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Role of Ti3C2 MXene as Prominent Schottky Barriers in Driving

Hydrogen Production through Photoinduced Water Splitting: A
Comprehensive Review
Areen Sherryna and Muhammad Tahir*
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ABSTRACT: Photocatalytic hydrogen generation through the

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utilization of the Ti3C2 MXene photocatalyst offers the best

alternatives to provide clean, sustainable, and renewable energy
sources. The unique structure, good metallic conductivity, and
excellent photochemical properties exhibited by Ti3C2 MXene
nominate it as a highly favored cocatalyst to derive hydrogen
generation compared to other noncommercial semiconductors.
This review highlights the role of Ti3C2 MXene and its potential in
promoting photocatalytic hydrogen production through the
formation of Schottky interfaces. First, the structural overview
and the basic principles of Ti3C2 MXene in photocatalysis are
summarized. Second, a brief introduction to the characteristics of
Ti3C2 MXene is made to give a firm understanding of its optoelectronic and electrical properties and its stability under thermal and
oxidative treatment. Besides, the role of Ti3C2 MXene in promoting photocatalytic hydrogen production is consistently discussed
with a focus on the photoactivity enhancement of Ti3C2 MXene-based Schottky junctions. Furthermore, insights into the different
morphological effects of Ti3C2 MXene on photocatalytic reactions are summarized. Finally, the future prospects and challenges are
discussed to give insights into the future development of Ti3C2 MXene. Hence, this review provides a significant overview for further
exploring the role of Ti3C2 MXene as an effective cocatalyst for photocatalytic H2 production and other energy applications.
KEYWORDS: Ti3C2 MXene, photocatalysis, hydrogen production, Schottky junction, heterojunction photocatalysts

1.0. INTRODUCTION water splitting by Fujishima and Honda.8 Despite its

The utilization of fossil fuels as a primary energy source leads
to major ecological problems. Its fleeting consumption is
inherently linked with anthropogenic climate change.1 Addi-
tionally, the depletion of fossil fuels due to rapid industrializa-
tion has become a global threat to sustainable economic
development.2,3 It has been noted that fossil fuel energy
problems and their deleterious effects on the environment are
two interwoven challenges that need prompt action.4 The
employment of hydrogen through energy scavenging to
substitute fossil fuels offers clean, sustainable, and renewable
energy production.5 Photocatalytic hydrogen production
through solar energy harvesting has been considered a
propitious maneuver in tackling the aforementioned issues.6
The attribution of photocatalytic water splitting in hydrogen
energy generation has garnered scientific interest to improve its
efficiency over various solar active catalysts to meet future
energy demands.7 Advances in the photocatalytic water
splitting system have led to the development of numerous
solar active photocatalysts such as TiO2, CuO, ZnO, CdS, ZnS,
and WO3.
The utilization of TiO2 semiconductors has been highly
favorable since the pioneering study of photoelectrocatalytic
availability and astounding photocatalytic activity, it suffers
from rapid recombination of photogenerated charges and low
quantum efficiency. This hinders the functionality and
applicability of TiO2 in the photocatalytic water splitting
process.9 A widely studied photocatalyst such as CdS possesses
remarkable photocatalytic performance and has displayed a
positive result toward photocatalytic hydrogen production over
the years. However, as a single photocatalyst, CdS is typically
subjected to photocorrosion, photoinstability, and low
separation efficiency of electron−hole pairs.10 Good solar to
energy conversion by the photocatalyst is one of the
compelling criteria to achieve higher efficiency in photo-
catalytic hydrogen production. Despite the abundance, cost-
effectiveness, and nontoxicity of CuO and ZnO, making them
Received: July 28, 2021
Accepted: October 28, 2021
Published: November 12, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acsaem.1c02241

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ACS Applied Energy Materials
highly preferable in the photocatalytic hydrogen production
process, they can only absorb light under UV spectra which
limits their role in large scale hydrogen production. Therefore,
to overcome the limitations of these solar-active semi-
conductors, modifications such as tuning the morphological
and architectural structures, bandgap engineering, and the
formation of hybrid composites were often studied to shift
toward the visible spectrum.
Recently, considerable attention has been given to two-
dimensional (2D) materials as cocatalysts to boost photo-
catalytic hydrogen production. Among them, Ti3C2 MXene is
known to exhibit beneficial advantages in the photocatalytic
process. The tunable terminal groups, metallic conductivity,
layered structure, and facile morphological configuration
nominated Ti3C2 MXene as a prominent cocatalyst to
profoundly enhance the photocatalytic activity. Herein, the
main objective of this review is to highlight the role of Ti3C2
MXene and its potential in promoting photocatalytic hydrogen
production through engineering modification. First, the
structural overview and the basic principle of Ti3C2 MXene
in photocatalysis are summarized. The insights into tailoring
the surface functional group of Ti3C2 MXene through different
synthesis processes are discussed in this section. Second, the
introduction to the characteristics of Ti3C2 MXene is made.
This is to give a firm understanding of its stability under
thermal and oxidation treatment, where insights into the
conversion of Ti3C2 MXene into TiO2 and TiC are
summarized. Besides, the optoelectronic and electrical proper-
ties of Ti3C2 MXene are also discussed to understand the
semiconducting and metallic properties of MXene materials. In
the next section, the role of Ti3C2 MXene in promoting
photocatalytic hydrogen production through Schottky barrier
formation is consistently discussed, highlighting the recent
progress in the field of photocatalysis. Focus is given to the
photoactivity enhancement of Ti3C2 MXene-based g-C3N4,
CdS, TiO2, MoS2, CdLa2S4, SnNb2O6, and ZnS hetero-
junctions. Furthermore, insights into different morphological
effects of Ti3C2 MXene on photocatalytic reactions are
summarized. Finally, the future prospects and challenges are
discussed to give insights into the future development of Ti3C2
MXene.
2.0. BASIC PRINCIPLE AND GENERAL OVERVIEW OF
MXENES
2.1. Structure of Ti3C2Tx MXenes and Modulation in
Termination Groups. Two-dimensional (2D) nanomaterials
have received a positive attribution in the photocatalysis
process due to their tailorable electronic structure. It has been
denoted that the structural and electronic properties of the
semiconductors play significant roles in determining the
efficacy of photocatalytic H2 production. Additionally,
substantial in-plane covalent bonding in 2D nanomaterials
provides sites for the formation of numerous heterojunctions.11
Among the class of 2D photocatalysts, MXenes in photo-
catalytic hydrogen production gained considerable attention
due to their positive contribution toward the fabrication of
visible light-active photocatalysts.12 The unique double layers,
good compositional flexibility, excellent metal conductivity,
and tailorable work function exhibited by MXenes nominate
them as highly favored cocatalysts for outstanding photo-
catalytic hydrogen production.13
MXenes predominantly are one of the subfamilies of MAX
phase materials. It has been suggested that the exfoliation of
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MAX material by using hydrofluoric acid (HF) solutions and
sonication will form 2D transition-metal, carbide, carboni-
trides, or nitride layers, known as MXenes.14 Some of the
distinctive properties of MXenes that distinguish them from
their intrinsic MAX phases is that they possess different
electronic, magnetic, optical, and electrochemical properties,
which strongly depend on the type of metal transition tuned
onto the surfaces, the surface functionalization, and the
thickness of MXenes.14 The structural composition of MXenes
can be signified by the formula Mn+1XnTx (n = 1, 2, 3), where
M is for transitional metals such as Sc, Ti, Zr, Hf, V, Nb, Ta,
and Mo, while X constitutes either C or N elements and Tx
stands for surface termination where x can be oxygen, hydroxyl,
or halogen groups such as fluorine and chlorine.15 The detailed
structural views of MXene and its composition are shown in
Figure 1. The first MXenes ever to be synthesized, in 2011, are
Figure 1. General structural classification of MXene with the
compositional formula in which M stands for transitional metal
elements, X consists of C and N, while T stands for surface
termination groups.
Ti3C2Tx. The potential of MXenes in different technological
fields has fostered their rapid development, in which 19
different types have been reported so far in 2017.16 One of the
most studied MXene types is Ti3C2 which is the most
attractive and profoundly used in the photocatalysis process.
Ti3C2 can develop a strong heterojunction with other
semiconductors due to the constitution of hydrophilic
functionalities such as −OH and −O on their surfaces. Besides
the exposure of the transitional metal sites, Ti preeminently
improves the redox activity outperforming carbon materials.
