ETL).83 containing cationic compounds (positively charged melamine or
The work function (Φ) of the perovskite/ETL interface has been CTAB). Han et al.91 fabricated carbon-doped TiO2 coupled with
engineered. Ultraviolet emission spectroscopy and DFT calculation g-C3 N4 (C–TiO2 /g-C3 N4 ) via a facile heat treatment of g-C3 N4 and
showed that adding Ti3 C2 T x to the halide perovskite and TiO2 layer Ti3 C2 T x . Liu et al.92 synthesized TiO2 @C/g-C3 N4 by a facile one-
could adjust Φ without affecting other electronic properties. In addi- step calcination of a mixture of Ti3 C2 T x and melamine. Wu et al.93
tion, dipoles induced by Ti3 C2 T x at the perovskite/ETL interface synthesized graphene/TiO2 /g-C3 N4 composites by one-step calcina-
could be used to change the band centering between these layers. The tion of melamine and Ti3 C2 T x .
combined effect of Φ tuning and interface engineering could sig- Although the MXene-derived photocatalysts contain semicon-
nificantly improve the performance of MXene-modified perovskite ductor oxides and MXene-derived carbon materials that acceler-
solar cells. ate the transfer and separation of electron–hole pairs, they cannot
truly reflect the role of the MXene in photocatalysis as an emerging
2D material. In this article, MXene-based photocatalysts containing
D. Effects of surface groups of MXene on ∣△GH∗ ∣
MXenes as indispensable components are mainly discussed, which
The Gibbs free energy of the intermediate adsorbed H∗ could be divided into two categories according to the composition,
(∣△GH∗ ∣) is usually regarded as a major indicator of the photocat- namely, titanium- and niobium-based MXene photocatalysts.
alytic H2 evolution reaction (HER) activity for various catalysts.84 A
∣△GH∗ ∣ value close to zero is desirable.85,86 The △GH∗ of the MXene A. Titanium-based MXene photocatalysts
is also closely related to its surface adsorption species. The DFT Titanium-based MXenes (Ti3 C2 T x , etc.) are the most widely
calculation showed that the △GH∗ of bare Ti3 C2 was −0.927 eV,77 used photocatalysts. Depending on the feature of MXenes, we

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-7

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

summarize them in four sub-sections to discuss multilayer MXene- (TBOT), and then the TiO2 nanofibers/Ti3 C2 T x MXene nanocom-
based, monolayer MXene-based, MXene quantum dot, and immo- posites were fabricated by the electrostatic self-assembly technique.
bilized MXene-based photocatalysts, respectively. Although the photocatalytic activity of these composites has been
significantly improved, due to the resistance at the interface between
1. Multilayered Ti3 C2 Tx MXene-based photocatalysts MXene and TiO2 , there is still much room for improvement in their
Multilayer MXenes here refer to the 2D carbides without photocatalytic activity.
further exfoliation, usually in the so-called accordion-like mor- The Ti3 C2 T x MXene, as a compound of titanium and carbon,
phology.61 Ti3 C2 T x photocatalysts are currently the most reported provides a natural platform for the construction of composite mate-
MXene-based photocatalyst. Starting from multilayer Ti3 C2 T x , rials of TiO2 and carbon-containing materials. The titanium atoms
TiO2 @Ti3 C2 T x composites can be synthesized with or without on Ti3 C2 T x may act as nucleation sites, allowing the growth of TiO2
adding external titanium sources during the synthesis process. photocatalysts. Therefore, an atomic-level interface heterojunction
Gao et al. and Chen et al. have synthesized TiO2 /Ti3 C2 T x between 2D Ti3 C2 T x and TiO2 can be easily formed to minimize
nanocomposites by the hydrothermal treatment of Ti3 C2 T x in the defect-induced recombination.
presence of TiSO4 and Ti(OBu)4 , respectively.94,95 Zhuang et al.96 Peng et al. successfully designed and prepared anatase
prepared TiO2 nanofibers by electrospinning tetrabutyl titanate (001)TiO2 /Ti3 C2 T x and rutile (111)TiO2-x /Ti3 C2 T x photocatalysts

FIG. 4. (a) TEM image of TiO2 /Ti3 C2 T x . [(b)–(e)] Close observations to the areas highlighted by yellow boxes in (a). [(b) and (c)] Intimate contact of layered Ti3 C2 T x with a
TiO2 crystal. (e) Growth of TiO2 perpendicular to the [001] direction of the Ti3 C2 T x sheet. (f) Tiny TiO2 crystal formed near the edge of Ti3 C2 T x . The insets (f1 ) and (f2 ) show
the lattice fringes of TiO2 and Ti3 C2 T x , respectively. The inset of (c) shows the indexed FFT image of TiO2 . The interface structure was shown in (d). (g) Initial and final
optimized interface structures simulated by DFT. The black, red, cyan, and green balls stand for C, O, Ti, and H elements, respectively. Two Ti–O–Ti bonds were labeled as
Ti1–O1–Ti2 and Ti3–O2–Ti4, whose PDOS analyses were shown in (h) and (j), respectively. (d) Reproduced with permission from Peng et al., ACS Appl. Mater. Interfaces
8(9), 6051–6060 (2016). Copyright 2016 American Chemical Society.

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-8

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

by the hydrothermal treatment of multi-layer Ti3 C2 T x as the of organic pollutants,103–106,110 water splitting,107–110 and CO2
precursor in the presence of morphology-directing reagent.22,97 reduction.108
The detailed crystallographic relationship between (001)TiO2 and In addition, g-C3 N4 /Ti3 C2 T x hybrids have been prepared by a
Ti3 C2 T x revealed the growth of TiO2 between two layers of Ti3 C2 T x one-step thermal annealing method for efficient visible-light pho-
(Fig. 4).22 A DFT calculation also suggested that chemical bonding tocatalytic hydrogen evolution.111,112 Wang et al. constructed a
could be generated at the interface through Ti–O–Ti.22 Low et al.98 microporous MIL-100(Fe)/Ti3 C2 T x composite as a non-noble metal
synthesized a rice-crust-like TiO2 /Ti3 C2 T x composite by a simple photocatalyst for the nitrogen fixation.113
annealing treatment of Ti3 C2 T x for the photocatalytic CO2 reduc- On the basis of binary multilayer Ti3 C2 T x -based photocata-
tion. Li et al.99 fabricated Ti3 C2 T x /TiO2 nanoflowers by simulta- lysts, ternary photocatalysts have also been developed to elevate the
neous oxidation and alkalization of the Ti3 C2 T x MXene. Recently, catalytic activity (Fig. 6). Peng et al. prepared Cu/TiO2 @Ti3 C2 T x 114
My Tran et al.100 and Hieu et al.101 developed an unusual synthe- and Cu2 O/TiO2 @Ti3 C2 T x 115 by an in situ photo-deposition method
sis of safflower-shaped TiO2 /Ti3 C2 T x heterostructures with three- and N, N-dimethylformamide (DMF) reduction method on the
dimensional (3D) porous frameworks and the Ti3 C2 T x -TiO2 com- (001)TiO2 @Ti3 C2 T x support, respectively. The introduction of
posite with a unique structure initiated from the two-dimensional Cu or Cu2 O improved their photocatalytic hydrogen produc-
Ti3 C2 T x MXene toward photocatalytic degradation of pollutants, tion performance. TMDs, as excellent co-catalysts for hydro-
respectively. Figure 5 summarizes the morphology of MXene–TiO2 gen evolution, have been applied to enhance the photocatalytic
hybrids reported in the literature. activity of (001)TiO2 @Ti3 C2 T x . This strategy has been demon-
Other binary multilayer Ti3 C2 T x -based photocatalysts have strated effective for MoS2 ,116 molybdenum vacancy rich MoS2
also been reported. Deng et al. developed a SrTiO3 /Ti3 C2 T x (Mox S),117 1T-WS2 ,118 and ZnIn2 S4 ,119 as illustrated in Fig. 6.
heterostructure by the superficial partly oxidation followed by the In addition, the strategy also worked well to boost the activ-
hydrothermal treatment in alkaline solution from multilayered ity of particulate TiO2 @Ti3 C2 T x , on which TiO2 photocata-
Ti3 C2 T x as a photocatalyst for efficiently photocatalytic reduction lysts have not preferentially exposed crystal planes. Among the
and removal of U(VI).102 In addition, Bi3 TaO7 /Ti3 C2 T x hybrids,103 ternary composite photocatalysts, CdS@Ti3 C2 T x @TiO2 ,120 quasi-
flower-like BiPO4 /Ti3 C2 T x ,104 Nix Mg4-x S4 (NMS) on Ti3 C2 T x core-shell In2 S3 /TiO2 @Ti3 C2 T x ,121 and BiOBr/TiO2 @Ti3 C2 T x 122
MXene nanocomposite (NMS@MXene),105 NiCo2 S4 @Ti3 C2 T x showed efficient photocatalytic degradation of phenol, methy-
photocatalyst,106 CdS/Ti3 C2 T x composite,107 Cd0.2 Zn0.8 S@Ti3 C2 Tx lene blue, rhodamine B, methyl orange, and sulfachloropyridazine.
(MXenes) nanocomposites,108 ZnS/Ti3 C2 T x hybrid,109 etc., The BPQDs/Ti3 C2 T x @TiO2 123 and UiO-66-NH2 /TiO2 @Ti3 C2 T x
composite photocatalysts have been synthesized by the similar hybrids124 were synthesized by the low-temperature hydrother-
hydrothermal or solvothermal treatment. Those materials have mal reaction and exhibited significant enhancement of the pho-
been demonstrated to be active in photocatalytic degradation tocatalytic degradation and hydrogen production reaction. Pt

FIG. 5. (a) SEM images of Ti3 C2 T x and (b)–(g) hybrids of layered Ti3 C2 T x and TiO2 prepared by different methods. Reproduced with permission from Naguib et al., ACS
Nano 6(2), 1322–1331 (2012).177 Copyright 2012 American Chemical Society. (b) Reproduced with permission from Chen et al., Ceram. Int. 46(16), 25895–25904 (2020).
Copyright 2020 Elsevier. (c) Reproduced with permission from Zhuang et al., Appl. Surf. Sci. 496, 143647 (2019). Copyright 2019 Elsevier. (d) Reproduced with permission
from Peng et al., ACS Appl. Mater. Interfaces 8(9), 6051–6060 (2016). Copyright 2016 American Chemical Society. (e) Reproduced with permission from Peng et al., Mater.
Res. Bull. 89, 16–25 (2017). Copyright 2017 Elsevier. (f) Reproduced with permission from Low et al., J. Catal. 361, 255–266 (2018). Copyright 2018 Elsevier. (g) Reproduced
with permission from Li et al., Appl. Mater. Today 13, 217–227 (2018). Copyright 2018 Elsevier.

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-9

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

FIG. 6. Hybrids of 2D Ti3 C2 T x and (001)TiO2 and their ternary composites. (a) (001)TiO2 @Ti3 C2 T x , reproduced with permission from Peng et al., ACS Appl. Mater.
Interfaces 8(9), 6051–6060 (2016). Copyright 2016 American Chemical Society. (b) Cu/(001)TiO2 @Ti3 C2 T x , reproduced with permission from Peng et al., Nano Energy
53, 97–107 (2018). Copyright 2018 Elsevier. (c) Cu2 O/(001)TiO2 @Ti3 C2 T x , reproduced with permission from Peng et al., Int. J. Hydrogen Energy 44(57), 29975–29985
(2019). Copyright 2019 Elsevier. (d) MoS2 /(001)TiO2 @Ti3 C2 T x , reproduced with permission from Li et al., Appl. Catal., B 246, 12–20 (2019). Copyright 2019 Elsevier. (e)
Mox S/(001)TiO2 @Ti3 C2 T x , reproduced with permission from Li et al., Chem. Eng. J. 383, 123178 (2020). Copyright 2020 Elsevier. (f) 1T-WS2 /TiO2 @Ti3 C2 T x , reproduced
with permission from Li et al., Nano-Micro Lett. 12(1), 6 (2020). Copyright 2020 Springer. (g) ZnIn2 S4 /TiO2 @Ti3 C2 T x , reproduced with permission from Huang et al., J. Colloid
Interface Sci. 580, 669–680 (2020). Copyright 2020 Elsevier.