The exceptional metallic conductivity typically associated with
the Schottky heterojunction profoundly enhances the separa-
tion and migration of the photogenerated charges. The
Schottky formation inhibits the backward return of the
photogenerated charges to their semiconductor counterparts,
indirectly prolonging the exciton lifetime.17 However, MXenes
are generally not semiconductors and cannot directly be
applied as photocatalysts. Therefore, MXenes are primarily
utilized as cocatalysts and electron mediators to promote solar
energy conversion and improve the photochemical properties
of the hybrid composites. The application of MXenes in
photocatalytic hydrogen production was proven to notably
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Figure 2. (a) General structure of Ti3AlC2 MAX and structural view of MXenes with termination groups after the etching treatment [Reproduced
with permission from ref 29. Copyright 2020 Elsevier]. (b) Detailed overview of MXenes synthesized through a water-free etching technique
[Reproduced with permission from ref 23. Copyright 2020 Elsevier].
enhance and boost the hydrogen generation rate, which has
been disclosed in many literature works.
MXenes are not only widely recognized in the photocatalysis
field, but their emergence in the electrocatalysis field has
gained scientific acclamation.18 In electrocatalysis, the reaction
activity is highly dependent on the adsorption of the hydrogen
atoms on the catalyst surface, which becomes the determining
factor for the efficiency of the electrocatalysts. MXenes as
ultrathin 2D materials exhibit flexible structure, which is
beneficial as conductive scaffolds and provides better
accessibility of the electrons to the catalyst substrate.19 The
intimate contact formation owing to ultrathin sheets of MXene
could minimize the electron transfer resistance, which in return
promotes the efficient mobilization of electrons through the
external circuit. In addition, the higher specific surface area of
the MXene sheets serves as a scaffold that could provide
excellent electrolyte wettability, enhancing the mass transport
kinetics and increasing the contact area with the electro-
lyte.20,21
Even though the conventional, first preparation technique to
synthesize MXenes has been disclosed by Naguib and co-
workers through direct HF etching and has been proven to
efficiently exfoliate the A layer of MAX phases, the higher
concentrations used in this process are not environmentally
feasible.22 In this preparation technique, HF has been used to
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break the Ti−Al bond of the Ti3AlC2 MAX to generate Ti3C2
MXenes where the surfaces of Ti were terminated by OH
groups. The use of a 50% concentration of HF acid was
noticed to be highly toxic to the environment, which therefore
results in the development of other preparation techniques to
substitute the usage of HF acid. In this case, several types of
etchants have been employed, such as using acid containing
fluoride ions, the milder concentration of acids, alkali
treatment, molten salts, and halogen-based etchants. There-
fore, by utilizing different types of etchants, new preparation
routes have been developed, such as in situ HF, electro-
chemical etching, molten salts substitution, alkali etching,
water-free etching, and the newest preparation technique
reported, halogen etching. It should be noted that the
termination groups (Tx) of MXenes can be tailored through
employing different types of etchants with different preparation
routes, which will be further elucidated and analyzed to
provide intelligible views on their structural properties by
varying the etchant types. Utilizing HF and HCl/H2SO4
containing fluoride salts as an etchant to etch the MAX phases
has been reported to generate Ti3C2−(OH)2, and Ti3C2−F2
MXenes by which after the removal of the Al group lead to the
substitution of the terminal groups (Tx = OH, F) as illustrated
in Figure 2a. On the other hand, Natu et al., for the first time,
adopted a technique that substitutes water with polar organic
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Figure 3. General mechanism of photocatalytic hydrogen generation process by Mxene Ti3C2 as a cocatalyst and the overview of its properties.
solvents as dissolving agents, which is known as the water-free
etching method.23 This route was ascribed to synthesized
Ti3C2Tx MXenes with reduced −OH functional groups due to
the absence of water. The detailed synthesis process was
illustrated in Figure 2b. It was believed that this technique
could improve the commercial readiness and applicability of
MXenes, especially in water-sensitive applications. The
utilization of ammonium dihydrogen fluoride (NH4HF2)
with propylene carbonate (PC) as solvents substantially
produced Ti3C2−F2 rich in −F termination, which is with
the approximation of 70% of −F functional groups while 30%
contain −O/−OH functional groups. The reduced number of
−OH functional groups is beneficial to enhance the oxidation
stability of MXenes as it was disclosed that the rapid oxidation
of MXenes is highly linked with the presence of −OH
termination.24 Additionally, the synthesis of MXenes with
other functional groups such as −Cl can be achieved via
electrochemical etching, molten salt substitution, and halogen
etching. In the context of electrochemical etching, the
techniques employed a Ti3AlC2 MAX as the working
electrodes and the A groups were electrochemically etched
with the assistance of the electrolyte. Different electrolytes
used such as H2SO4, HNO3, NaOH, NH4Cl, and FeCl3 will
result in different types of functionalized Ti3C2−Tx.25
Furthermore, it was also disclosed by Sun et al. that
electrochemical etching would result in the formation of
MXenes without terminal F.26 Cl containing electrolytes, on
the other hand, could generate MXenes with −Cl functional
groups. The schematic representation of the electrochemical
etching of the A element from MAX phases by utilizing a
NH4Cl electrolyte with TMAOH as the intercalating agent is
shown in Figure S1a. Furthermore, S1b provides clear details
on how the Al element from the MAX was stripped away from
the M−X layer with the presence of NH4Cl. On the other
hand, in generating MXenes with −Cl functional groups
through molten salts substitution, the technique employed the
usage of molten salts such as ZnCl2 and CuCl2, where the Zn
and Cu elements from the molten salts undergo a substitution
reaction with the A layer of the MAX to be further exfoliated to
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form Ti3C2−Cl2.16 The schematic representation of the
substitution mechanism can be observed from Figure S2a.
Correspondingly, the Cl terminated MXene can also be
achieved through solvent-based halogen etching, with the use
of halogen-based etchants such as I2, Cl2, ICl, and IBr, which
involved the reaction of a halogen radical with the A element
of MAX phases to control the surface chemistries of
synthesized MXenes.27 Additionally, this method could also
generate MXenes with halogen functionals depending on the
types of etchants used. Furthermore, the etching process
through the utilization of iodine as an etchant, proposed by Shi
et al. as shown in Figure S2b, successfully synthesized an
MXene with abundant −O functional groups with excellent
mechanical strength and higher stability than fluoride-
terminated MXenes.28 The newly developed halogen-based
etching is another alternative to develop a fluoride-free MXene
and is a notable technique to generate MXenes with halogen
functional groups where their features and unique character-
istics can be further analyzed in various technological fields.
2.2. Photocatalytic Hydrogen Production Mecha-
nism. In general, photocatalytic water splitting reaction
involves six principal processes: photon absorption, exciton
separation, carrier diffusion, carrier transport, catalytic
efficiency, and mass transfer of reactants and products.30
Equations 1−6 denote the overall system of photocatalytic
water splitting. The initial reaction of photocatalysis starts with
photon absorption as shown in eq 1, where the resulting
energy produced will transfer to photocatalysts with the
generation of electrons and holes. This is followed by the
separation and transportation of the photogenerated charges to
the surface of the photocatalyst; and these undergo redox
reactions. As denotes in eq 3, the shorter lifetimes of the
photocarriers lead to the recombination of electron−hole pairs
with the release of unproductive heat, which lowers the
efficiency of the photocatalyst and constrains the generation of
hydrogen. Such that, in eq 4, the holes that remained at the
valence band (VB) of the photocatalysts will undergo
oxidation reaction with water to produce oxygen and protons
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(H+), while in eq 5, the resulting protons will react with
electrons to be reduced into hydrogen.31
catalyst + h v → e− + h+ (1)
catalyst(e−) + Ti3C2 → Ti3C2(e−)
(2)
e− + h+ → heat (3)
1 different efficiencies when reacting with different types of
H 2O + 2h+ → O2 + 2H+
2 (4)
2H+ + 2e− → H 2 (5)
CH3OH + H 2O → CO2 + 3H 2 (6)
Additionally, the band potentials and bandgap energy are the
primary criteria for the redox reaction to happen and generate
hydrogen. The bandgap energy of the photocatalyst should be
higher than 1.23 eV to attain a thermodynamically stable
photocatalytic process.32 Besides, matching the band position
with the redox potential of water is significant to promote the
redox reaction. Such that, in eq 5, the conduction band (CB)
of the semiconductor needed to be more negative than the
reduction potential of H+/H2 (−0.41 eV vs NHE at pH 7). On
the other hand, the VB potential should be more positive than
the oxidation potential of O2/H2O (+0.82 eV vs NHE at pH
7), as in eq 4.33 The addition of the sacrificial reagents would
facilitate the separation of the electron−hole pairs by
consuming holes and minimized the recombination rate of
the photocarriers, which directly increases the quantum yield.
MXene as a cocatalyst is primarily linked with the Schottky
heterojunction. The role of MXene in photocatalytic water
splitting is to enhance the performances of the hybrid
composites by providing a spatial separation and inhibit the
recombination of the photogenerated charges owing to its
unique metallic properties. The charge transfer mechanism in
the MXene-based composite, as denoted in Figure 3, is
achieved through the difference in the work function between
metallic MXene and the semiconductor. When MXenes and
the semiconductor form an intimate contact, strong interfacial
charges are built between the metal−semiconductor interfaces
forming a Schottky barrier.34 Under light irradiation, photo-
generated charges will be generated at the semiconductor. The
electrons will be excited to the CB of the semiconductor,
leaving the photogenerated holes at the VB. MXene serves as
an electron acceptor, generally having a larger work function,
associated with a lower Fermi level than its semiconductor
pair.35 The electron will migrate from the higher Fermi level
semiconductor toward the MXene until the Fermi level is
aligned. The strong interfacial charges promote electron
migration toward the MXene cocatalyst. The electrons will
then be accumulated and undergo a reduction reaction to
produce hydrogen. As designated in eq 2, the Schottky barrier
induced by MXenes will trap the electrons and inhibit the
accumulated electrons at the surfaces from migrating back to
the semiconductor fragment and recombining with the holes.36
The Schottky barrier, which serves as an electron sink,
promotes efficient separation between the photogenerated
charges and enhances the photocatalytic activity of the
photocatalyst.
Generally, in optimizing the photocatalytic performance,
factors such as the efficiency of the photocatalyst, design of the
photoreactor, sacrificial agents used, and the supply of light
should be given attention. This is because not only does the
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reaction performance depend on the efficiency of the
photocatalyst but the mentioned factors could also affect the
generation of products such as oxygen and hydrogen. On the
other hand, sacrificial reagents play a significant role as hole
scavengers to improve the separation of the photogenerated
charges.37 Different types of sacrificial agents contain different
adsorption abilities with various numbers of available protons.
Therefore, different types of photocatalysts might contain
sacrificial reagents. Such that, in eq 6, it has been disclosed that
having methanol as an electron donor could possibly generate
hydrogen through the methanol conversion, and it has been
highlighted that the number of carbon chains could contribute
to higher generation of hydrogen through alcohol conver-
sion.38 For achieving higher photocatalytic efficiency, the best
method is to improve the performances of the photocatalyst
through various engineering modifications such as the
formation of a hybrid photocatalyst, incorporation of metal-
based materials, tailoring the morphology, and also with
engineering defects. Therefore, optimizing all the reaction
parameters could substantially generate a higher reaction
efficiency.
3.0. CHARACTERISTICS OF MXENE
3.1. Stability of MXene. The distinct properties exhibited
by Ti3C2 MXene drive its emergence in the electrochemical
energy storage field, photocatalysis, electromagnetic interfer-
ence shielding, lithium-ion batteries, and electrochromic
devices. Ti3C2 MXene has been reported to display low
oxidation stability regardless of its unique morphological and
structural tunability. Under ambient conditions and aqueous
environments, Ti3C2 MXene is readily oxidized, in which the
titanium atoms will undergo oxidation reaction forming
titanium dioxide while the carbon atoms in Ti3C2 are
maintained in their intrinsic form.39 The formation of TiO2
is highly beneficial in some technological fields, such as in
photocatalysis. This is because the highly active material
forming through the oxidation of Ti3C2 MXene could improve
its photocatalytic properties and enhance the solar conversion
through the synergistic effects between Ti3C2 and its oxide
form.40,41 As denoted by Iqbal et al., factors affecting the
oxidative degradation of Ti3C2 MXene are not only due to
synthesis parameters and the quality of the MAX phases.
However, details such as etchant concentration, postetching
treatment, storage media, temperature, and dispersion
concentrations considerably affect the stability of the Ti3C2
MXene.42 Additionally, the termination group linking with
defect formation energy was believed to affect the oxidation
stability of Ti3C2 MXene. The inclusion of −OH-terminated
groups in Ti3C2 MXene is typically linked with lower oxidation
stability due to the minimum energy formation of the vacancy.
On the other hand, Ti3C2 MXene with O terminations,
associated with higher energy formation of Ti vacancies, is
more oxidatively stable.43 This corresponds to the study done
by Wan et al. on the inter-relation of surface functional groups
with the oxidation of Ti3C2 MXene.44 Through computational
analysis, it was revealed that the exposure of Ti−OH species
facilitates the oxidation of Ti3C2 MXene. Besides, Ti3C2
MXene with −OH termination groups exhibits the lowest
work function highlighting its highest reactivity. Therefore,
improving the oxidation stability can be accomplished through
the elimination of the −OH group, which was proved by Lee et
al. through the hydrogen annealing method.24 The finding
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Figure 4. (a) SEM images of accordion-like sheets of Ti3C2 MXene. (b) Formation of TiO2 on Ti3C2 MXene at the thermal treatment of 180 °C
[Reproduced with permission from ref 47. Copyright 2015 Elsevier]. (c) XRD analysis of Ti3C2 MXene at different thermal temperatures (0−650
°C) [Reproduced with permission from ref 48. Copyright 2018 Elsevier]. (d) Stability pathways of Ti3C2 MXene at different temperatures and (e)
Raman analysis of Ti3C2 MXene at 0, 1000, 1500 °C [Reproduced with permission from ref 46. Copyright 2019 American Chemical Society].

suggested that Ti3C2 MXene shows the fastest degradation rate
in the liquid media and the slowest in the solid media. It was
also revealed that Ti3C2 MXene exhibits better oxidation
stability and is less likely to degrade in organic solvents than in
water environments. Even though the study shows that the
colloidal particles of Ti3C2 MXene might be oxidized in the
organic solvent, they are still colloidally stable compared to
their state with water exposure. Besides, Ti3C2 MXene in
organic solvents such as in acetone and acetonitrile still
possesses higher conductivity than it would in water after
exposure for 21 days. This highly suggests that the oxidation of
Ti3C2 MXene occurs at a lower rate when it is exposed to
organic solvents. Nevertheless, studies have shown that
incorporating Ti3C2 MXene could still enhance the photo-
stability of the various composites in a water-mixture
environment with retained catalytic activity. For instance, the
photostability of CdS was highly improved after incorporating
Ti3C2 MXene while maintaining hydrogen production after
five consecutive cycles.45 Correspondingly, similar results were
observed in the composite g-C3N4/Ti3C2 MXene where the
photostability was highly enhanced and no deterioration in
catalytic activity was observed even after 10 h of irradiation in a
water-mixture environment. Besides, the crystal structure of
the composite remained in tact after long hours of reaction.
In the context of thermal stability, Ti3C2 MXene is a
thermally stable compound; its stability is highly dependent on
its chemical composition and the type of transitional element
(Ti) that makes up the compound. It was also hardly
decomposed and noted to have a decomposition temperature
in the range of 2000−3000 °C.46 However, it was noticed that,
under heat treatment, Ti3C2 MXene could also easily be
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converted into TiO2, which corresponds with the findings of
Gao et al.47 They suggested that under hydrothermal
treatment at 180 °C as shown in Figure 4a,b, the TiO2
nanoparticle nucleated on the surface of Ti3C2 MXene forming
a heterojunction composite. They also revealed that the
composite exhibits better photocatalytic activity than TiO2 and
Ti3C2 alone, highly proving that the formation of the hybrid
Ti3C2/TiO2 gives promotional effects to efficient carrier
dynamics. Likewise, a finding by Low et al. highlighted that
higher heat treatment of Ti3C2 MXene could result in an
increased concentration of TiO2.48 As ascribed by XRD
analysis in Figure 4c, at 350 °C, the crystallinity of the Ti3C2
MXene shows an increment with a slight formation of anatase
TiO2. On the other hand, as the temperature was increased to
450 °C, the diffraction intensity of TiO2 is obvious, indicating
an increased formation of TiO2. However, as the temperature
reached 650 °C, a complete transformation of TiO2 from
Ti3C2 MXene can be observed. In another study, we
investigated the growth of TiO2 on Ti3C2 MXene through
thermal oxidation, whereby the effects of oxidation time from 3
to 5 h with different heat treatments of 300−500 °C on the
photocatalytic activity of Ti3C2 MXene under air exposure
were also studied.48 The findings suggested that, when Ti3C2
MXene was oxidized under air atmosphere, a greater amount
of TiO2 was produced, resulting in more superior photo-
catalytic activity of the hybrid TiO2/Ti3C2 MXene. Calcining
the Ti3C2 MXene at 300 °C at 3 h under atmospheric exposure
showed the highest hydrogen production rate with the trend of
300 °C-TiO2/Ti3C2 MXene-ox (3 h) > 500 °C-TiO2/Ti3C2
MXene-ox (3 h) > 300 °C-TiO2/Ti3C2 MXene-ox (5 h) >
TiO2/Ti3C2 MXene-HF. The correlation between the thermal
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Figure 5. Overview of the nature and electronic properties of different types of MXene materials based on theoretical calculation.
treatment with the conversion of TiO2 from Ti3C2 MXene is
beneficial in controlling the amount of TiO2 loading on Ti3C2
MXene, which in return helps to give a firm understanding on
the properties of Ti3C2 MXene for maximizing its photo-
catalytic performance.