nanoparticles supported on N-doped TiO2 @Ti3 C2 T x (MXene) het- reduction toxic Cr(VI) in water. The magnetic property of α-Fe2 O3
erojunctions were employed as photocatalysts for the tandem reac- made it easy to be recovered from water.
tions between aromatic nitro compounds and carboxylic acids to
produce amide products, exhibiting excellent amidation activity and 2. Monolayer Ti3 C2 Tx MXene-based photocatalysts
chemoselectivity.125 Compared with monolayer Ti3 C2 T x MXenes, the specific sur-
Besides TiO2 derived from MXenes, ternary systems using face area of the multilayer MXene-based photocatalyst is smaller,
other materials as photosensitive components have also been which limits its photocatalytic activity. It is desired to combine 2D
reported. Khan et al. have fabricated the TiO2 /g-C3 N4 /Ti3 C2 T x MXenes into photocatalysts to further improve the photocatalytic
heterojunction126 and 2D/2D/2D O-doped g-C3 N4 /layered ben- activity.
tonite (Bt)/Ti3 C2 T x heterojunction127 via self-assembly, which can Some common semiconductors have been coupled with a single
be applied to photocatalytic reforming of methane and photocat- layer Ti3 C2 T x MXene, including Ti3 C2 T x /TiO2 , Ti3 C2 T x /g-C3 N4 ,
alytic CO2 reduction under visible light, respectively. The light Ti2 CT x /g-C3 N4 , and Ti3 C2 T x /CdS hybrids. Su et al.132 synthesized
absorption and carrier separation efficiency were promoted by the Ti3 C2 T x /TiO2 composites from single-layered Ti3 C2 T x and TiO2
delaminated Ti3 C2 T x nanosheets126 and Ti3 C2 T x /Bt composite.127 nanoparticles (P25). The photocatalytic hydrogen production rate
An Ag3 PO4 /AgBr/Ti3 C2 T x composite128 was prepared by a simple of the optimized monolayer Ti3 C2 T x /TiO2 composite was over 2.5
in situ deposition ion exchange method. In this design, dual car- times higher than the multilayer counterpart [Figs. 7(a)1 –7(a)3 ].
rier transfer channels enhanced the photocatalytic activity: Ag3 PO4 Yang et al. constructed an ultrathin 2D/2D Ti3 C2 T x /g-C3 N4 hetero-
and AgBr constituted the first carrier transfer channel, and the pho- junction via direct calcination of the mixture of multilayer Ti3 C2 T x
toinduced holes transfer from Ag3 PO4 and AgBr to Ti3 C2 T x formed and urea, where urea not only acted as the gas template to exfoliate
the second carrier transfer channel. The Bi2 WO6 /g-C3 N4 /Ti3 C2 T x Ti3 C2 T x into monolayer nanosheets but also acted as the precur-
composites129 and Bi/BiOCl/Ti3 C2 T x heterojunction130 were pre- sor of g-C3 N4 . The photocatalytic CO2 reduction performance of
pared by hydrothermal/solvothermal methods for the efficient as-prepared 2D/2D Ti3 C2 T x /g-C3 N4 photocatalysts was about 8.1-
photocatalytic hydrogenation and amidation of nitroaromatics times higher than that of pure g-C3 N4 [Figs. 7(b)1 –7(b)3 ].133 Alter-
with carboxylic acids and photocatalytic degradation of antibiotic natively, the 2D/2D Ti3 C2 T x /g-C3 N4 hybrids can also be fabricated
ciprofloxacin (CIP), respectively, showing the promise of MXene- via the ultrasonic assisted self-assembly method134 and electrostatic
based photocatalysis in synthesis. layer-by layer assembly route,135 for photocatalytic degradation of
Recently, magnetic α-Fe2 O3 /ZnFe2 O4 @Ti3 C2 T x hybrids131 diclofenac and hydrogen (H2 ) evolution, respectively. In addition,
were fabricated by an ultrasonic assisted self-assembly approach for Ti2 CT x /g-C3 N4 was fabricated toward photocatalytic H2 evolution,
the photocatalytic elimination rhodamine B (RhB) pollutant and which is 14.4 times as much as that in the case using pure g-C3 N4 .136

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-10

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

FIG. 7. (a1 ) SEM and (a2 ) and (a3 ) TEM

images of Ti3 C2 T x /TiO2 . Reproduced
with permission from Su et al., ACS
Appl. Energy Mater. 2(7), 4640–4651
(2019). Copyright 2019 American Chem-
ical Society. (b1 ) SEM image, (b2 )
AFM image, and (b3 ) corresponding
height profiles of 2D/2D Ti3 C2 T x /g-C3 N4 .
Reproduced with permission from Yang
et al., Appl. Catal., B 268, 118738 (2020).
Copyright 2020 Elsevier. (c1 ) SEM, (c2 )
TEM image, and (c3 ) elemental map-
ping images of 1D/2D CdS/Ti3 C2 T x .
Reproduced with permission from Li
et al., Appl. Catal., B 269, 118783
(2020). Copyright 2020 Elsevier. (d1 )
SEM image, (d2 ) AFM image, and (d3 )
corresponding height profiles of 2D/2D
Ti3 C2 T x /Bi2 WO6 . Reproduced with per-
mission from Cao et al., Adv. Funct.
Mater. 28(21), 1800136 (2018). Copy-
right 2018 Wiley. TEM image of (e1 )
MoS2 , (e2 ) Ti3 C2 T x , and (e3 ) 2D/2D
Ti3 C2 T x /MoS2 composites. Reproduced
with permission from Zou et al., J. Haz-
ard. Mater. 413, 125424 (2021). Copy-
right 2021 Elsevier.

Since the surface of the 2D Ti3 C2 T x MXene prepared by etching method. The Schottky junction between the interface of CdS and
reaction is negatively charged, CdS positively charged due to surface Ti3 C2 T x effectively suppressed the recombination of photogener-
Cd2+ leaching can be composited facilely. 1D CdS nanorods and 2D ated charge carriers and boosted the photocatalytic activity for
CdS nanosheets have been composited with 2D Ti3 C2 T x MXenes. hydrogen evolution.
Xu’s group fabricated 1D/2D CdS/Ti3 C2 T x [Figs. 7(c)1 –7(c)3 ]137 As a category of excellent photocatalysts, bismuth-based semi-
and 2D/2D CdS/Ti3 C2 T x composites138 via a simple electrostatic conductors have also been hybridized with a monolayer Ti3 C2 T x
self-assembly method. In this design, 2D Ti3 C2 T x acts as a Janus MXene. Both 2D/2D Ti3 C2 T x /Bi2 WO6 [Figs. 7(d)1 –7(d)3 ]141 and
co-catalyst for simultaneously promoting electron-driven photore- 2D/2D Ti3 C2 T x /Bi2 MoO6 142 have been prepared via a simple one-
duction reaction and inhibiting hole-induced photocorrosion of pot in situ hydrothermal route. Thanks to the excellent carrier
semiconductor CdS. Meanwhile, 1D/2D CdS/Ti3 C2 T x 139 and 2D/2D mobility of a single-layer Ti3 C2 T x MXene and improved separation
CdS/Ti3 C2 T x 140 hybrids were also synthesized by a solvothermal efficiency of photogenerated carriers, those composites exhibited

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-11

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

excellent photocatalytic CO2 reduction141 and tetracycline degra- physicochemical properties, more abundant active edge sites, and
dation/Cr(VI) reduction activity, respectively. Recently, Li et al. better dispersibility.146,147
synthesized the 2D/2D heterostructure of ultrathin Ti3 C2 T x /BiVO4 Qiao’s group integrated Ti3 C2 Ox nanoparticles with CdS via a
nanosheets through the electrostatic interaction for the photocat- hydrothermal strategy to induce a high visible-light photocatalytic
alytic overall water splitting.143 hydrogen production activity superior to Pt/CdS.77 This unusually
More 2D/2D heterojunction photocatalysts based on Ti3 C2 T x high activity can be attributed to the synergetic effect of the highly
MXenes have been documented in the literature, including 2D/2D efficient charge separation and migration from CdS to Ti3 C2 Ox
Ti3 C2 T x /TiO2 -black phosphorus (BP) nanohybrids144 and 2D/2D nanoparticles and the rapid H2 evolution on numerous Ti3 C2 Ox
Ti3 C2 T x /CoAl-LDHs composite.145 The 2D Ti3 C2 T x MXene could nanoparticles. Ai et al. developed Ti3 C2 T x (TiO2 )@CdS/MoS2 com-
not only prolong the photoexcited electron lifetime, accelerate the posites148 and CdS@Ti3 C2 T x @CoO hierarchical tandem p–n het-
photoinduced electron transfer, and hinder the electron/hole pairs erojunctions [Figs. 8(a)1 –8(a)3 ]149 for photocatalytic hydrogen evo-
recombination but also markedly improve the stability of BP and lution in pure water. Recently, Xu et al.150 prepared 0D/1D
CoAl-LDHs. Ti3 C2 Ox /TiO2 nanowire photocatalysts through a facile hydrother-
mal method and post-annealing processes [Figs. 8(b)1 and 8(b)2 ],
3. Ti3 C2 Tx MXene nanodot-based photocatalysts showing excellent photocatalytic activity and selectivity for selec-
Theoretical and experimental studies have shown that zero tive oxidation of benzyl alcohol with molecular oxygen under visible
dimensional nanodots or quantum dots (QDs) may exhibit dis- light. The Ti3 C2 Ox nanodots not only contributed to the enhance-
tinct properties compared to their 2D counterparts, such as ment of optical absorption but also improved the electrical conduc-
bandgap widening due to quantum confinement, better tunability in tivity of the material. In addition, the Ti3 C2 T x MXene nanoparticles

FIG. 8. (a1 ) SEM and (a2 ) and (a3 ) TEM images of CdS@Ti3 C2 T x @CoO. Reproduced with permission from Ai et al., Chem. Eng. J. 383, 123130 (2020). Copyright 2020
Elsevier. (b1 ) and (b2 ) TEM images of 0D/1D Ti3 C2 Ox /TiO2 nanowires. Reproduced with permission from Xu et al., J. Catal. 383, 1–12 (2020). Copyright 2020 Elsevier.
(c1 ) SEM and (c2 ) and (c3 ) TEM images of Ti3 C2 T x MQDs/Cu2 O NWs/Cu. Reproduced with permission from Zeng et al., Adv. Funct. Mater. 29, 1806500 (2018). Copyright
2018 Wiley.

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-12

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

were electrostatically adsorbed on Bi2 WO6 nanoplates for efficient MQDs can also be used to decorate various 2D materials, such as
electron/hole separation.151 g-C3 N4 nanosheets156 and core/shell 2D/2D van der Waals hetero-
Recently, Ti3 C2 T x MXene quantum dots (MQDs) have been junction (TiO2 /g-C3 N4 ).157
prepared from 2D Ti3 C2 T x MXenes, with ultra-small size and
luminescence properties.152–154 The MQDs were exploited as co-
catalysts of photocatalysts. Zeng et al. incorporated Ti3 C2 T x MQDs B. Niobium-based MXene photocatalysts
onto Cu2 O nanowires through an electrostatic self-assembly strat- The Nb2 CT x MXene has been used as a co-catalyst of TiO2
egy [Figs. 8(c)1 –8(c)3 ] for solar-driven CO2 conversion.155 Ti3 C2 T x for photocatalytic water splitting. Compared with TiO2 /Ti3 C2 T x ,

FIG. 9. (a) SEM and (b)–(d) TEM images of 1D/2D Nb2 O5 @Nb2 CT x . (e) TEM images and (f) elemental mapping images of 0D/1D/2D Ag/Nb2 O5 @Nb2 CT x . Reproduced
with permission from Peng et al., Chem. Eng. J. 421, 128766 (2021). Copyright 2021 Elsevier. (g) SEM image and [(h) and (i)] TEM images of the CdS/Nb2 O5 /Nb2 CT x
heterojunction. Reproduced with permission from Zu et al., Appl. Catal., B 277, 119140 (2020). Copyright 2020 Elsevier.