Additionally, it was also ascribed that a higher etchant
concentration could result in the increase of TiO2 conversion
with anatase and rutile phase formation resulting from the
stronger oxidation reaction of Ti3C2 MXene.49 Higher
concentrations of HF considerably enable more conversion
of TiO2 from Ti3C2 MXene. A stronger oxidation process
provides higher quality of the produced TiO2 (rutile)
compared to TiO2 (anatase), indicating that more conversion
of rutile phase TiO2 could occur during the oxidation process.
Besides, according to Ghassemi et al., a slower heating rate will
lead to the formation of rutile TiO2, while a quick heating rate
will result in the formation of its anatase phase.50 Further
analysis through thermogravimetric (TG) and differential
scanning calorimetric (DSC) measurement on Ti3C2 MXene
by Li et al. revealed that Ti3C2 MXene undergoes a weight
change when heat is supplied. Increasing the temperature from
RT to 200 °C led to 0.38% weight loss. Correspondingly,
4.48% loss was observed when the temperature was raised to
800 °C, and 2.47% weight loss was found from 800 to 1000
°C. This analysis was done under inert conditions, which
shows clear evidence that the weight loss was not due to the
oxidation of Ti3C2 MXene but to thermal degradation.
However, the small losses in weight by Ti3C2 MXene under
a higher heat treatment indicated the good thermal stability
exhibited by Ti3C2 MXene.
According to Seredych et al., the postheat treatment above
and below the critical temperature of phase transformation
could affect the surface chemistry and chemical structure of
Ti3C2 MXene.46 Figure 4d denotes the schematic of the
thermal stability pathway of Ti3C2 MXene. Additionally,
multilayer Ti3C2 MXene with different termination groups
can undergo chemical and structural modifications under a
thermal treatment above the critical temperature of phase
transformation between 750 and 900 °C. On the other hand,
treatment below the critical temperature leads to a change in
the surface chemistry and decomposition of the termination
groups. Under inert conditions and at 5% HF concentration,
the dissociation of the functional groups, including O2 and H2,
occurred at the temperature of 530 °C. As the temperature
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reaches above 740 °C, the degradation of functional groups
with the release of CO occurred, wherein the degradation
process is at its maximum in the temperature range of 830−
850 °C. The release of CO further denotes the conversion of
Ti3C2 MXene into titanium carbide (TiC) as the thermal
temperature goes beyond 850 °C. A lower amount of −F
termination leads to a higher amount of CO released due to
the smaller amount of HF concentration used. Complete
conversion into TiC was observed at the temperature of 1500
°C while there was still a small amount of Ti3C2 MXene
remaining at 1000 °C. Indicatively, the Raman spectroscopy
shown in Figure 4e, revealed the presence of TiO2 and free
carbon at 1000 °C. Even when the Ti3C2 MXene was thermally
treated without atmospheric exposure where inert He was
supplied, the oxidation of Ti3C2 can still occur at a higher
temperature which can be due to the presence of the reactive
forms of oxygen. This finding suggests that, during heat
treatment, the hydroxyl radicals and superoxide anions were
generated even without any additional supply of oxygen and
partial oxidation can still happen on the Ti group of Ti3C2
MXene, leading to a small conversion to TiO2. However, when
the heat was supplied up to ∼800 °C, Ti3C2 MXene did not
undergo any compositional changes and remained stable. It is
worth mentioning that the concentration of the etchant affects
the thermal stability of the Ti 3 C 2 MXene, a lower
concentration of HF results in higher thermal efficiency,
which might be due to the reduced defect density. It was noted
that the structural and chemical composition of the MXene
positively contributed to its thermal stability, and it was
revealed that Ti3C2 MXene is more thermally stable than other
types of MXene. The type of transitional metal used in the
MXene is hypothetically one of the contributing factors for the
stability of MXene. Therefore, a fundamental understanding of
the Ti3C2 MXene thermal stability is significant to tune their
properties through heat treatment which is beneficial to meet
the application requirements.
3.2. Optoelectronic Properties of MXene. Ti 3C2
MXene manifests good optical properties, which are semi-
transparent and conductive. The ability to sustain higher laser
radiation power than graphene nominates them as one of the
most prominent supporting materials in many wider spectra
applications such as optoelectronic and photonic devices.51 It
was ascribed by Khazaei et al. that different types of MXene
can exhibit either metallic or semiconducting properties.52
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Figure 5 denotes the overview on the electronic properties and
the nature of MXene-based materials upon functionalization.
Even though most of the MXene was known to be metallic in
nature, through different elemental constitutions and surface
functionalizations, MXene can exhibit semiconducting proper-
ties. The metallic MXene was noted to have a work function
ranging from 1.8 to 8 eV, while MXene with semiconducting
properties has a bandgap ranging from 0.05 to 2.87 eV, tuned
by the different compositional institutions.13 For instance, the
theoretical bandgap energy of MXene with semiconducting
properties has been disclosed through PBE functional
computations. As denoted, after functionalization, Ti2CO2,
Zr2CO2, Hf2CO2, Sc2CF2, Sc2C(OH)2, and Sc2CO2 were
predicted to have band gaps of 0.24, 0.88, 1.0, 1.03, 0.45, and
1.80 eV, respectively. Contrarily, functionalized Cr2C and
Cr2N MXenes are magnetic in nature, while Ti3C2, Ti4C3,
Ti5C4, Ti4N3, V3C2, V4C3, Nb4C3, Nb4C4, Ta3C2, and Ta4C3,
on the other hand, maintained their metallic properties
regardless of any surface functionalization. The charge transfer
between the functional group and MXene as well as the
changes in the total surface dipole moments due to surface
relaxation leading to the formation of induced dipole moments
which control the work functions of the metallic −OH, −O,
and −F terminated Tin+1Xn MXenes. In this context, −OH
terminated MXenes exhibit work functions ranging from 1.6 to
2.8 eV, while higher work functions can be observed in −O
terminated MXenes, between 5.75 and 6.25 eV.53 This is
relative to the study done by Zhang et al. reporting on the
metallic characteristics exhibited by Ti3C2Tx MXene.54
Therefore, the presence of surface termination could alter
the optoelectronic properties of some MXenes from originally
metallic in nature into semiconducting. The alteration of the
electronic properties in some of the MXene can be due to the
hybridization of the electron orbitals resulting in the variation
of the bandgap energy.55 This can be deduced by taking the
semiconducting properties of Sc2CTx into the account where
the variations in the bandgap energy are observed with
different types of surface terminations incorporated following
the order of −O2 > −F2 > −(OH)2. The similar effects noticed
in −F and −OH termination could be due to the electronic
structures of the functional groups as both can only receive one
electron, whereby −O require two electrons.
Additionally, it was reported that the optical transmittance
was linked with the thickness of the Ti3C2 MXene film, in
which the thickness can be tuned by controlling the types of
intercalating agents instituted into the Ti3C2 MXene sheets.56
For instance, the alteration in the transmittance properties of
Ti3C2 MXene was observed under treatment with different
intercalating agents such as DMSO, urea, and hydrazine, as
reported by Kannan et al.57 On the other hand, Hart et al. for
the first time performed a theoretical study by correlating the
chemical analysis with in situ resistance and negative
temperature-dependence of resistance (dR/dT) measurements
to investigate the effects of intercalating solvents on the
electronic properties of MXenes.58 They revealed that the
nature of the intercalating solvents could result in a transition
between metallic and semiconducting properties in several
types of MXenes via interflake effects. They also highlighted
that an intercalating solvent could modulate the device
resistance by a unit due to the alteration in the interflake
spacing, dependent on the size of the intercalants. The study
on the electronic transport behavior was performed by
intercalating a large organic ion of TBA+ with H2O into
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different types of MXenes (Ti 3 C 2 Tx, Ti 3 CNTx, and
Mo2TiC2Tx). Additionally, the effects of deintercalation on
the electronic properties of MXenes were also stressed.
Findings suggested that Mo2TiC2Tx and Ti3CNTx undergo
an alteration in the optoelectronic properties upon dein-
tercalation of TBA+ where the electronic behavior changes
from semiconducting properties into metallic-like materials. It
was ascribed for all the studied MXenes, the deintercalation
resulting in higher electronic conductivity compared to with
the presence of intercalating solvents. Deintercalation of H2O
in Ti3CNTx revealed a 36% decrease in the resistance, which
transformed dR/dT from negative to positive, indicating the
transformation from semiconducting to metallic properties.
This strongly suggests that the alteration in the electronic
properties of the MXenes is due to the changes of interflake
resistance, which is positively linked to the nature of
intercalating solvents. It is worth mentioning that, even if
both Ti3C2Tx and Ti3CNTx are metallic in nature, the
intercalation of H2O in Ti3C2Tx results in metallic conduction.
On the other hand, intercalation of H2O in Ti3CNTx results in
semiconductor-like conductivity.
In the prospect of optical absorption, Jhon et al. conducted
Z-scan analysis on the nonlinear absorption, scattering, and
refractive index of Ti3C2 MXene. It has been disclosed that
Ti3C2 MXene possesses a large nonlinear optical absorption
coefficient and a higher threshold for light-induced damage
with 50% increase in nonlinear transmittance, highlighting
excellent optical properties.59 Besides through DFT studies by
Berdiyorov et al., the inter-relation between surface termi-
nation, Tx on the optical properties of Ti3C2Tx MXene has
been unveiled.60 They disclosed that, in the visible region
spectrum, −F and −OH terminated Ti3C2 MXene exhibit
smaller absorption and reflectivity than Ti3C2 MXene without
any termination, while −O terminated Ti3C2 MXene shows
excellent absorption and reflectivity. However, Ti3C2 MXene
with all surface termination (Tx = −F, −OH, −O) possesses
larger reflectivity than pure Ti3C2 MXene when observed in
the UV range spectrum. Therefore, it can be concluded that
the optical properties of the MXene are positively associated
with the transitional metal making up MXene and different
surface functionalizations.61 This ultimately increases the role
of MXene in various technological applications, as their
electronic and optical properties can be easily tuned by
considering the discussed factors to meet the specific demands
and requirements.
3.3. Electrical Properties of MXene. The excellent
electrical conductivity exhibited by Ti3C2 MXene makes it
highly favored in many energy applications. High electrical
conductivity (≈6500 S cm−1) appoints it to serve as an
electron sink for improving the solar absorption and the energy
conversion of the hybrid photocatalyst.62 This contributes to
the formation of the Schottky junction, regarded as the
fundamental factor for ameliorating the photoactivity observed
in various hybrid photocatalysts.36,63 Additionally, the
institution of different transitional metals and X elements
accords the Ti3C2 MXene with electrical conductivity ranging
from 1 S cm−1 to as high as 20 000 S cm−1 under controlled
synthesis conditions.53 It was noted that morphological
tunability, compositional configuration, and surface termina-
tion are contributing factors that control the conductivity of
Ti3C2 MXene.
The electrical conductivity of Ti3C2 MXene was observed to
improve (4.52 × 10−4 S m−1) when it was modified with epoxy
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Figure 6. Properties of noble metals and general overview of MXene in Schottky heterojunctions and all-solid-state Z-scheme heterojunction
systems.
resin.44 Tuning the morphology of Ti3C2 MXene into a
hierarchical structure hypothetically improves the electrical
properties of the Ti3C2 MXene. The porous “skin/skeleton”-
like structure constructed by Sun et al. was revealed to
effectively facilitate the transfer of electrons and ions associated
with excellent electrochemical performance.64 Besides, this
hierarchical structure exhibits a high capacitance efficiency of
7.14 F cm−3 and 357 F g−1, which renders it favor in the energy
storage field. Compared to graphite carbon, Ti3C2 MXene
anodes display a higher charge/discharge rate as they exhibit a
lower lithium diffusion barrier (0.07 eV) than graphite carbon
(≈0.3 eV).65 On the other hand, a study by Ling et al.
described that pure Ti3C2 MXene exhibits greater electrical
conductivity of 2.4 × 105 S m−1 compared to the electrical
conductivity of 2.2 × 104 S m−1 of polymerized Ti3C2 MXene
with (poly(vinyl alcohol)) (PVA) and poly(diallyldimethyl-
ammonium chloride).66 Shi et al. mentioned that the electrical
conductivity of Ti3C2 MXene could be configured through
surface functionalization.28 The formation of a fluoride-free,
rich in −O termination Ti3C2 MXene through the iodine
etching preparation method demonstrated a higher electrical
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conductivity of 1250 S cm−1 which is close to that of those
with −F termination, 1500 S cm−1. This indicates that tailoring
the functional groups could also affect the electrical properties
of Ti3C2 MXene. This is because the flakes of Ti3C2(O,OH)
with oxygen content of 18.7 wt % were observed to be thin in
size with 71% of the flakes being thinner than 5 nm. This made
it easier to prepare the Ti3C2 MXene film by filtration of the
MXene dispersion. These thinner sizes contributed to higher
electrical conductivity.
On the other hand, Ti3C2 MXene, with the exclusion of −F
termination, manifests an excellent gravimetric capacitance of
293 F g−1 which is comparatively higher than those with the
inclusion of −F terminating groups 50−290 F g−1. It is
denoted that functionalized MXenes can exist as metallic
materials or as semiconductors. In this context, metallic
MXenes were noticed to exhibit excellent electrical con-
ductivities compared to semiconducting MXenes. However,
the Seebeck coefficient, which is the measure of the
thermoelectric voltage in metallic MXenes, is very small. On
the other hand, semiconducting MXenes exhibit higher
Seebeck coefficients resulting in good electrical conductivity
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Figure 7. Electron transmission and redox reaction in (a) bulk and (b) mesoporous surface photocatalysts. [Reproduced with permission from ref
71. Copyright 2007 Elsevier]. (c) Rate of hydrogen production and (d) DRS analysis by pure Ti3C2 MXene, g-C3N4, and different ratios of g-
C3N4/Ti3C2 MXene [Reproduced with permission from ref 72. Copyright 2020 Elsevier]. (e) Schematic diagram of Ti3C2 MXene along with its
functional group and (f) Schematic illustration of the reaction mechanism in the g-C3N4/p-Ti3C2Tx MXene composite [Reproduced with
permission from ref 80. Copyright 2019 John Wiley and Sons].

and higher power factor, which can be ideally applied in
thermoelectric applications.14
4.0. TI3C2 MXENE AS A PHOTOACTIVITY ENHANCER
The formation of Schottky heterojunctions is normally
associated with the integration of noble metals such as Au,
Pd, Ag, and Pt which have been extensively studied to improve
photocatalytic performances, specifically in hydrogen produc-
tion. However, the fact that noble metals are expensive and not
commercially available makes them less pertinent in the field of
photocatalysis.67 Hence, rigorous efforts have been made to
study new materials that exhibit the same functionality and
efficiency as those of noble metals, and among them, Ti3C2
MXene has been nominated as one of the best candidates.
MXene has been noted as a photocatalytic enhancer in various
semiconductor composites, owing to the Schottky junction
formation and its role as an electron mediator. For instance,
the utilization of Ti3C2 MXene as a cocatalyst in promoting the
photocatalytic activity of g-C3N4, CdS, TiO2, MoS2, CdLa2S4,
SnNb2O6, and ZnS was extensively studied. Figure 6 shows the
main properties of noble metals, their limitations, and the role
of MXene as an electron mediator and in the formation of the
Schottky junctions.