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-13

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

TiO2 /Nb2 CT x exhibited the higher photocatalytic hydrogen produc- (O termination always increases Φ, even higher than Pt).24,25
tion activity.158 Moreover, since Nb2 O5 is a semiconductor with a The detailed crystallographic relationship between (001)TiO2 and
bandgap of 3.1–4.0 eV showing considerable photocatalytic activity, Ti3 C2 T x revealed the growth of TiO2 between two layers of Ti3 C2 T x
niobium-based MXenes (Nb2 CT x , etc.) are emerging as an attractive (Fig. 4). At the interface, Ti3 C2 and TiO2 connect seamlessly on the
platform to synthesize niobium-based MXene photocatalysts. atomic level, benefited from the small mismatch between (103) of
A Nb2 O5 /C/Nb2 CT x composite was synthesized by CO2 oxi- Ti3 C2 T x and (11-1) of TiO2 .22 A DFT calculation also suggested
dation of Nb2 CT x and applied to photocatalytic hydrogen evolu- that chemical bonding could be generated at the interface through
tion.159 Nb2 O5 /C/Nb2 CT x /g-C3 N4 heterojunctions were obtained Ti–O–Ti. Depending on whether the oxygen atom origins from
by means of simple calcination of the mixture of Nb2 O5 /C/Nb2 CT x TiO2 or –OH, two Ti–O–Ti bonds could be formed, both of which
and melamine for nitrogen photo-fixation.160 Subsequently, rod-like contributed to the interface formation via overlapping of the Ti
Nb2 O5 /Nb2 CT x composites and ternary CdS/Nb2 O5 /Nb2 CT x het- d-orbital and O p-orbital.22 Low et al.98 synthesized the rice-crust-
erojunctions [Figs. 9(g)–9(i)]161 were fabricated from Nb2 CT x as like TiO2 /Ti3 C2 T x composite by a simple annealing treatment of
the precursor, which were applied to the degradation of organic Ti3 C2 T x for the photocatalytic CO2 reduction. Li et al.99 fabricated
pollutants. Ti3 C2 T x /TiO2 nanoflowers by simultaneous oxidation and alkaliza-
Recently, Peng et al.23 grew 1D Nb2 O5 nanorod arrays along the tion of Ti3 C2 T x MXenes. Figure 5 summarizes the morphology of
[001] direction on the 2D Nb2 CT x MXene via a simple hydrothermal MXene–TiO2 hybrids reported in the literature, and the Gibbs free
reaction. Ag nanoparticles (NPs) on Nb2 O5 nanorods were subse- energy of the hydrogen evolution reaction (∣△GH∗ ∣) of the –O ter-
quently loaded by the photodeposition method to form 0D/1D/2D minated MXene was close to the ideal value (0 eV) [Fig. 10(a)],75
Ag/Nb2 O5 @Nb2 CT x nanohybrids [Figs. 9(a)–9(f)]. In this design, so the –O terminated MXene acted as an electron acceptor in the
photogenerated holes and electrons generated from the highly active photocatalytic reaction.
Nb2 O5 nanorods could be separated by 2D Nb2 CT x and 0D Ag The –O terminated Ti3 C2 Ox was demonstrated that greatly
NPs as traps of holes and electrons, respectively. This 0D/1D/2D enhanced charge separation, photoelectron chemical response,
hierarchical structure guaranteed the efficient separation of pho- and the photocatalytic uranium (VI) removal activity of SrTiO3 .
togenerated carriers and the highly active HER over metallic Ag Ti3 C2 Ox has a great possibility to be used as an exceptional cocata-
NPs. lyst because of its promising electron transportation ability, excellent
MXenes exhibit a significant photothermal (light-to-heat con- electrical conductivity, and large work function. A Schottky bar-
version) effect.162,163 Wu et al.164 applied the Ni/Nb2 CT x catalyst to rier has been formed in the interface of Ti3 C2 Ox /SrTiO3 , in which
hydrogenate CO2 and found that the Nb2 CT x MXene had a pho- Ti3 C2 Ox acted as an electron reservoir, suppressing the recombina-
tothermal effect and thus boosted the photothermal catalytic activity tion of photogenerated e− /h+ pairs of SrTiO3 , thereby enhancing the
of Ni nanoparticles. photocatalytic activity [Fig. 10(b)].102
The Ti3 C2 Ox nanoparticles were integrated on CdS to induce
a super high visible-light photocatalytic hydrogen production activ-
V. CATALYTIC MECHANISM OF MXene-BASED ity of 14342 μmol h−1 g−1 , which is even higher than that of Pt/CdS.
PHOTOCATALYST Since the original EF of n-type CdS [slightly lower than its CB posi-
As the bandgap of various MXene adsorbing different surface tion of −0.91 V vs Standard Hydrogen Electrode (SHE)] was much
groups was close to zero,76 the role of MXenes in the photocat- more negative than the original EF of Ti3 C2 Ox (1.88 V vs SHE), the
alytic reaction was similar to metal. In MXene-based hybrid photo- intimate interfacial CdS/Ti3 C2 Ox led to the electron transfer from
catalysts, the superior electrical conductivity and ultra-high carrier CdS to Ti3 C2 Ox ; meanwhile, band bent “upward” of CdS and a
mobility of MXenes improved the spatial separation efficiency of Schottky junction of CdS and Ti3 C2 Ox were formed. The Schottky
electron–hole pairs generated in semiconductors, thereby improv- junction could serve as an electron trapping to efficiently capture
ing the quantum efficiency and photocatalytic activity of the pho- the photoinduced electrons, without impeding the electron trans-
tocatalyst. Because the electronic properties (work function Φ and fer from CdS to Ti3 C2 Ox [Fig. 10(d)]. After being transferred to
Gibbs free energy of hydrogen evolution ∣△GH∗ ∣) of the MXene Ti3 C2 Ox , the photogenerated electrons were further rapidly shuttled
with different termination groups were completely different,24,25,75 to the Ti3 C2 Ox surface and reduced the protons to hydrogen pro-
its performance in photocatalytic reactions was also completely dif- duction reaction, which could be attributed to the excellent metallic
ferent. At present, the reaction mechanism of MXenes in the pho- conductivity and minimum overpotential for H2 evolution.77
tocatalytic reaction was mainly divided into the following three The types of adsorption groups on the surface of MXenes,
types. which prepared by wet chemical etching method might be –OH, –O,
and –F, coexist. After treatment by high temperature annealing, the
surface –F and adjacent –OH would be removed and dehydrated,
A. As an electronic promoter respectively. Then, the surface terminated group mainly became to
For a large number of noble metal based cocatalysts, platinum be –O dominated.65,66
(Pt) had a greater work function (Φ, 5.65 eV) and minimum Gibbs The Ti3 C2 Ox /TiO2 nanowires were prepared by hydrothermal
free energy of the hydrogen evolution reaction (∣△GH∗ ∣) and was the and post-annealing treatment for photocatalytic oxidation of aro-
most attractive cocatalyst.165 matic alcohols to aldehydes. During the reaction, Ti3 C2 Ox was con-
MXene adsorbed –O (such as Ti3 COx ) exhibited an out- sidered as a metallic material because of its very narrow bandgap
standing electrical conductivity and exceptional capability to trans- and high carrier mobility. The photoinduced e− on the CB of TiO2
port photogenerated electrons77 and had a high work function nanowires could rapidly migrate to Ti3 C2 Ox with a high work

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-14

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

FIG. 10. (a) Volcano curve of exchange current (i0 ) as a function of the average Gibbs free energy of hydrogen adsorption (∣△GH∗ ∣). Reproduced with permission from Gao
et al., ACS Catal. 7(1), 494–500 (2017). Copyright 2017 American Chemical Society. (b) Photocatalytic mechanism and charge transfer processes of the Ti3 C2 Ox /SrTiO3
hybrid system under simulated sunlight irradiation. The photogenerated electrons and holes were marked by red (−) and blue (+) spheres, respectively. Reproduced with
permission from Deng et al., ACS Appl. Nano Mater. 2(4), 2283–2294 (2019). Copyright 2019 American Chemical Society. (c) Charge transfer of TiO2 –Ti3 C2 T x /Ru in the
photocatalytic process. Reproduced with permission from Liu et al., ACS Nano 14(10), 14181–14189 (2020). Copyright 2020 American Chemical Society. (d) Proposed
mechanism for photocatalytic H2 production in the CdS/Ti3 C2 Ox system under visible-light illumination. The green sphere denotes H+ . White, gray, red, yellow, cyan, and
gold spheres denote H, C, O, S, Ti, and Cd atoms, respectively. Reproduced with permission from Ran et al., Nat. Commun. 8, 13907 (2017). Copyright 2017 Nature
Publishing Group. (e) Proposed mechanism of the photocatalytic selective oxidation of benzyl alcohol over the Ti3 C2 Ox /TiO2 nanowire photocatalyst. Reproduced with
permission from Xu et al., J. Catal. 383, 1–12 (2020). Copyright 2020 Elsevier.

function (Φ), and the energy band of TiO2 nanowires was bent a similar electron trapping mechanism in the photocatalytic hydro-
“upward” and established a Schottky barrier through their interfaces gen production reaction.99 The TiO2 –Ti3 C2 T x /Ru photocatalyst
[Fig. 10(e)], which would promote the separation of photogenerated was fabricated by in situ formation of TiO2 nanosheets on
electron–hole pairs.150 the Ti3 C2 T x /Ru toward photocatalytic H2 evolution. The lower
The Ti3 C2 Ox /TiO2 nanoflowers were fabricated by oxida- Fermi level of the nanoconfined Ti3 C2 T x /Ru cocatalyst enabled
tion alkalization, ion exchange, and post-heat treatment exhibited it to accept electrons for H2 evolution, meanwhile maintaining a

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-15

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

stable surface structure. The separation of electron–hole pairs played co-catalysts (such as CoOx )168 and also was unlikely to act as a
a decisive role in the photocatalytic reaction of TiO2 –Ti3 C2 T x /Ru passivation layer169 to suppress the surface recombination because
[Fig. 10(c)].166 the wrapping of the TiO2 semiconductor by MXenes has not
Surface oxygen terminated Ti3 C2 Ox integrated g-C3 N4 could been observed [Fig. 11(e)].22,97,114,115 Subsequently, the hole trap-
improve the separation of electron–hole pairs, resulting in a 105% ping mechanism was also reported in the PtO@Ti3 C2 T x /TiO2 com-
enhancement in the production ratio of hydrogen evolution com- posite [Fig. 11(g)],170 BiPO4 /Ti3 C2 T x hybrid,104 BiOBr/Ti3 C2 T x
pared with the control samples, and the increased HER activity was heterojunction [Fig. 11(h)],110 BiVO4 /Ti3 C2 T x [Fig. 11(i)],171 and
attributed to the more hydrogen evolution active sites of the –O ter- MoS2 /Ti3 C2 T x and MoS2 /Ti3 C2 T x. 172
minated Ti3 C2 Ox , and the electron trapping of Ti3 C2 Ox improved A novel ternary Ag3 PO4 /AgBr/Ti3 C2 Tx photocatalyst was pre-
the separation of the electron–hole pairs.112 pared and applied to photocatalytic degradation of pollutants, and
However, the electron transfer and trapping mechanism still the calculated work function (Φ) values of Ag3 PO4 and AgBr were
had many defects. On one hand, these studies did not clar- 5.16 and 4.75 eV, respectively; the calculated Φ values of Ti3 C2 T x
ify that the surface of the MXene was indeed –O adsorbed on range from 3.4 to 4.2 eV, and their corresponding Fermi level (EF )
surface chemistry techniques; on the other hand, this interfacial value was −5.16, −4.75, and −4.2∼-3.4 eV, respectively. In other
charge mechanism is judged by DFT theoretical calculations, lacking words, the EF value of the Ti3 C2 T x MXene was more positive than
in situ spectroscopy technology, transient technology, or in situ that of AgBr/Ag3 PO4 . When AgBr and Ag3 PO4 contacted with
photodeposition to confirm the direction of photogenerated charge Ti3 C2 T x to form the Schottky barrier, the photogenerated holes of
transfer. AgBr and Ag3 PO4 transferred to the Ti3 C2 T x MXene, rather than
photoexcited electrons. In situ irradiated x-ray photoelectron spec-
troscopy (ISI-XPS) was conducted to determine the hole trapping
B. As a hole promoter mechanism by the change of binding energy. After the illumina-
Contrary to the –O terminated MXene, the surface –OH tion of Ag3 PO4 /AgBr/Ti3 C2 T x , the signal of Ti–C had a positive
adsorption MXene exhibited an ultra-low work function; on the shift, while the Ag 3d peak had an obviously negative migration,
other hand, the –OH terminated MXene still had a high carrier which indicated that the hole density in Ti3 C2 T x has increased and
mobility. Therefore, the –OH terminated MXene exhibited com- reduced in Ag3 PO4 and AgBr, which exactly demonstrated that
pletely different characteristics between –O terminated MXenes in photogenerated holes transferred from Ag3 PO4 /AgBr to Ti3 C2 T x
the photocatalytic reaction. [Figs. 12(a)–12(c)].128
X-ray diffraction and inelastic neutron scattering indicated that The Ti3 C2 T x MXene modified hematite nanorods
the surface of the MXene prepared by the wet chemical etching (α-Fe2 O3 /MXene NRs) were fabricated with enhanced photo-
method adsorbed a large amount of –OH.65 Peng et al. demon- electrochemical (PEC) performance. In situ ultrafast transient
strated the presence of –OH on the surface of the MXene pre- absorbance spectra (TAS) of different α-Fe2 O3 NRs demonstrated
pared by the wet chemical method through the x-ray photoelectron that an intra-bandgap state absorption signal at ∼576 nm were
spectroscopy(XPS) and characterized the work function (Φ) of the observed with a decay, which was dominated by the absorption
–OH adsorbed MXene for the first time through UV photoelec- of photogenerated holes. The normalized TAS decays further
tron spectroscopy (UPS), and the work functions of Ti3 C2 (OH)x and proved that the duration of the photo-induced holes for optimumα-
Nb2 C(OH)x were 3.4 eV [Fig. 11(b)]114 and 2.7 eV [Fig. 11(c)],23 Fe2 O3 /MXene NRs was ten times longer than pristine α-Fe2 O3
respectively. Agresti et al. elucidated the surface groups of the NRs, which directly proved that the transfer of photogenerated
Ti3 C2 T x MXene carefully via XPS technology, the ratio between holes were transferred from α-Fe2 O3 to the MXene derived layer
the F/OH/O groups was estimated to be 1.6/0.65/0.34, and fur- [Figs. 12(d)–12(l)].173
thermore, the detected work function of the Ti3 C2 T x MXene was Recently, 0D/1D/2D Ag/Nb2 O5 @Nb2 CT x nanohybrids were
3.69 eV by ultraviolet photoelectron spectroscopy (UPS) technology toward the photocatalytic H2 evolution reaction, and a large amount
[Fig. 11(a)].83 of –OH adsorbed on the surface of Nb2 CT x [Nb2 C(OH)x ] was
Ti3 C2 (OH)x had an ultra-low work function of 3.4–3.7 eV, measured using surface chemical XPS technology; the work func-
while the work function of TiO2 was about 4.9 eV,167 which exhib- tions of Nb2 C(OH)x and Nb2 O5 were 2.7 and 3.6 eV, respectively,
ited the potential of Ti3 C2 (OH)x MXenes to be as a low-work func- which were measured by UPS technology, respectively, while the
tion hole trapper to modify the electronic property of TiO2 pho- work function of Ag was 4.7 eV.174 That is, the Fermi level posi-
tocatalysts at the interface between Ti3 C2 (OH)x and TiO2 . Specif- tions of Nb2 C(OH)x , Nb2 O5 , and Ag were −2.7, −3.6, and −4.7 eV,
ically, after TiO2 was excited, electron–hole pairs were generated, respectively, and the Fermi level position was Nb2 C(OH)x > Nb2 O5 >
the photogenerated h+ excited by TiO2 were rapidly captured by Ag. At the interface of Ag/Nb2 O5 and Nb2 O5 @Nb2 C(OH)x , two
Ti3 C2 (OH)x , and Ti3 C2 (OH)x could form a hole trapping effect. Schottky junctions were formed, and Ag and metallic Nb2 C(OH)x
Given the large gap in the work function between Ti3 C2 (OH)x acted as electron capture and hole trapping effects, respectively
and TiO2 through their interface, a Schottky barrier has been pre- [Fig. 11(f)].23
dicted by Peng et al.22,97 Therefore, this Schottky barrier could hin- The hole trapping of the –OH terminated MXene [includ-
der the electron transfer from TiO2 to Ti3 C2 (OH)x but allow the ing Ti3 C2 (OH)x and Nb2 C(OH)x ] was further illustrated by
flow of photogenerated h+ [Fig. 11(d)]. Thus, the barrier effec- in situ photodeposition technology (Fig. 13), Ag and Pt nanopar-
tively prevented the backflow of h+ from the TiO2 @Ti3 C2 (OH)x ticles were deposited mainly on the Nb2 O5 nanorods of 1D/2D
interface. In this situation, the Ti3 C2 (OH)x MXene was not an Nb2 O5 @Nb2 C(OH)x ,23 and Cu species were deposited mainly on
oxygen evolution catalyst as the widely documented metal oxide the TiO2 nanosheets of 2D/2D TiO2 @Ti3 C2 (OH)x .114