4.1. Construction of Schottky Junctions. Good
electrical conductivity and metallic properties promote the
11991
formation of Schottky junctions between metallic Ti3C2
MXene and semiconductor pairs. The Schottky junction was
generally formed at the interface of metal and semiconductors,
while the migration of electrons is based on the Fermi level of
metal/semiconductor pairs. The close contact between
metallic materials and semiconductors induced a built-in
internal electric field which promotes the migration and
separation of the photogenerated charges. The synergistic
combination of metal and semiconductor ameliorates the
photocatalyst performances through the confinement of
electrons at the metallic region. The metal work function
value (ϕ) associated with Schottky barrier formation is defined
as the energy required to transfer an electron from the Fermi
level into the vacuum level, where the higher work function
value denotes the lower Fermi level energy. The vacuum level
is known as the reference level, where the electrons exhibit an
energy level outside of the metal with zero kinetic energy. The
work function value (ϕ) is normally associated with the
efficiency of the photocatalyst. In this context, a higher
Schottky barrier that leads to more hydrogen production could
be attained when the difference in the metal work functions
with the semiconductors is greater.33 The band alignment at
metal−semiconductor junctions and the difference of the work
functions between metals and semiconductors lead to the
formation of the electronic potential barrier which assisted the
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capture of the electrons at the metal surfaces. In order for the
electron−hole pairs to be spatially separated with the
promotion of the Schottky junction, the CB of the semi-
conductors must be higher than the Fermi level of the metal so
that electrons could be transferred and trapped at the metal
counterpart while holes remain at the VB of semiconductors to
undergo the oxidation reaction. Therefore, the promotion of
the Schottky junction by Ti3C2 MXene could enhance the
photocatalytic performance with regard to efficient carriers
dynamics.
4.2. Development of Ti3C2 MXene-Based Schottky
Junctions. 4.2.1. Design of Schottky-Based g-C3N4. The
abundancy, economic, and excellent properties of graphitic
carbon nitride (g-C3N4) have increased their reputability as a
single and hybrid composite for photocatalytic water
splitting.68 It has been noted that g-C3N4 possesses good
electrochemical stability, appropriate bandgap, and shows
positive results for the HER and OER.69,70 Compared to
other conventional photocatalysts, g-C3N4 has a bandgap of 2.7
eV, better solar absorption, and a mesoporous surface area
below 10 m2/g which are excellent indicators for hydrogen
production through photocatalysis. The mesoporosity of g-
C3N4 undeniably is one of the significant properties that
positively affect its photocatalytic efficiency. It was highlighted
that, on mesoporous surfaces, shorter distances were taken by
the photogenerated electron−hole pairs to reach the surface of
the photocatalyst than in bulk, as shown in Figure 7a,b. The
longer the time for the photogenerated charges to reach the
photocatalyst surfaces, the higher their chances of recombining
due to low exciton energy. However, in the mesoporous
photocatalyst, the redox reaction might occur at the pore wall,
reducing the chances of charge recombination.71 Even though
g-C3N4 possesses various advantages in the photocatalysis field,
it has been reported that they exhibit a significant electrostatic
potential barrier leading to higher recombination rates of
electrons and holes. Additionally, the low solar absorption
performances in g-C3N4 lower their photocatalytic efficiency
toward hydrogen production. Therefore, employing a highly
conductive Ti3C2 MXene as a cocatalyst was noted to reduce
the potential barrier of g-C3N4, providing proficient charge
separation and promoting maximal photon absorption.
The photocatalytic activity of Ti3C2 MXene integrated g-
C3N4 was investigated by Li et al. using a closed glass
photoreactor.72 In this study, the composite of g-C3N4/Ti3C2
MXene was prepared via a one-step thermal annealing method
under a heat treatment at 550 °C. The hydrogen production
was observed to increase up to 116.2 μmol g−1 h−1 which is six
times higher than pure g-C3N4, as shown in Figure 7c. In the
prospect of the optical absorption, it was noticed that pure g-
C3N4 shows prominent absorption edge characteristics in the
range of 480 nm, indicating poor optical performance. As
depicted in DRS analysis in Figure 7d, the introduction of
Ti3C2 MXene successfully shifts the absorption spectrum in the
visible range of 450−700 nm. The introduction of Ti3C2
MXene, which exhibits metallic electronic band structures,
serves as an electron sink to prevent the reverse injection of
electrons back to g-C3N4.73 PL analysis further confirmed that
the recombination of the photocarriers in the hybrid g-C3N4/
Ti3C2 MXene was greatly hindered, benefiting from the
formation of the Schottky junction. It was disclosed that the
introduction of 80 wt % Ti3C2 MXene remarkably promotes
the photocatalytic activity of the hybrid composite due to the
following reasons: (1) Stronger electrostatic interaction
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between the two semiconductors provides a shorter electron
transmission pathway fostering the electron migration from g-
C3N4 to Ti3C2 MXene. (2) The replacement of −F into −O
termination in Ti3C2 MXene through the annealing process
provides stronger bridging effects to connect the g-C3N4 with
Ti3C2 MXene without the assistance of other surface-active
agents.74 (3) The induced internal electric field at the metal−
semiconductor interface provides a proficient separation of
electrons and holes, subsequently improving the photocatalytic
activity. (4) Introduction of highly conductive Ti3C2 MXene
promotes maximum photon absorption in the visible region.
In a different study, the integration between two-dimen-
sional (2D) Ti3C2 MXene sheets with one-dimensional (1D)
g-C3N4 was extensively studied by Huang and his co-
workers.75 The fabrication of the 1D/2D composite was
attained through an electrostatic self-assembly process. In this
study, the delamination of 2D multilayer Ti3C2 MXene was
first achieved through the in situ HF etching of a MAX
precursor with HF/LiF etchant, directly producing a single
layer Ti3C2 MXene sheet.76 The g-C3N4 was synthesized via
the supramolecular self-assembly method to obtain the g-C3N4
in tubular form, followed by a calcination process to fabricate a
P-doped tubular g-C3N4 (PTCN). The addition of an optimal
amount of Ti3C2 MXene sheets into the PTCN displays a
notable increase in hydrogen production with a 5.3- and 3.0-
fold rate higher than in pure bulk g-C3N4 and PTCN,
respectively. Additionally, modulating g-C3N4 into tubular
form could provide an oriented charges transfer pathway along
the longitudinal dimension, at the same time improving the
specific surface area, which could reduce the mass transfer
resistance as proclaimed by Tong et al.77 The BET surface area
indicates that tailoring the morphology of bulk g-C3N4 into the
tubular form eminently improves the surface area from 2.3 to
17.4 m2/g. On the other hand, decorating Ti3C2 MXene into
the PTCN could supply the composite with plenty of catalytic
active sites and provide a stronger redox reactivity than those
by the carbon materials, owing to the exposed terminal metal
sites of Ti from Ti3C2 MXene.78 Accordingly, Kang et al.
highlighted that the g-C3N4 integrated with Ti3C2 MXene
hollow spheres profoundly generated 1.22-fold higher hydro-
gen than the intrinsic g-C3N4/Ti3C2 MXene composite.79 An
improved photocatalytic activity was ascribed due to the
hollow structure morphology enhancing the specific surface
area from 77.4 to 100.1 m2 g−1, which aided in the reactant
adsorption.
Additionally, the comparison study between PTCN/Ti3C2
MXene and PTCN/RGO further revealed that PTCN/Ti3C2
MXene exhibits better carrier separation than the hybrid
PTCN/RGO, benefiting from the Schottky junction by a
highly conductive Ti3C2 MXene material. The hydrogen
generation by PTCN integrated with metallic Ti3C2 MXene
was 1.6 times higher than with RGO, further validating the role
of Ti3C2 MXene as a photoactivity enhancer. Furthermore, the
apparent quantum efficiency of PTCN/Ti3C2 MXene at 420
nm was observed to be profoundly higher (5.9%) than those
by the PTCN/RGO (2.3%). The distinctive Schottky
formation along with the induced internal electric field by
Ti3C2 MXene serves as an electron sink and photon collector,
which shows substantial promise as a leading cocatalyst for
promoting the photocatalytic activity in other hybrid
composites.
The role of Ti3C2 MXene as a photoactivity enhancer was
further explored by Xu and co-workers by modifying the
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Figure 8. (a) Electron transfer mechanism of g-C3N4/Ti3C2 MXene and (b) hydrogen evolution rate of g-C3N4, protonated g-C3N4, and g-C3N4/
Ti3C2 Mxene (Ti3C2 = 10, 20, 40) [Reproduced with permission from ref 81. Copyright 2021 Elsevier]. (c) Synthesis process of Ti3C2 MXene/O-
doped g-C3N4 Schottky junction, (d) SEM image of 2D/2D stacked MX/HCN heterostructures, and (e) electrostatic potentials of the Ti3C2
MXene and O-doped g-C3N4 [Reproduced with permission from ref 82. Copyright 2019 Elsevier].

surface functional groups of Ti3C2 MXene via the plasma-
treatment method.80 The ultrathin 2D layered Ti3C2Tx MXene
was first synthesized via HF etching of the MAX precursor with
intercalation in DMSO. The resulting Ti3C2Tx MXene then
underwent plasma treatment under the N2/H2 atmosphere
with a reaction temperature of 500 °C. An illustration of the
detailed synthesis of g-C3N4/p-Ti3C2Tx MXene is depicted in
Figure 7e. The thermal diffusion and ionization of H+ from the
plasma induction of p-Ti3C2Tx MXene facilitates the diffusion
of Ti atoms to react with O at the edges of the p-Ti3C2Tx
MXene sheets and form Ti−O bonds. This results in the
formation of a highly defective graphitic carbon structure due
to the reduction of Ti−C bonds in the p-Ti3C2Tx MXene.
Besides, the effects of H+ ionization were also revealed to
generate the Ti4+ cations, eliminating the −F and −OH
functional groups and increasing the surface vacancies. This
further elucidates the finding that p-Ti3C2Tx MXene under-
went a change in structural chemistry and exhibited different
photocatalytic properties from the original Ti3C2Tx MXene.
The integration of p-Ti3C2Tx MXene nanosheets with a
tailored surface functional group increased the specific surface
area and expanded the space between the g-C3N4 layers,
resulting in an extended carrier lifetime from 16.76 to 19.32 ns,
which gave subsequent improvement in the photocatalytic
performance with 25.4 times higher than in pure g-C3N4. It
11993
was also worth mentioning that the plasma-treated Ti3C2Tx
MXene hybrid shows a higher photocatalytic efficiency
compared to the original Ti3C2Tx MXene hybrid with 2.4
times more activity enhancement. This photoactivity enhance-
ment was highly attributed to the formation of Ti4+ groups in
the p-Ti3C2Tx MXene framework, functioning as an electron
trapping center that provides a maximal separation of electrons
and holes. The reaction between generated Ti3+ with H+
favorably promotes the generation of hydrogen. The schematic
illustration of the reaction mechanism of g-C3N4/p-Ti3C2Tx
MXene composite is depicted in Figure 7f. The utilization of
Ti3C2 MXene as a cocatalyst in driving the photocatalytic
hydrogen production in the g-C3N4 composite can be further
explained through the study performed by Xu et al.81 and Lin
et al.82 The introduction of Ti3C2 MXene into the protonated
g-C 3 N4 (PCN) substantially augmented the hydrogen
generation up to 2181 μmol g−1 h−1 which was 5.5 times
higher than that in bulk g-C3N4 with an apparent quantum
efficiency (AQE) of 8.6% at 420 nm. Besides, PCN/Ti3C2
MXene shows stable hydrogen production after five cycles,
while maintaining the photocatalytic activity. The composite of
PCN/Ti3C2 MXene was synthesized via electrostatic-driven
interactions. Protonating g-C3N4 with dilute HCl was believed
to alter its surface charge to be more positive, strengthening
the electrostatic interaction between g-C3N4 and Ti3C2
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Figure 9. (a) Rate of hydrogen production for pure Cds and different loadings of Ti3C2 MXene/CdS and (b) PL analysis for pure CdS and 10%
Ti3C2 MXene/CdS [Reproduced with permission from ref 88. Copyright 2020 Elsevier]. (c) Hydrogen generation rate of pristine CdS and
different ratio Ti3C2 MXene-CdS, (d) SEM image of 1D CdS/2D Ti3C2 MXene, and (e) photocatalytic mechanism of electron transfer from CdS
to the surface of Ti3C2 MXene [Reproduced with permission from ref 45. Copyright 2020 Elsevier].

MXene. The zeta potentials of g-C3N4, PCN, and Ti3C2
MXene were revealed to be −9.5, 27.3, and 11.4 mV,
respectively. The stronger electrostatic contact between PCN
and Ti3C2 MXene shortened the transfer pathway of the
electrons undergoing the redox reaction, accelerating the
charge migration. The schematic photocatalytic mechanism of
PCN/Ti3C2 is shown in Figure 8a. The integration of Ti3C2
MXene with higher electrical mobility is noted to extend the
spectral response above 500 nm and lower the electron transfer
resistances in the PCN. Additionally, the role of Ti3C2 MXene
in the composite of PCN/Ti3C2 MXene is unveiled by varying
the amount of Ti3C2 MXene loading into 10, 20, and 40 mg.
As shown in Figure 8b, altering the amount of Ti3C2 MXene
loading affects the hydrogen generation rate, further affirming
that Ti3C2 MXene indeed plays a critical role as a photoactivity
enhancer. Accordingly, the composite of O-doped g-C3N4/
Ti3C2 MXene shows a notable increment in the hydrogen
production up to 25 124 μmol g−1 h−1 with an AQE of 6.53%
at 420 nm. As shown in Figure 8c, the bulk g-C3N4 undergoes
thermal exfoliation at 500 °C, which is then protonated to
form a positively charged O-doped g-C3N4. The prepared O-
doped g-C3N4 is assembled with Ti3C2 MXene via electrostatic
assembly forming an intense 2D/2D stacked MX/HCN
heterostructures as observed from the SEM image in Figure
8d. The stronger interaction between Ti3C2 MXene and O-
doped g-C3N4 is achieved by modulating the surface charge of
the g-C3N4, thereby forming a stacked multicharged MX/HCN
hybrid. Through the computational analysis by DFT, the
electrostatic potentials of the Ti3C2 MXene and O-doped g-
C3N4 are confirmed to be 3.32 and 5.19 eV, respectively, as
denoted in Figure 8e. The lower work function exhibited by
11994
Ti3C2 MXene drives the electrons generated at the CB of HCN
to migrate toward the metallic Ti3C2 MXene nanosheets. The
close interfacial contact between them reduces the charge
transfer resistances, which facilitates the transferring of
electrons. The gathered electrons at the surfaces of Ti3C2
MXene then react with adsorbed water molecules to produce
the hydrogen. The formation of the Schottky junction
promotes the separation of the photogenerated carriers,
which prolongs their lifetimes in undergoing the redox
reaction, giving a subsequent improvement in the hydrogen
production rate.
4.2.2. Design of Schottky-Based CdS. One of the critical
elements in the fabrication of the photocatalyst for photo-
catalytic hydrogen production is the ability to maximize the
solar absorption performances, which is mainly associated with
the bandgap energy.83 Among the traditional photocatalysts,
cadmium sulfide (CdS) is known to exhibit excellent
photochemical and structural properties, making it one of
the most extensively studied semiconductors. It is noted that
CdS has appropriate band potential and a narrow bandgap of
2.4 eV, which are considered to be features of a good visible-
active photocatalyst. The major constraint in the application of
CdS as a photocatalyst is that they are typically subjected to
photocorrosion.84 It is indisputable that the low rate of
hydrogen generation is indicatively caused by the low chemical
stability of the photocatalyst, generally due to photocorrosion.
Besides, the charge recombination in bulk CdS is considerably
higher, restraining their functionality and applicability in large-
scale photocatalytic hydrogen production. The shortcoming of
the CdS photocatalyst could be overcome by integrating a
cocatalyst to enhance its photocatalytic efficiency and chemical
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properties. Introducing noble metals such as Pt auspiciously
improves the stability of the photocatalyst.85 The inclusion of
noble metals acting as electron sinks could reduce the
recombination rate of electron−hole pairs, prolonging the
excitation time and increasing the quantum efficiency. In
addition, the best substitution for noncommercial noble metals
is a widely studied Ti3C2 MXene by which their functionality
has been scientifically recognized.86,87
The study of Ti3C2 MXene as a cocatalyst in improving the
photocatalytic efficiency of CdS has been reported by Li et al.88
They disclosed that fabricating CdS nanowires with Ti3C2
MXene could improve the hydrogen production rate up to
15.4 mmol g−1 h−1, which is superior than pristine CdS (4.8
mmol g−1 h−1). Optimal control of Ti3C2 MXene could
maximize the efficiency of the hybrid photocatalyst, while
excessive inclusion is typically associated with shielding effects
which could decrease their photocatalytic efficiency.89 This is
because an excessive amount of Ti3C2 MXene could impede
light from reaching the photocatalyst surface, and only a small
amount of light could penetrate to activate the inner surfaces.