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-16

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

FIG. 11. (a) UPS spectra measured with a photon energy of 40.81 eV on the Ti3 C2 T x MXene flakes and FTO substrate supporting showing the secondary electron
cutoff. Reproduced with permission from Agresti et al., Nat. Mater. 18(11), 1228–1234 (2019). Copyright 2019 Nature Publishing Group. (b) UPS spectra of Ti3 C2 T x
and TiO2 @Ti3 C2 T x photocatalysts. Reproduced with permission from Peng et al., Nano Energy 53, 97–107 (2018). Copyright 2018 Elsevier. (c) UPS of Nb2 CT x and
Nb2 O5 @Nb2 CT x photocatalysts. Reproduced with permission from Peng et al., Chem. Eng. J. 421, 128766 (2021). Copyright 2021 Elsevier. (d) Schematic of band align-
ments and charge flows at (001)TiO2 @Ti3 C2 (OH)x interfaces. Reproduced with permission from Peng et al., ACS Appl. Mater. Interfaces 8(9), 6051–6060 (2016). Copyright
2016 American Chemical Society. (e) Charge transfer at the interface of Cu/TiO2 @Ti3 C2 (OH)x of the water splitting reaction. Reproduced with permission from Peng et al.,
Nano Energy 53, 97–107 (2018). Copyright 2018 Elsevier. (f) Charge transfer at the interface of Ag/Nb2 O5 @Nb2 C(OH)x of the water splitting reaction. Reproduced with per-
mission from Peng et al., Chem. Eng. J. 421, 128766 (2021). Copyright 2021 Elsevier. (g) Schematic photocatalytic reaction mechanism for PtO@Ti3 C2 T x /TiO2 composites
under solar light irradiation. Reproduced with permission from Yang et al., Chem. Eng. J. 420(18), 129695 (2021). Copyright 2020 Elsevier. (h) Schematic of band alignments
and charge flows at BiOBr/Ti3 C2 T x interfaces (vs NHE). Reproduced with permission from Li et al., J. Photochem. Photobiol., A 386, 112099 (2020). Copyright 2020 Elsevier.
(i) Proposed charge transfer mechanism of the BiVO4 /Ti3 C2 T x photoanodes. Reproduced with permission from Ye et al., Chem. Eng. J. 361, 853–861 (2019). Copyright
2019 Elsevier.

C. As electron–hole transporter viewpoint that the MXene mainly acted as an electron/hole transfer
bridge in photocatalytic reactions.
In addition to the above mechanisms as a hole trapping or The layered CdS@Ti3 C2 T x @TiO2 composites were fabricated
electron reservoir, there was also another interfacial charge kinetic and applied to efficient organic pollutant degradation; as the

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-17

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

FIG. 12. In situ irradiated x-ray photoelectron spectroscopy of (a) C 1s and (b) Ag 3d of the Ag3 PO4 /AgBr/Ti3 C2 T x photocatalyst. (c) Carrier transfer mechanism
for photocatalytic degradation of RhB on the Ag3 PO4 /AgBr/Ti3 C2 T x photocatalyst. Reproduced with permission from Wang et al., Sep. Purif. Technol. 253, 117486
(2020). Copyright 2020 Elsevier. (d) Schematic illustrations comparing the recombination of photoinduced charges in α-Fe2 O3 NRs (left) and α-Fe2 O3 /MXene NRs
(right). (e) Transient photocurrent responses measured at 1.23 V vs RHE. (f) Photoluminescence emission spectra under 450 nm excitation at room temperature.
Time-resolved transient absorption spectra (TAS) of (g) α-Fe2 O3 NRs, (h) Ti: α-Fe2 O3 NRs, and (i) α-Fe2 O3 /MXene NRs when excited with 400 nm light. The
color bars are in the same scale. (j)–(l) Normalized TAS decays with global fitting from 450 to 750 nm of different α-Fe2 O3 NRs after 400 nm excitation with
(j) no bias potential, (k) 0.8 V vs RHE, and (l) 1.0 V vs RHE. Reproduced with permission from Ye et al., Appl. Catal., B 291, 120107 (2021). Copyright 2021
Elsevier.

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-18

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

VI. CONCLUSIONS
MXenes exhibited an excellent conductivity, a high specific
surface area, and unique physiochemical properties.175 Notably,
the work function (Fermi level) and ∣△GH∗ ∣ of the MXene heav-
ily depended on the surface terminated groups. This article sum-
marized the preparation and characteristics of MXenes (Ti3 C2 T x ,
Nb2 CT x , etc.) and their composites and focused on the structure,
surface terminated group, fabrication, performance, and interfacial
charge kinetics of the MXene-based photocatalyst.
In order to meet the application requirements of MXene-based
photocatalysts in the photocatalytic reaction of degradation pollu-
tants, water splitting, CO2 reduction, and organic synthesis, there
would be still many challenges ahead, which are as follows:
(a) The surface terminated group and defects of MXenes would
inevitably be produced through the preparation process, and
the fabrication scheme is not friendly to the environment.
Moreover, the types of surfaced adsorbed groups of MXenes
have a decisive influence on the electronic properties of
MXenes and their role in photocatalytic reactions. Therefore,
how to prepare MXenes on a large scale with low cost and
high efficiency while freely controlling the surface functional
groups is a key issue that needs to be solved.
FIG. 13. (a) STEM image and EDS elemental mapping of Cu/TiO2 @Ti3 C2 (OH)x
(b) The photocatalytic performance of the existing MXene-based
prepared by the in situ photodeposition method. Reproduced with permission photocatalysts still has a large room for improvement. How
from Peng et al., Nano Energy 53, 97–107 (2018). Copyright 2018 Elsevier. (b) to make good use of the co-catalyst function of MXenes as
and (c) TEM images and (d) HADDF-STEM image/EDX elemental mapping of a guide to prepare high-efficiency MXene-based photocata-
Pt/Nb2 O5 @Nb2 C(OH)x . Reproduced with permission from Peng et al., Chem. Eng. lysts, such as MXene quantum dot (MQD) photocatalysts,
J. 421, 128766 (2021). Copyright 2021 Elsevier. is very important. On the other hand, the application range
of the MXene-based photocatalyst should be broadened, for
example, applying it to the overall water splitting reaction.
conduction band (CB) of TiO2 [−0.25 V vs Normal Hydrogen Elec- (c) The surface terminated groups of MXenes have a crucial
trode (NHE)] was more negative than Ti3 C2 T x (−0.15 V), the photo- influence on the electronic properties and interfacial charge
generated electrons could be easily transferred from the CB of TiO2 transfer mechanism of MXene-based photocatalysts. How-
to Ti3 C2 T x , while the photogenerated holes from the valence band ever, the current research on the surface chemistry and inter-
of CdS migrated to Ti3 C2 T x . The Ti3 C2 T x MXene played the role of facial carrier dynamics of MXene-based photocatalysts is still
a carrier transporter in the CdS@Ti3 C2 T x @TiO2 hybrid.120 insufficient, and there are controversies between the existing
The Bi2 WO6 /g-C3 N4 /Ti3 C2 T x composite could be used as a studies. Therefore, more in situ photoelectron-chemical anal-
photocatalyst for efficient degradation of ciprofloxacin and hydro- ysis and time-resolved characterization techniques should
gen evolution. The ECB and EVB of Bi2 WO6 were determined to be applied to clarify the interfacial charge transfer mecha-
be 0.03 and 2.61 eV (vs NHE), respectively, while the ECB and EVB nism, which will greatly helpfully guide the fabrication of a
of g-C3 N4 were measured to be −0.59 and 1.91 eV, respectively. MXene-based photocatalyst and its applicable reactions (such
After illuminated by the visible light, the photogenerated e− from as water splitting hydrogen evolution or oxygen production).
CB of Bi2 WO6 and h+ from VB of g-C3 N4 would be transferred
to the interface, and the Ti3 C2 T x MXene transmitted photogener-
ated electron/hole pairs at the interface of Bi2 WO6 and g-C3 N4 ,
which accelerated the transfer of electrons and holes, and Bi2 WO6 /g- ACKNOWLEDGMENTS
C3 N4 /Ti3 C2 T x followed the Z-scheme mechanism and enhanced the This work was supported by the National Natural Sci-
photocatalytic performance.129 ence Foundation of China (Grant No. 21802019), the Charac-
The CdS@Ti3 C2 T x @CoO hierarchical photocatalyst was fab- teristic Innovation Project of Guangdong Province University
ricated toward the photocatalytic water splitting, and Ti3 C2 T x (Grant No. 2019KTSCX185), the Youth Innovation Project of
MXenes function as a carrier bridge to build a special tandem p–n Guangdong Province University (Grant No. 2020KQNCX088), the
heterojunction where two secondary internal electric fields were set Guangdong Basic and Applied Basic Research Foundation (Grant
up and combined into the strong internal electric field existing in No. 2020A1515110427), the COVID-19 Epidemic Prevention and
the p–n heterojunction.149 As for the Ti3 C2 T x (TiO2 )@CdS/MoS2 Control Project of Wuyi University (Grant No. 2020FKZX02),
nanosphere hybrid photocatalyst, the Z-scheme between CdS and the Innovation and Entrepreneurship Training Project of Wuyi
TiO2 transformed fromTi3 C2 T x was gradually formed in the pure University (Grant No. 2020CX18), and the Education Depart-
water splitting reaction.148 ment of Guangdong Province (Grant No. 2020KSYS004). The

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-19

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

18
authors also acknowledge support from the Science and Technol- M. R. Lukatskaya, O. Mashtalir, C. E. Ren, Y. Dall’Agnese, P. Rozier, P. L.
ogy Development Fund from Macau SAR (FDCT) (Grant Nos. Taberna, M. Naguib, P. Simon, M. W. Barsoum, and Y. Gogotsi, “Cation inter-
0102/2019/A2, 0035/2019/AGJ, 0154/2019/A3, 0081/2019/AMJ, and calation and high volumetric capacitance of two-dimensional titanium carbide,”
Science 341(6153), 1502–1505 (2013).
0033/2019/AMJ) and Multi-Year Research Grants (MYRG2018- 19
M. Ghidiu, M. R. Lukatskaya, M.-Q. Zhao, Y. Gogotsi, and M. W.
00003-IAPME) from the University of Macau. Barsoum, “Conductive two-dimensional titanium carbide ‘clay’ with high volu-
metric capacitance,” Nature 516(7529), 78–81 (2014).
DATA AVAILABILITY 20
Z. Guo, J. Zhou, L. Zhu, and Z. Sun, “MXene: A promising photocatalyst for
water splitting,” J. Mater. Chem. A 4(29), 11446–11452 (2016).
Data sharing is not applicable to this article as no new data were 21
M. Khazaei, A. Ranjbar, M. Arai, T. Sasaki, and S. Yunoki, “Electronic proper-
created or analyzed in this study. ties and applications of MXenes: A theoretical review,” J. Mater. Chem. C 5(10),
2488–2503 (2017).
22
REFERENCES C. Peng, X. Yang, Y. Li, H. Yu, H. Wang, and F. Peng, “Hybrids of two-
dimensional Ti3 C2 and TiO2 exposing {001} facets toward enhanced photocat-
1
P. Miró, M. Audiffred, and T. Heine, “An atlas of two-dimensional materials,” alytic activity,” ACS Appl. Mater. Interfaces 8(9), 6051–6060 (2016).
23
Chem. Soc. Rev. 43(18), 6537–6554 (2014). C. Peng, X. Xie, W. Xu, T. Zhou, P. Wei, J. Jia, K. Zhang, Y. Cao, H.
2
G. R. Bhimanapati, Z. Lin, V. Meunier, Y. Jung, J. Cha, S. Das, D. Xiao, Y. Son, M. Wang, F. Peng, R. Yang, X. Yan, H. Pan, and H. Yu, “Engineering highly
S. Strano, V. R. Cooper, L. Liang, S. G. Louie, E. Ringe, W. Zhou, S. S. Kim, R. R. active Ag/Nb2 O5 @Nb2 CTx (MXene) photocatalysts via steering charge kinetics
Naik, B. G. Sumpter, H. Terrones, F. Xia, Y. Wang, J. Zhu, D. Akinwande, N. Alem, strategy,” Chem. Eng. J. 421, 128766 (2021).
24
J. A. Schuller, R. E. Schaak, M. Terrones, and J. A. Robinson, “Recent advances M. Khazaei, M. Arai, T. Sasaki, A. Ranjbar, Y. Liang, and S. Yunoki, “OH-
in two-dimensional materials beyond graphene,” ACS Nano 9(12), 11509–11539 terminated two-dimensional transition metal carbides and nitrides as ultralow
(2015). work function materials,” Phys. Rev. B 92(7), 075411 (2015).
3 25
R. Tong, K. W. Ng, X. Wang, S. Wang, X. Wang, and H. Pan, “Two-dimensional Y. Liu, H. Xiao, and W. A. Goddard III, “Schottky-barrier-free contacts with
materials as novel co-catalysts for efficient solar-driven hydrogen production,” two-dimensional semiconductors by surface-engineered MXenes,” J. Am. Chem.
J. Mater. Chem. A 8(44), 23202–23230 (2020). Soc. 138(49), 15853–15856 (2016).
4 26
H. Pan, “Principles on design and fabrication of nanomaterials as photocatalysts X. Xie and N. Zhang, “Positioning MXenes in the photocatalysis landscape:
for water-splitting,” Renewable Sustainable Energy Rev. 57, 584–601 (2016). Competitiveness, challenges, and future perspectives,” Adv. Funct. Mater. 30(36),
5
M. Shao, Y. Shao, S. Ding, R. Tong, X. Zhong, L. Yao, W. F. Ip, B. Xu, X.-Q. 2002528 (2020).
27
Shi, Y.-Y. Sun, X. Wang, and H. Pan, “Carbonized MoS2 : Super-active co-catalyst L. Verger, C. Xu, V. Natu, H.-M. Cheng, W. Ren, and M. W. Barsoum,
for highly efficient water splitting on CdS,” ACS Sustainable Chem. Eng. 7(4), “Overview of the synthesis of MXenes and other ultrathin 2D transition metal
4220–4229 (2019). carbides and nitrides,” Curr. Opin. Solid State Mater. Sci. 23(3), 149–163 (2019).
6 28
M. Shao, Y. Shao, S. Ding, J. Wang, J. Xu, Y. Qu, X. Zhong, X. Chen, W. F. Ip, P. Eklund, J. Rosen, and P. O. Å. Persson, “Layered ternary Mn+1 AXn phases and
N. Wang, B. Xu, X. Shi, X. Wang, and H. Pan, “Vanadium disulfide decorated their 2D derivative MXene: An overview from a thin-film perspective,” J. Phys. D:
graphitic carbon nitride for super-efficient solar-driven hydrogen evolution,” Appl. Phys. 50, 113001 (2017).
Appl. Catal., B 237, 295–301 (2018). 29
P. O. Å. Persson and J. Rosen, “Current state of the art on tailoring the MXene
7
R. Tong, Z. Sun, X. Wang, S. Wang, and H. Pan, “Ultrafine WC1−x nanocrystals: composition, structure, and surface chemistry,” Curr. Opin. Solid State Mater. Sci.
An efficient cocatalyst for the significant enhancement of photocatalytic hydrogen 23(6), 100774 (2019).
evolution on g-C3 N4 ,” J. Phys. Chem. C 123(43), 26136–26144 (2019). 30
A. Sreedhar and J.-S. Noh, “Recent advances in partially and completely derived
8
M. Shao, W. Chen, S. Ding, K. H. Lo, X. Zhong, L. Yao, W. F. Ip, B. Xu, X. 2D Ti3 C2 MXene based TiO2 nanocomposites towards photocatalytic applica-
Wang, and H. Pan, “WXy /g-C3 N4 (X = C, N & S) composites for highly efficient tions: A review,” Sol. Energy 222, 48–73 (2021).
photocatalytic water splitting,” ChemSusChem 12(14), 3355–3362 (2019). 31
J. K. Im, E. J. Sohn, S. Kim, M. Jang, A. Son, K.-D. Zoh, and Y. Yoon, “Review
9
M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. Niu, M. Heon, L. Hultman, of MXene-based nanocomposites for photocatalysis,” Chemosphere 270, 129478
Y. Gogotsi, and M. W. Barsoum, “Two-dimensional nanocrystals produced by (2021).
exfoliation of Ti3 AlC2 ,” Adv. Mater. 23(37), 4248–4253 (2011). 32
V. M. Hong Ng, H. Huang, K. Zhou, P. S. Lee, W. Que, J. Z. Xu, and L.
10
M. W. Barsoum, “The Mn+1 AXn phases: A new class of solids: Thermodynami- B. Kong, “Recent progress in layered transition metal carbides and/or nitrides
cally stable nanolaminates,” Prog. Solid State Chem. 28, 201–281 (2000). (MXenes) and their composites: Synthesis and applications,” J. Mater. Chem. A
11
Q. Ye, P. Xiao, W. Liu, K. Chen, T. Chen, J. Xue, S. Du, and Q. Huang, 5(7), 3039–3068 (2017).
33
“Exploring the potential of exfoliated ternary ultrathin Ti4 AlN3 nanosheets for T. P. Nguyen, D. M. Tuan Nguyen, D. L. Tran, H. K. Le, D.-V. N. Vo, S. S. Lam,
fabricating hybrid patterned polymer brushes,” RSC Adv. 5(86), 70339–70344 R. S. Varma, M. Shokouhimehr, C. C. Nguyen, and Q. V. Le, “MXenes: Appli-
(2015). cations in electrocatalytic, photocatalytic hydrogen evolution reaction and CO2
12
H. D. Lee and W. T. Petuskey, “New ternary nitride in the Ti-Al-N system,” reduction,” Mol. Catal. 486, 110850 (2020).
34
J. Am. Ceram. Soc. 80(3), 604–608 (1997). A. D. Handoko, S. N. Steinmann, and Z. W. Seh, “Theory-guided materi-
13
T. Rackl and D. Johrendt, “The MAX phase borides Zr2 SB and Hf2 SB,” Solid als design: Two-dimensional MXenes in electro- and photocatalysis,” Nanoscale
State Sci. 106, 106316 (2020). Horiz. 4(4), 809–827 (2019).
14 35
T. Rackl, L. Eisenburger, R. Niklaus, and D. Johrendt, “Syntheses and physical L. Biswal, S. Nayak, and K. Parida, “Recent progress on strategies for the prepa-
properties of the MAX phase boride Nb2 SB and the solid solutions Nb2 SBx C1−x ration of 2D/2D MXene/g-C3 N4 nanocomposites for photocatalytic energy and
(x = 0-1),” Phys. Rev. Mater. 3(5), 054001 (2019). environmental applications,” Catal. Sci. Technol. 11(4), 1222–1248 (2021).
15 36
M. Naguib, V. N. Mochalin, M. W. Barsoum, and Y. Gogotsi, “25th anniversary Á. Morales-García, F. Calle-Vallejo, and F. Illas, “MXenes: New horizons in
article: MXenes: A new family of two-dimensional materials,” Adv. Mater. 26(7), catalysis,” ACS Catal. 10(22), 13487–13503 (2020).
37
992–1005 (2014). P. Eklund, M. Beckers, U. Jansson, H. Högberg, and L. Hultman, “The Mn+1 AXn
16
B. Anasori, M. R. Lukatskaya, and Y. Gogotsi, “2D metal carbides and nitrides phases: Materials science and thin-film processing,” Thin Solid Films 518(8),
(MXenes) for energy storage,” Nat. Rev. Mater. 2(2), 16098 (2017). 1851–1878 (2010).
17 38
J. Peng, X. Chen, W.-J. Ong, X. Zhao, and N. Li, “Surface and heterointerface B. Anasori, Y. Xie, M. Beidaghi, J. Lu, B. C. Hosler, L. Hultman, P. R. C. Kent,
engineering of 2D MXenes and their nanocomposites: Insights into electro- and Y. Gogotsi, and M. W. Barsoum, “Two-dimensional, ordered, double transition
photocatalysis,” Chem 5(1), 18–50 (2019). metals carbides (MXenes),” ACS Nano 9(10), 9507–9516 (2015).

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-20

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

39 57
I. Persson, A. El Ghazaly, Q. Tao, J. Halim, S. Kota, V. Darakchieva, J. Palisaitis, O. Mashtalir, M. Naguib, V. N. Mochalin, Y. Dall’Agnese, M. Heon, M. W.
M. W. Barsoum, J. Rosen, and P. O. A. Persson, “Tailoring structure, composi- Barsoum, and Y. Gogotsi, “Intercalation and delamination of layered carbides and
tion, and energy storage properties of MXenes from selective etching of in-plane, carbonitrides,” Nat. Commun. 4, 1716 (2013).
chemically ordered MAX phases,” Small 14(17), e1703676 (2018). 58
Michael et al., “Large-scale delamination of multi-layers transition metal car-
40
Q. Tao, M. Dahlqvist, J. Lu, S. Kota, R. Meshkian, J. Halim, J. Palisaitis, L. bides and carbonitrides “MXenes”,” Dalton Trans. 44, 9253–9358 (2015).
Hultman, M. W. Barsoum, P. O. Å. Persson, and J. Rosen, “Two-dimensional 59
J. Xuan, Z. Wang, Y. Chen, D. Liang, L. Cheng, X. Yang, Z. Liu, R. Ma,
Mo1.33 C MXene with divacancy ordering prepared from parent 3D laminate with T. Sasaki, and F. Geng, “Organic-base-driven intercalation and delamination
in-plane chemical ordering,” Nat. Commun. 8, 14949 (2017). for the production of functionalized titanium carbide nanosheets with superior
41
S. K. Nemani, B. Zhang, B. C. Wyatt, Z. D. Hood, S. Manna, R. Khaledialidusti, photothermal therapeutic performance,” Angew. Chem. 128(47), 14789–14794
W. Hong, M. G. Sternberg, S. Sankaranarayanan, and B. Anasori, “High-entropy (2016).
2D carbide MXenes,” 10.26434/chemRxiv:14346953.v1 (2021). 60
C. E. Shuck, A. Sarycheva, M. Anayee, A. Levitt, Y. Zhu, S. Uzun, V. Balitskiy, V.
42
W. Bao, X.-G. Wang, H. Ding, P. Lu, C. Zhu, G.-J. Zhang, and F. Xu, Zahorodna, O. Gogotsi, and Y. Gogotsi, “Scalable synthesis of Ti3 C2 Tx MXene,”
“High-entropy M2 AlC-MC (M = Ti, Zr, Hf, Nb, Ta) composite: Synthesis and Adv. Eng. Mater. 22(3), 1901241 (2020).
microstructures,” Scr. Mater. 183, 33–38 (2020). 61
M. Naguib and Y. Gogotsi, “Synthesis of two-dimensional materials by selective
43
C. Xu, L. Wang, Z. Liu, L. Chen, J. Guo, N. Kang, X.-L. Ma, H.-M. Cheng, and extraction,” Acc. Chem. Res. 48(1), 128–135 (2015).
W. Ren, “Large-area high-quality 2D ultrathin Mo2 C superconducting crystals,” 62
M. Khazaei, M. Arai, T. Sasaki, C.-Y. Chung, N. S. Venkataramanan, M. Estili,
Nat. Mater. 14(11), 1135–1141 (2015). Y. Sakka, and Y. Kawazoe, “Novel electronic and magnetic properties of two-
44
M. Alhabeb, K. Maleski, T. S. Mathis, A. Sarycheva, C. B. Hatter, S. Uzun, dimensional transition metal carbides and nitrides,” Adv. Funct. Mater. 23(17),
A. Levitt, and Y. Gogotsi, “Selective etching of silicon from Ti3 SiC2 (MAX) to 2185–2192 (2013).
obtain 2D titanium carbide (MXene),” Angew. Chem., Int. Ed. 57(19), 5444–5448 63
L. H. Karlsson, J. Birch, J. Halim, M. W. Barsoum, and P. O. Å. Persson,
(2018). “Atomically resolved structural and chemical investigation of single MXene
45
J. Halim, M. R. Lukatskaya, K. M. Cook, J. Lu, C. R. Smith, L.-Å. Näslund, S. sheets,” Nano Lett. 15(8), 4955–4960 (2015).
64
J. May, L. Hultman, Y. Gogotsi, P. Eklund, and M. W. Barsoum, “Transparent X. Sang, Y. Xie, M. W. Lin, M. Alhabeb, K. L. Van Aken, Y. Gogotsi, P. R.
conductive two-dimensional titanium carbide epitaxial thin films,” Chem. Mater. Kent, K. Xiao, and R. R. Unocic, “Atomic defects in monolayer titanium carbide
26(7), 2374–2381 (2014). (Ti3 C2 Tx ) MXene,” ACS Nano 10(10), 9193–9200 (2016).
46 65
A. Feng, Y. Yu, F. Jiang, Y. Wang, L. Mi, Y. Yu, and L. Song, “Fabrication and Y. Xie, M. Naguib, V. N. Mochalin, M. W. Barsoum, Y. Gogotsi, X. Yu, K.-W.
thermal stability of NH4 HF2 -etched Ti3 C2 MXene,” Ceram. Int. 43(8), 6322–6328 Nam, X.-Q. Yang, A. I. Kolesnikov, and P. R. C. Kent, “Role of surface structure
(2017). on Li-ion energy storage capacity of two-dimensional transition-metal carbides,”
47
A. Feng, Y. Yu, Y. Wang, F. Jiang, Y. Yu, L. Mi, and L. Song, “Two-dimensional J. Am. Chem. Soc. 136(17), 6385–6394 (2014).
66
MXene Ti3 C2 produced by exfoliation of Ti3 AlC2 ,” Mater. Des. 114, 161–166 S. Lai, J. Jeon, S. K. Jang, J. Xu, Y. J. Choi, J.-H. Park, E. Hwang, and S. Lee,
(2017). “Surface group modification and carrier transport properties of layered transi-
48
T. Zhang, L. Pan, H. Tang, F. Du, Y. Guo, T. Qiu, and J. Yang, “Synthesis of tion metal carbides (Ti2 CTx , T: –OH, –F and –O),” Nanoscale 7(46), 19390–19396
two-dimensional Ti3 C2 Tx MXene using HCl + LiF etchant: Enhanced exfoliation (2015).
67
and delamination,” J. Alloys Compd. 695, 818–826 (2017). I. Persson, L.-Å. Näslund, J. Halim, M. W. Barsoum, V. Darakchieva, J.
49 Palisaitis, J. Rosen, and P. O. Å. Persson, “On the organization and thermal behav-
F. Liu, A. Zhou, J. Chen, J. Jia, W. Zhou, L. Wang, and Q. Hu, “Preparation
of Ti3 C2 and Ti2 C MXenes by fluoride salts etching and methane adsorptive ior of functional groups on Ti3 C2 MXene surfaces in vacuum,” 2D Mater. 5(1),
properties,” Appl. Surf. Sci. 416, 781–789 (2017). 015002 (2017).
50 68
X. Wang, C. Garnero, G. Rochard, D. Magne, S. Morisset, S. Hurand, P. I. Persson, J. Halim, T. W. Hansen, J. B. Wagner, V. Darakchieva, J. Palisaitis, J.
Chartier, J. Rousseau, T. Cabioc’h, C. Coutanceau, V. Mauchamp, and S. Celerier, Rosen, and P. O. Å. Persson, “How much oxygen can a MXene surface take before
“A new etching environment (FeF3 /HCl) for the synthesis of two-dimensional it breaks?,” Adv. Funct. Mater. 30(47), 1909005 (2020).
69
titanium carbide MXenes: A route towards selective reactivity vs. water,” J. Mater. J. Halim, K. M. Cook, P. Eklund, J. Rosen, and M. W. Barsoum, “XPS of cold
Chem. A 5, 22012 (2017). pressed multilayered and freestanding delaminated 2D thin films of Mo2 TiC2 Tz
51 and Mo2 Ti2 C3 Tz (MXenes),” Appl. Surf. Sci. 494, 1138–1147 (2019).
C. Peng, P. Wei, X. Chen, Y. Zhang, F. Zhu, Y. Cao, H. Wang, H. Yu, and F.
70
Peng, “A hydrothermal etching route to synthesis of 2D MXene (Ti3 C2 , Nb2 C): J. Halim, K. M. Cook, M. Naguib, P. Eklund, Y. Gogotsi, J. Rosen, and M.
Enhanced exfoliation and improved adsorption performance,” Ceram. Int. 44(15), W. Barsoum, “X-ray photoelectron spectroscopy of select multi-layered transition
18886–18893 (2018). metal carbides (MXenes),” Appl. Surf. Sci. 362, 406–417 (2016).
52 71
L. Wang, H. Zhang, B. Wang, C. Shen, C. Zhang, Q. Hu, A. Zhou, and B. M. Benchakar, L. Loupias, C. Garnero, T. Bilyk, C. Morais, C. Canaff, N.
Liu, “Synthesis and electrochemical performance of Ti3 C2 Tx with hydrothermal Guignard, S. Morisset, H. Pazniak, S. Hurand, P. Chartier, J. Pacaud, V.
process,” Electron. Mater. Lett. 12(5), 702–710 (2016). Mauchamp, M. W. Barsoum, A. Habrioux, and S. Célérier, “One MAX phase, dif-
53 ferent MXenes: A guideline to understand the crucial role of etching conditions
T. Li, L. Yao, Q. Liu, J. Gu, R. Luo, J. Li, X. Yan, W. Wang, P. Liu, B. Chen,
W. Zhang, W. Abbas, R. Naz, and D. Zhang, “Fluorine-free synthesis of high- on Ti3 C2 Tx surface chemistry,” Appl. Surf. Sci. 530, 147209 (2020).
72
purity Ti3 C2 Tx (T = OH, O) via alkali treatment,” Angew. Chem., Int. Ed. 57(21), A. Sarycheva and Y. Gogotsi, “Raman spectroscopy analysis of the structure
6115–6119 (2018). and surface chemistry of Ti3 C2 Tx MXene,” Chem. Mater. 32(8), 3480–3488
54 (2020).
W. Sun, S. A. Shah, Y. Chen, Z. Tan, H. Gao, T. Habib, M. Radovic, and
73
M. J. Green, “Electrochemical etching of Ti2 AlC to Ti2 CTx (MXene) in low- K. J. Griffith, M. A. Hope, P. J. Reeves, M. Anayee, Y. Gogotsi, and C. P. Grey,
concentration hydrochloric acid solution,” J. Mater. Chem. A 5(41), 21663–21668 “Bulk and surface chemistry of the niobium MAX and MXene phases from multi-
(2017). nuclear solid-state NMR spectroscopy,” J. Am. Chem. Soc. 142(44), 18924–18935
55 (2020).
M. Li, J. Lu, K. Luo, Y. Li, K. Chang, K. Chen, J. Zhou, J. Rosen, L. Hultman,
74
P. Eklund, P. O. Å. Persson, S. Du, Z. Chai, Z. Huang, and Q. Huang, “Element M. Seredych, C. E. Shuck, D. Pinto, M. Alhabeb, E. Precetti, G. Deysher, B.
replacement approach by reaction with lewis acidic molten salts to synthesize Anasori, N. Kurra, and Y. Gogotsi, “High-temperature behavior and surface
nanolaminated MAX phases and MXenes,” J. Am. Chem. Soc. 141(11), 4730–4737 chemistry of carbide MXenes studied by thermal analysis,” Chem. Mater. 31(9),
(2019). 3324–3332 (2019).
56 75
V. Natu, R. Pai, M. Sokol, M. Carey, V. Kalra, and M. W. Barsoum, “2D Ti3 C2 Tz G. Gao, A. P. O’Mullane, and A. Du, “2D MXenes: A new family of promis-
MXene synthesized by water-free etching of Ti3 AlC2 in polar organic solvents,” ing catalysts for the hydrogen evolution reaction,” ACS Catal. 7(1), 494–500
Chem 6(3), 616–630 (2020). (2017).

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-21

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

76 96
Q. Tang, Z. Zhou, and P. Shen, “Are MXenes promising anode materials for Li Y. Zhuang, Y. Liu, and X. Meng, “Fabrication of TiO2 nanofibers/MXene Ti3 C2
ion batteries? Computational studies on electronic properties and Li storage capa- nanocomposites for photocatalytic H2 evolution by electrostatic self-assembly,”
bility of Ti3 C2 and Ti3 C2 X2 (X = F, OH) monolayer,” J. Am. Chem. Soc. 134(40), Appl. Surf. Sci. 496, 143647 (2019).
16909–16916 (2012). 97
C. Peng, H. Wang, H. Yu, and F. Peng, “(111)TiO2 -x/Ti3 C2 : Synergy of active
77
J. Ran, G. Gao, F.-T. Li, T.-Y. Ma, A. Du, and S.-Z. Qiao, “Ti3 C2 MXene co- facets, interfacial charge transfer and Ti3+ doping for enhance photocatalytic
catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic activity,” Mater. Res. Bull. 89, 16–25 (2017).
hydrogen production,” Nat. Commun. 8, 13907 (2017). 98
J. Low, L. Zhang, T. Tong, B. Shen, and J. Yu, “TiO2 /MXene Ti3 C2 compos-
78
H. A. Tahini, X. Tan, and S. C. Smith, “The origin of low work functions in OH ite with excellent photocatalytic CO2 reduction activity,” J. Catal. 361, 255–266
terminated MXenes,” Nanoscale 9(21), 7016–7020 (2017). (2018).
79 99
N. M. Caffrey, “Effect of mixed surface terminations on the structural and Y. Li, X. Deng, J. Tian, Z. Liang, and H. Cui, “Ti3 C2 MXene-derived Ti3 C2 /TiO2
electrochemical properties of two-dimensional Ti3 C2 T2 and V2 CT2 MXenes nanoflowers for noble-metal-free photocatalytic overall water splitting,” Appl.
multilayers,” Nanoscale 10(28), 13520–13530 (2018). Mater. Today 13, 217–227 (2018).
80 100
K. Niu, L. Chi, J. Rosen, and J. Björk, “C-H activation of light alkanes on MXenes N. My Tran, Q. Thanh Hoai Ta, and J.-S. Noh, “Unusual synthesis of
predicted by hydrogen affinity,” Phys. Chem. Chem. Phys. 22(33), 18622–18630 safflower-shaped TiO2 /Ti3 C2 heterostructures initiated from two-dimensional
(2020). Ti3 C2 MXene,” Appl. Surf. Sci. 538, 148023 (2021).
81 101
K. Niu, L. Chi, J. Rosen, and J. Björk, “Structure-activity correlation of V. Q. Hieu, T. K. Phung, T.-Q. Nguyen, A. Khan, V. D. Doan, V. A. Tran,
Ti2 CT2 MXenes for C-H activation,” J. Phys.: Condens. Matter 33(23), 235201 and V. T. Le, “Photocatalytic degradation of methyl orange dye by Ti3 C2 -TiO2
(2021). heterojunction under solar light,” Chemosphere 276, 130154 (2021).
82 102
T. Schultz, N. C. Frey, K. Hantanasirisakul, S. Park, S. J. May, V. B. Shenoy, H. Deng, Z.-j. Li, L. Wang, L.-y. Yuan, J.-h. Lan, Z.-y. Chang, Z.-f. Chai, and
Y. Gogotsi, and N. Koch, “Surface termination dependent work function and W.-q. Shi, “Nanolayered Ti3 C2 and SrTiO3 composites for photocatalytic reduc-
electronic properties of Ti3 C2 Tx MXene,” Chem. Mater. 31(17), 6590–6597 tion and removal of uranium(VI),” ACS Appl. Nano Mater. 2(4), 2283–2294
(2019). (2019).
83 103
A. Agresti, A. Pazniak, S. Pescetelli, A. Di Vito, D. Rossi, A. Pecchia, M. K. Li, X. Lu, Y. Zhang, K. Liu, Y. Huang, and H. Liu, “Bi3 TaO7 /Ti3 C2 het-
Auf der Maur, A. Liedl, R. Larciprete, D. V. Kuznetsov, D. Saranin, and A. Di erojunctions for enhanced photocatalytic removal of water-borne contaminants,”
Carlo, “Titanium-carbide MXenes for work function and interface engineering in Environ. Res. 185, 109409 (2020).
perovskite solar cells,” Nat. Mater. 18(11), 1228–1234 (2019). 104
L. Zhang, J. Yang, T. Xie, S. Feng, and L. Xu, “Boosting visible-light-driven
84
Y. Jiao, Y. Zheng, M. Jaroniec, and S. Z. Qiao, “Design of electrocatalysts for photocatalytic activity of BiPO4 via constructing Schottky junction with Ti3 C2
oxygen- and hydrogen-involving energy conversion reactions,” Chem. Soc. Rev. MXene,” Mater. Des. 192, 108772 (2020).
44(8), 2060–2086 (2015). 105
S. Vigneshwaran, B.-M. Jun, S. Muthu Prabhu, S. S. Elanchezhiyan, Y. S. Ok, S.
85
B. Hinnemann, P. G. Moses, J. Bonde, K. P. Jørgensen, J. H. Nielsen, S. Horch, Meenakshi, and C. M. Park, “Enhanced sonophotocatalytic degradation of bisphe-
I. Chorkendorff, and J. K. Nørskov, “Biomimetic hydrogen evolution: MoS2 nol A using bimetal sulfide-intercalated MXenes, 2D/2D nanocomposite,” Sep.
nanoparticles as catalyst for hydrogen evolution,” J. Am. Chem. Soc. 127(15), Purif. Technol. 250, 117178 (2020).
5308–5309 (2005). 106
S. Vigneshwaran, C. M. Park, and S. Meenakshi, “Designed fabrication
86
J. K. Nørskov, T. Bligaard, A. Logadottir, J. R. Kitchin, J. G. Chen, S. Pande- of sulfide-rich bi-metallic-assembled MXene layered sheets with dramatically
lov, and U. Stimming, “Trends in the exchange current for hydrogen evolution,” enhanced photocatalytic performance for Rhodamine B removal,” Sep. Purif.
J. Electrochem. Soc. 152(3), J23 (2005). Technol. 258, 118003 (2021).
87 107
C. Ling, L. Shi, Y. Ouyang, and J. Wang, “Searching for highly active catalysts Y. Yang, D. Zhang, and Q. Xiang, “Plasma-modified Ti3 C2 Tx /CdS hybrids
for hydrogen evolution reaction based on O-terminated MXenes through a simple with oxygen-containing groups for high-efficiency photocatalytic hydrogen
descriptor,” Chem. Mater. 28(24), 9026–9032 (2016). production,” Nanoscale 11(40), 18797–18805 (2019).
88 108
C. Ling, L. Shi, Y. Ouyang, Q. Chen, and J. Wang, “Transition metal-promoted A. Saeed, W. Chen, A. H. Shah, Y. Zhang, I. Mehmood, and Y. Liu,
V2 CO2 (MXenes): A new and highly active catalyst for hydrogen evolution “Enhancement of photocatalytic CO2 reduction for novel Cd0.2 Zn0.8 S@Ti3 C2
reaction,” Adv. Sci. 3(11), 1600180 (2016). (MXenes) nanocomposites,” J. CO2 Util. 47, 101501 (2021).
89 109
W. Yuan, L. Cheng, Y. Zhang, H. Wu, S. Lv, L. Chai, X. Guo, and L. Zheng, L. Tie, S. Yang, C. Yu, H. Chen, Y. Liu, S. Dong, J. Sun, and J. Sun, “In
“2D-Layered carbon/TiO2 hybrids derived from Ti3 C2 MXenes for photocatalytic situ decoration of ZnS nanoparticles with Ti3 C2 MXene nanosheets for effi-
hydrogen evolution under visible light irradiation,” Adv. Mater. Interfaces 4(20), cient photocatalytic hydrogen evolution,” J. Colloid Interface Sci. 545, 63–70
1700577 (2017). (2019).
90 110
H. Huang, Y. Song, N. Li, D. Chen, Q. Xu, H. Li, J. He, and J. Lu, “One-step Z. Li, H. Zhang, L. Wang, X. Meng, J. Shi, C. Qi, Z. Zhang, L. Feng, and
in-situ preparation of N-doped TiO2 @C derived from Ti3 C2 MXene for enhanced C. Li, “2D/2D BiOBr/Ti3 C2 heterojunction with dual applications in both water
visible-light driven photodegradation,” Appl. Catal., B 251, 154–161 (2019). detoxification and water splitting,” J. Photochem. Photobiol., A 386, 112099
91 (2020).
X. Han, L. An, Y. Hu, Y. Li, C. Hou, H. Wang, and Q. Zhang, “Ti3 C2 MXene-
111
derived carbon-doped TiO2 coupled with g-C3 N4 as the visible-light photocata- J. Li, L. Zhao, S. Wang, J. Li, G. Wang, and J. Wang, “In situ fabrica-
lysts for photocatalytic H2 generation,” Appl. Catal., B 265, 118539 (2020). tion of 2D/3D g-C3 N4 /Ti3 C2 (MXene) heterojunction for efficient visible-light
92 photocatalytic hydrogen evolution,” Appl. Surf. Sci. 515, 145922 (2020).
Q. Liu, L. Ai, and J. Jiang, “MXene-derived TiO2 @C/g-C3 N4 heterojunctions
112
for highly efficient nitrogen photofixation,” J. Mater. Chem. A 6(9), 4102–4110 Y. Sun, D. Jin, Y. Sun, X. Meng, Y. Gao, Y. Dall’Agnese, G. Chen, and X.-F.
(2018). Wang, “g-C3 N4 /Ti3 C2 Tx (MXenes) composite with oxidized surface groups for
93 efficient photocatalytic hydrogen evolution,” J. Mater. Chem. A 6(19), 9124–9131
Z. Wu, Y. Liang, X. Yuan, D. Zou, J. Fang, L. Jiang, J. Zhang, H. Yang, and Z.
Xiao, “MXene Ti3 C2 derived Z–scheme photocatalyst of graphene layers anchored (2018).
113
TiO2 /g–C3 N4 for visible light photocatalytic degradation of refractory organic H. Wang, R. Zhao, J. Qin, H. Hu, X. Fan, X. Cao, and D. Wang, “MIL-
pollutants,” Chem. Eng. J. 394, 124921 (2020). 100(Fe)/Ti3 C2 MXene as a Schottky catalyst with enhanced photocatalytic
94 oxidation for nitrogen fixation activities,” ACS Appl. Mater. Interfaces 11(47),
Y. Gao, L. Wang, A. Zhou, Z. Li, J. Chen, H. Bala, Q. Hu, and X. Cao,
“Hydrothermal synthesis of TiO2 /Ti3 C2 nanocomposites with enhanced photo- 44249–44262 (2019).
114
catalytic activity,” Mater. Lett. 150, 62–64 (2015). C. Peng, P. Wei, X. Li, Y. Liu, Y. Cao, H. Wang, H. Yu, F. Peng, L. Zhang,
95 B. Zhang, and K. Lv, “High efficiency photocatalytic hydrogen production over
L. Chen, X. Ye, S. Chen, L. Ma, Z. Wang, Q. Wang, N. Hua, X. Xiao, S. Cai,
and X. Liu, “Ti3 C2 MXene nanosheet/TiO2 composites for efficient visible light ternary Cu/TiO2 @Ti3 C2 Tx enabled by low-work-function 2D titanium carbide,”
photocatalytic activity,” Ceram. Int. 46(16), 25895–25904 (2020). Nano Energy 53, 97–107 (2018).

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-22

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

115 134
C. Peng, W. Xu, P. Wei, M. Liu, L. Guo, P. Wu, K. Zhang, Y. Cao, H. Wang, J. He, J. Yang, F. Jiang, P. Liu, and M. Zhu, “Photo-assisted peroxymono-
H. Yu, F. Peng, and X. Yan, “Manipulating photocatalytic pathway and activity sulfate activation via 2D/2D heterostructure of Ti3 C2 /g-C3 N4 for degradation of
of ternary Cu2 O/(001)TiO2 @Ti3 C2 Tx catalysts for H2 evolution: Effect of surface diclofenac,” Chemosphere 258, 127339 (2020).
coverage,” Int. J. Hydrogen Energy 44(57), 29975–29985 (2019). 135
J. Kang, S. Byun, S. Kim, J. Lee, M. Jung, H. Hwang, T. W. Kim, S. H. Song,
116
Y. Li, Z. Yin, G. Ji, Z. Liang, Y. Xue, Y. Guo, J. Tian, X. Wang, and H. Cui, and D. Lee, “Design of three-dimensional hollow-sphere architecture of Ti3 C2 Tx
“2D/2D/2D heterojunction of Ti3 C2 MXene/MoS2 nanosheets/TiO2 nanosheets MXene with graphitic carbon nitride nanoshells for efficient photocatalytic hydro-
with exposed (001) facets toward enhanced photocatalytic hydrogen production gen evolution,” ACS Appl. Energy Mater. 3(9), 9226–9233 (2020).
activity,” Appl. Catal., B 246, 12–20 (2019). 136
M. Shao, Y. Shao, J. Chai, Y. Qu, M. Yang, Z. Wang, M. Yang, W. F. Ip, C. T.
117
Y. Li, L. Ding, Z. Liang, Y. Xue, H. Cui, and J. Tian, “Synergetic effect of Kwok, X. Shi, Z. Lu, S. Wang, X. Wang, and H. Pan, “Synergistic effect of 2D Ti2 C
defects rich MoS2 and Ti3 C2 MXene as cocatalysts for enhanced photocatalytic and g-C3 N4 for efficient photocatalytic hydrogen production,” J. Mater. Chem. A
H2 production activity of TiO2 ,” Chem. Eng. J. 383, 123178 (2020). 5(32), 16748–16756 (2017).
118 137
Y. Li, L. Ding, S. Yin, Z. Liang, Y. Xue, X. Wang, H. Cui, and J. Tian, J.-Y. Li, Y.-H. Li, F. Zhang, Z.-R. Tang, and Y.-J. Xu, “Visible-light-driven
“Photocatalytic H2 evolution on TiO2 assembled with Ti3 C2 MXene and metallic integrated organic synthesis and hydrogen evolution over 1D/2D CdS-Ti3 C2 Tx
1T-WS2 as Co-catalysts,” Nano-Micro Lett. 12(1), 6 (2019). MXene composites,” Appl. Catal., B 269, 118783 (2020).
119 138
K. Huang, C. Li, and X. Meng, “In-situ construction of ternary Ti3 C2 X. Xie, N. Zhang, Z.-R. Tang, M. Anpo, and Y.-J. Xu, “Ti3 C2 Tx MXene
MXene@TiO2 /ZnIn2 S4 composites for highly efficient photocatalytic hydrogen as a Janus cocatalyst for concurrent promoted photoactivity and inhibited
evolution,” J. Colloid Interface Sci. 580, 669–680 (2020). photocorrosion,” Appl. Catal., B 237, 43–49 (2018).
120 139
Q. Liu, X. Tan, S. Wang, F. Ma, H. Znad, Z. Shen, L. Liu, and S. Liu, “MXene R. Xiao, C. Zhao, Z. Zou, Z. Chen, L. Tian, H. Xu, H. Tang, Q. Liu, Z. Lin, and X.
as a non-metal charge mediator in 2D layered CdS@Ti3 C2 @TiO2 composites Yang, “In situ fabrication of 1D CdS nanorod/2D Ti3 C2 MXene nanosheet Schot-
with superior Z-scheme visible light-driven photocatalytic activity,” Environ. Sci.: tky heterojunction toward enhanced photocatalytic hydrogen evolution,” Appl.
Nano 6(10), 3158–3169 (2019). Catal., B 268, 118382 (2019).
121 140
H. Wang, Y. Wu, T. Xiao, X. Yuan, G. Zeng, W. Tu, S. Wu, H. Y. Lee, Y. Z. M. Ding, R. Xiao, C. Zhao, D. Bukhvalov, Z. Chen, H. Xu, H. Tang, J. Xu, and
Tan, and J. W. Chew, “Formation of quasi-core-shell In2 S3 /anatase TiO2 @metallic X. Yang, “Evidencing interfacial charge transfer in 2D CdS/2D MXene Schottky
Ti3 C2 Tx hybrids with favorable charge transfer channels for excellent visible-light- heterojunctions toward high-efficiency photocatalytic hydrogen production,” Sol.
photocatalytic performance,” Appl. Catal., B 233, 213–225 (2018). RRL 5(2), 2000414 (2020).
122 141
T. Xu, J. Wang, Y. Cong, S. Jiang, Q. Zhang, H. Zhu, Y. Li, and X. Li, “Ternary S. Cao, B. Shen, T. Tong, J. Fu, and J. Yu, “2D/2D heterojunction of ultrathin
BiOBr/TiO2 /Ti3 C2 Tx MXene nanocomposites with heterojunction structure and MXene/Bi2 WO6 nanosheets for improved photocatalytic CO2 reduction,” Adv.
improved photocatalysis performance,” Chin. Chem. Lett. 31(4), 1022–1025 Funct. Mater. 28(21), 1800136 (2018).
(2020). 142
D. Zhao and C. Cai, “Preparation of Bi2 MoO6 /Ti3 C2 MXene heterojunction
123
Z. Yao, H. Sun, H. Sui, and X. Liu, “Construction of BPQDs/Ti3 C2 @TiO2 photocatalysts for fast tetracycline degradation and Cr(VI) reduction,” Inorg.
composites with favorable charge transfer channels for enhanced photocatalytic Chem. Front. 7(15), 2799–2808 (2020).
activity under visible light irradiation,” Nanomaterials 10(3), 452 (2020). 143
Y. Li, Y. Liu, D. Xing, J. Wang, L. Zheng, Z. Wang, P. Wang, Z. Zheng, H.
124
P. Tian, X. He, L. Zhao, W. Li, W. Fang, H. Chen, F. Zhang, Z. Huang, and H. Cheng, Y. Dai, and B. Huang, “2D/2D heterostructure of ultrathin BiVO4 /Ti3 C2
Wang, “Enhanced charge transfer for efficient photocatalytic H2 evolution over nanosheets for photocatalytic overall water splitting,” Appl. Catal., B 285, 119855
UiO-66-NH2 with annealed Ti3 C2 Tx MXenes,” Int. J. Hydrogen Energy 44(2), (2021).
788–800 (2019). 144
B. Shao, J. Wang, Z. Liu, G. Zeng, L. Tang, Q. Liang, Q. He, T. Wu, Y.
125
H. Jiang, Z. Hu, C. Gan, B. Sun, S. Kong, and F. Bian, “Visible- Liu, and X. Yuan, “Ti3 C2 Tx MXene decorated black phosphorus nanosheets
light induced one-pot hydrogenation and amidation of nitroaromatics with with improved visible-light photocatalytic activity: Experimental and theoretical
carboxylic acids over 2D MXene-derived Pt/N-TiO2 /Ti3 C2 ,” Mol. Catal. 504, studies,” J. Mater. Chem. A 8(10), 5171–5185 (2020).
111490 (2021). 145
B. Shao, Z. Liu, G. Zeng, Y. Liu, Q. Liang, Q. He, T. Wu, Y. Pan, J. Huang,
126
A. A. Khan, M. Tahir, and A. Bafaqeer, “Constructing a stable 2D layered Z. Peng, S. Luo, C. Liang, X. Liu, S. Tong, and J. Liang, “Synthesis of 2D/2D
Ti3 C2 MXene cocatalyst-assisted TiO2 /g-C3 N4 /Ti3 C2 heterojunction for tailoring CoAl-LDHs/Ti3 C2 Tx Schottky-junction with enhanced interfacial charge trans-
photocatalytic bireforming of methane under visible light,” Energy Fuels 34(8), fer and visible-light photocatalytic performance,” Appl. Catal., B 286, 119867
9810–9828 (2020). (2021).
127 146
M. Tahir and B. Tahir, “2D/2D/2D O-C3 N4 /Bt/Ti3 C2 Tx heterojunction with D. Huang, Z. Li, G. Zeng, C. Zhou, W. Xue, X. Gong, X. Yan, S. Chen, W.
novel MXene/clay multi-electron mediator for stimulating photo-induced CO2 Wang, and M. Cheng, “Megamerger in photocatalytic field: 2D g-C3 N4 nanosheets
reforming to CO and CH4 ,” Chem. Eng. J. 400, 125868 (2020). serve as support of 0D nanomaterials for improving photocatalytic performance,”
128 Appl. Catal., B 240, 153–173 (2019).
S. Wang, Y. Wang, J. Wan, Y. Ma, Z. Yan, and G. Zhang, “Dual channel carrier
147
transfer based on Ti3 C2 Tx improves carrier utilization of Z-scheme Ag3 PO4 /AgBr M.-Y. Ye, Z.-H. Zhao, Z.-F. Hu, L.-Q. Liu, H.-M. Ji, Z.-R. Shen, and T.-Y.
heterojunction photocatalyst,” Sep. Purif. Technol. 253, 117486 (2020). Ma, “0D/2D heterojunctions of vanadate quantum dots/graphitic carbon nitride
129
K. Wu, S. Song, H. Wu, J. Guo, and L. Zhang, “Facile synthesis nanosheets for enhanced visible-light-driven photocatalysis,” Angew. Chem., Int.
of Bi2 WO6 /C3 N4 /Ti3 C2 composite as Z-scheme photocatalyst for efficient Ed. 56, 8407–8411 (2017).
148
ciprofloxacin degradation and H2 production,” Appl. Catal., A 608, 117869 (2020). Z. Ai, Y. Shao, B. Chang, B. Huang, Y. Wu, and X. Hao, “Effective ori-
130
S. Wu, Y. Su, Y. Zhu, Y. Zhang, and M. Zhu, “In-situ growing Bi/BiOCl micro- entation control of photogenerated carrier separation via rational design of a
spheres on Ti3 C2 nanosheets for upgrading visible-light-driven photocatalytic Ti3 C2 (TiO2 )@CdS/MoS2 photocatalytic system,” Appl. Catal., B 242, 202–208
activity,” Appl. Surf. Sci. 520, 146339 (2020). (2019).
131 149
H. Zhang, M. Li, C. Zhu, Q. Tang, P. Kang, and J. Cao, “Preparation Z. Ai, K. Zhang, B. Chang, Y. Shao, L. Zhang, Y. Wu, and X. Hao,
of magnetic α-Fe2 O3 /ZnFe2 O4 @Ti3 C2 MXene with excellent photocatalytic “Construction of CdS@Ti3 C2 @CoO hierarchical tandem p-n heterojunction for
performance,” Ceram. Int. 46(1), 81–88 (2020). boosting photocatalytic hydrogen production in pure water,” Chem. Eng. J. 383,
132 123130 (2020).
T. Su, Z. D. Hood, M. Naguib, L. Bai, S. Luo, C. M. Rouleau, I. N. Ivanov, H. Ji,
150
Z. Qin, and Z. Wu, “Monolayer Ti3 C2 Tx as an effective co-catalyst for enhanced C. Xu, F. Yang, B. Deng, Y. Zhuang, D. Li, B. Liu, W. Yang, and Y. Li,
photocatalytic hydrogen production over TiO2 ,” ACS Appl. Energy Mater. 2(7), “Ti3 C2 /TiO2 nanowires with excellent photocatalytic performance for selective
4640–4651 (2019). oxidation of aromatic alcohols to aldehydes,” J. Catal. 383, 1–12 (2020).
133 151
C. Yang, Q. Tan, Q. Li, J. Zhou, J. Fan, B. Li, J. Sun, and K. Lv, “2D/2D G. Huang, S. Li, L. Liu, L. Zhu, and Q. Wang, “Ti3 C2 MXene-modified Bi2 WO6
Ti3 C2 MXene/g-C3 N4 nanosheets heterojunction for high efficient CO2 reduction nanoplates for efficient photodegradation of volatile organic compounds,” Appl.
photocatalyst: Dual effects of urea,” Appl. Catal., B 268, 118738 (2020). Surf. Sci. 503, 144183 (2020).

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-23

© Author(s) 2021
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

152 165
Q. Xue, H. Zhang, M. Zhu, Z. Pei, H. Li, Z. Wang, Y. Huang, Y. Huang, Q. J. Yang, D. Wang, H. Han, and C. Li, “Roles of cocatalysts in photocatalysis and
Deng, J. Zhou, S. Du, Q. Huang, and C. Zhi, “Photoluminescent Ti3 C2 MXene photoelectrocatalysis,” Acc. Chem. Res. 46(8), 1900–1909 (2013).
quantum dots for multicolor cellular imaging,” Adv. Mater. 29(15), 1604847 166
Y. Liu, Y.-H. Li, X. Li, Q. Zhang, H. Yu, X. Peng, and F. Peng, “Regulating
(2017). electron-hole separation to promote photocatalytic H2 evolution activity of
153
Q. Xu, L. Ding, Y. Wen, W. Yang, H. Zhou, X. Chen, J. Street, A. Zhou, nanoconfined Ru/MXene/TiO2 catalysts,” ACS Nano 14(10), 14181–14189
W.-J. Ong, and N. Li, “High photoluminescence quantum yield of 18.7% by using (2020).
nitrogen-doped Ti3 C2 MXene quantum dots,” J. Mater. Chem. C 6, 6360–6369 167
Z. Zhao, Z. Li, and Z. Zou, “Surface properties and electronic structure of low-
(2018). index stoichiometric anatase TiO2 surfaces,” J. Phys.: Condens. Matter 22(17),
154
S. Lu, L. Sui, Y. Liu, X. Yong, G. Xiao, K. Yuan, Z. Liu, B. Liu, B. Zou, and 175008 (2010).
B. Yang, “White photoluminescent Ti3 C2 MXene quantum dots with two-photon 168
S. Chen, S. Shen, G. Liu, Y. Qi, F. Zhan, and C. Li, “Interface engineer-
fluorescence,” Adv. Sci. 6(6), 1801470 (2019). ing of a CoOx /Ta3 N5 photocatalyst for unprecedented water oxidation perfor-
155
Z. Zeng, Y. Yan, J. Chen, P. Zan, Q. Tian, and P. Chen, “Boosting the photocat- mance under visible-light-irradiation,” Angew. Chem., Int. Ed. 54(10), 3047–3051
alytic ability of Cu2 O nanowires for CO2 conversion by MXene quantum dots,” (2015).
Adv. Funct. Mater. 29(2), 1806500 (2019). 169
F. Huang, J. Hou, Q. Zhang, Y. Wang, R. C. Massé, S. Peng, H. Wang, J. Liu,
156
Y. Li, L. Ding, Y. Guo, Z. Liang, H. Cui, and J. Tian, “Boosting the photocat- and G. Cao, “Doubling the power conversion efficiency in CdS/CdSe quantum
alytic ability of g-C3 N4 for hydrogen production by Ti3 C2 MXene quantum dots,” dot sensitized solar cells with a ZnSe passivation layer,” Nano Energy 26, 114–122
ACS Appl. Mater. Interfaces 11(44), 41440–41447 (2019). (2016).
157 170
F. He, B. Zhu, B. Cheng, J. Yu, W. Ho, and W. Macyk, “2D/2D/0D J.-X. Yang, W.-B. Yu, C.-F. Li, W.-D. Dong, L.-Q. Jiang, N. Zhou, Z.-P. Zhuang,
TiO2 /C3 N4 /Ti3 C2 MXene composite S-scheme photocatalyst with enhanced CO2 J. Liu, Z.-Y. Hu, H. Zhao, Y. Li, L. Chen, J. Hu, and B.-L. Su, “PtO nanodots pro-
reduction activity,” Appl. Catal., B 272, 119006 (2020). moting Ti3 C2 MXene in-situ converted Ti3 C2 /TiO2 composites for photocatalytic
158 hydrogen production,” Chem. Eng. J. 420(18), 129695 (2021).
H. Wang, R. Peng, Z. D. Hood, M. Naguib, S. P. Adhikari, and Z. Wu,
171
“Titania composites with 2D transition metal carbides as photocatalysts for hydro- D. Yan, X. Fu, Z. Shang, J. Liu, and H. Luo, “A BiVO4 film photoanode
gen production under visible-light irradiation,” ChemSusChem 9(12), 1490–1497 with re-annealing treatment and 2D thin Ti3 C2 Tx flakes decoration for enhanced
(2016). photoelectrochemical water oxidation,” Chem. Eng. J. 361, 853–861 (2019).
159 172
T. Su, R. Peng, Z. D. Hood, M. Naguib, I. N. Ivanov, J. K. Keum, Z. Qin, Z. X. Zou, X. Zhao, J. Zhang, W. Lv, L. Qiu, and Z. Zhang, “Photocatalytic
Guo, and Z. Wu, “One-step synthesis of Nb2 O5 /C/Nb2 C (MXene) composites degradation of ranitidine and reduction of nitrosamine dimethylamine forma-
and their use as photocatalysts for hydrogen evolution,” ChemSusChem 11(4), tion potential over MXene–Ti3 C2 /MoS2 under visible light irradiation,” J. Hazard.
688–699 (2018). Mater. 413, 125424 (2021).
160 173
H. Jiang, C. Zang, Y. Zhang, W. Wang, C. Yang, B. Sun, Y. Shen, and F. R.-K. Ye, S.-S. Sun, L.-Q. He, S.-R. Yang, X.-Q. Liu, M.-D. Li, P.-P. Fang,
Bian, “2D MXene-derived Nb2 O5 /C/Nb2 C/g-C3 N4 heterojunctions for efficient and J.-Q. Hu, “Surface engineering of hematite nanorods by 2D Ti3 C2 -MXene:
nitrogen photofixation,” Catal. Sci. Technol. 10(17), 5964–5972 (2020). Suppressing the electron-hole recombination for enhanced photoelectrochemical
161
D. Zu, H. Song, Y. Wang, Z. Chao, Z. Li, G. Wang, Y. Shen, C. Li, and J. performance,” Appl. Catal., B 291, 120107 (2021).
174
Ma, “One-pot in-situ hydrothermal synthesis of CdS/Nb2 O5 /Nb2 C heterojunction J.-P. Hong, A.-Y. Park, S. Lee, J. Kang, N. Shin, and D. Y. Yoon, “Tuning of Ag
for enhanced visible-light-driven photodegradation,” Appl. Catal., B 277, 119140 work functions by self-assembled monolayers of aromatic thiols for an efficient
(2020). hole injection for solution processed triisopropylsilylethynyl pentacene organic
162
R. Li, L. Zhang, L. Shi, and P. Wang, “MXene Ti3 C2 : An effective 2D light-to- thin film transistors,” Appl. Phys. Lett. 92(14), 143311 (2008).
175
heat conversion material,” ACS Nano 11(4), 3752–3759 (2017). A. VahidMohammadi, J. Rosen, and Y. Gogotsi, “The world of two-
163
H. Lin, S. Gao, C. Dai, Y. Chen, and J. Shi, “A two-dimensional biodegradable dimensional carbides and nitrides (MXenes),” Science 372, eabf1581 (2021).
176
niobium carbide (MXene) for photothermal tumor eradication in NIR-I and NIR- F. Shahzad, M. Alhabeb, C. B. Hatter, B. Anasori, S. M. Hong, C. M. Koo,
II biowindows,” J. Am. Chem. Soc. 139(45), 16235–16247 (2017). and Y. Gogotsi, “Electromagnetic interference shielding with 2D transition metal
164
Z. Wu, C. Li, Z. Li, K. Feng, M. Cai, D. Zhang, S. Wang, M. Chu, C. Zhang, J. carbides (MXenes),” Science 353(6304), 1137–1140 (2016).
177
Shen, Z. Huang, Y. Xiao, G. A. Ozin, X. Zhang, and L. He, “Niobium and titanium M. Naguib, O. Mashtalir, J. Carle, V. Presser, J. Lu, L. Hultman, Y. Gogotsi,
carbides (MXenes) as superior photothermal supports for CO2 photocatalysis,” and M. W. Barsoum, “Two-dimensional transition metal carbides,” ACS Nano
ACS Nano 15(3), 5696–5705 (2021). 6(2), 1322–1331 (2012).

APL Mater. 9, 070703 (2021); doi: 10.1063/5.0055711 9, 070703-24

© Author(s) 2021