This therefore explains the observed results shown in Figure 9a
that 10% Ti3C2 MXene gives the optimal efficiency. Besides,
higher photocatalytic activity was shown by CdS/Ti3C2
MXene when compared to that of pure CdS positively
associated with the Schottky heterojunction formation, which
aided the electron mobility and hindered the recombination of
photogenerated charges.90 This was further confirmed through
the distinct reduction in the peak observed by CdS/Ti3C2
MXene compared to pure CdS from the PL analysis suggested
in Figure 9b. Additionally, the higher production rate of
hydrogen is also linked with the exposure of the termination
group −O on Ti3C2 MXene surfaces to expedite the reaction
and hydrogen generation. It was mutually beneficial that
integrating CdS/Ti3C2 MXene could enhance the perform-
ances of CdS photocatalyst and simultaneously inhibit the
agglomeration in of the nanoparticles. Besides, the photo-
stability of the composite was observed to increase under long
exposure of light with retained catalytic activity for 24 h of
reaction, showing that the photocorrosion in CdS was greatly
hindered.
In another study, Xiao et al. successfully constructed 1D
CdS/2D Ti3C2 MXene Schottky heterojunction composites
through in situ assembly.45 The formation of a Schottky
junction and the synergistic integration of n-type semi-
conductor CdS with highly conductive Ti3C2 MXene
propitiously augmented the photocatalytic hydrogen produc-
tion. Xiao et al. highlighted that the employment of 20 mg
Ti3C2 MXene into the pristine CdS nanorod ameliorated the
hydrogen rate up to 2407 μmol g−1 h−1 which is seven times
higher than that of pristine CdS nanorods, as observed in
Figure 9c. The controlled morphology of the composite 1D
CdS/2D Ti3C2 MXene can be discerned through the SEM
image in Figure 9d, showing the successful embedding of CdS
nanorods onto the Ti3C2 MXene. The confinement effect from
negatively charged Ti3C2 MXene inherently altered the length
of CdS nanorods in the composite. The charge transfer in the
composite of 1D CdS/2D Ti3C2 MXene is as illustrated in
Figure 9e. Under light irradiation, the photogenerated
electrons will migrate to the CB of CdS which is then quickly
transferred to the metallic MXene surface through the intimate
coupling interface. The migration of electrons from CdS to
MXene is due to the higher Fermi energy level possessed by
MXene than the conduction band energy of CdS. The electron
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trap at the MXene surface impedes them from returning to the
semiconductor, which then undergoes a reduction process to
produce hydrogen. Notably, the remarkable metal conductivity
exhibited by MXene and the sinking of electrons through the
Schottky heterojunction on the Ti3C2 MXene−CdS interface
positively facilitate the separation of electron−hole pairs and
prolong the exciton lifetime.91
The formation of a Ti3C2 MXene-CdS hybrid with a 3D
structure prepared hydrothermally induced superior photo-
catalytic hydrogen production and was noticed to be the
highest reported so far among Ti3C2 MXene-CdS hybrids.17
The favorable position of the Fermi level in the composite
accompanied by higher electrical conductivity of the metallic
Ti3C2 MXene substantially generated 14 342 mmol h−1 g−1
hydrogen production with a quantum efficiency of 40.1% at
420 nm. This performance was ascribed to the specific surface
area and the pore volume additionally affecting the photo-
catalytic activity. The correlation study between the surface
area and photocatalytic activity attested that a higher specific
surface area indeed generated more hydrogen compared to
photocatalysts with lower surface areas. The composite of
Ti3C2 MXene-CdS with an optimal amount of 2.5% Ti3C2
MXene loading was observed to exhibit the largest specific
surface area of 120 m2 g−1. A gradual increase in the surface
area was shown as the amount of Ti3C2 MXene loading was
increased. On the other hand, excessive loading of Ti3C2
MXene at 5% and 7.5% considerably decreased the surface
area to 3.8 and 3.7 m2 g−1. This happened due to the tendency
of the Ti3C2 MXene NPs to aggregate on the CdS surface. The
trend of hydrogen production was in parallel with the surface
area exhibited by the composite, as a gradual increase in
hydrogen production was observed when the loading of Ti3C2
MXene increased to 2.5% (SBET = 120 m2 g−1) and a gradual
decrease in the activity was seen when loading was increased to
5% (SBET = 3.8 m2 g−1). Hypothetically, higher surface area
promoted the photocatalytic reaction by supplying more active
sites on the catalyst surface.
4.2.3. Design of Schottky-Based TiO2. Titanium dioxide
(TiO2), a significantly attractive compound, has been widely
used in the field of photocatalysis due to its excellent stability,
abundance, and easy preparation method.92 Since the
discovery of TiO2 in 1956, many studies have been conducted
to unravel the role of TiO2 in various technological
applications, specifically in photocatalytic water splitting.
Additionally, the distinct properties of TiO2 nanostructure
can be discerned through the higher surface to volume ratio
compared to other bulk photocatalysts.93 As mentioned
previously, a large specific surface area is primarily attributed
to a higher photocatalytic efficiency due to the shorter
migration of electrons and holes for undergoing redox
reactions. Even though TiO2 has been broadly recognized as
a prominent photocatalyst since the pioneering study by
Fujishima and Honda, the shortcomings of TiO2 can be
discerned through various aspects such as its lower quantum
efficiency and poor carrier dynamics which limit its role as a
single individual photocatalyst for water splitting. However, the
low photocatalytic efficiency of a single TiO2 can be
preeminently improved by incorporating metallic conductive
materials such as Ti3C2 MXene. It was noted that the addition
of Ti3C2 MXene as a cocatalyst could assist the migration of
charges on the photocatalyst’s surfaces. Also, the unique
morphological structure of Ti3C2 MXene with abundant
exposed active sites could expedite the redox reaction.
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Figure 10. (a) Effect of Ti3C2 MXene loading on the hydrogen generation (5%, 10%, 25%, 50%, 5%) [Reproduced with permission from ref 94.
Copyright 2016 John Wiley and Sons]. (b) Schematic illustration synthesis of ternary Cu/TiO2@Ti3C2Tx with difference morphological images of
Ti3AlC2, Ti3C2Tx, TiO2@Ti3C2Tx, and Cu/TiO2@Ti3C2Tx and (c) schematic of Cu2O/TiO2 without incorporation of Ti3C2Tx and with Ti3C2Tx
nanosheets [Reproduced with permission from ref 96. Copyright 2018 Elsevier]. (d) Schematic mechanism for a combined semiconductor of
TiO2−Ti3C2−Ru (above) and detached semiconductor-co-catalyst of TiO2−Ti3C2/Ru (below) and (e) PL spectra analysis of different samples
[Reproduced with permission from ref 97. Copyright 2020 American Chemical Society].

Furthermore, the association of Schottky interfaces between
Ti3C2 MXene and TiO2 profoundly improves the overall
photocatalytic activity as Ti3C2 MXene can trap the electrons
and confine them from recombining. The formation of
composite TiO2/Ti3C2 MXene can also be achieved through
thermal oxidation of Ti3C2 MXene, where the Ti group will be
oxidized to form TiO2. Therefore, TiO2 can be grown on the
2D Ti3C2 MXene sheets, where a highly stable composite with
excellent photoactivity can be formed.
Inspired by this, Wang et al. have designed TiO 2
incorporated with Ti3C2 MXene as cocatalyst to investigate
their role as a noble metal substitution.94 In this study, the
rutile TiO2 was successfully grown on Ti3C2 MXene
hydrothermally and was observed to give outstanding catalytic
performances compared to single rutile TiO2. The difference in
Fermi level drove the electrons to migrate and be trapped at
the Ti3C2 MXene surfaces to undergo the reaction with
protons to generate hydrogen. Higher hydrogen production
can be observed due to more electrons participating in the
redox reaction. Furthermore, optimal loading of the cocatalyst
was also being stressed as it is critical in optimizing the solar to
energy conversion. As depicted in Figure 10a, 5% loading of
Ti3C2 MXene demonstrated the highest hydrogen production
while excessive loading could decrease the photocatalytic
activity due to its tendency to aggregate and prevent the
penetration of solar light to the semiconductor surfaces. The
controlled growth of TiO2 on Ti3C2 MXene surfaces is crucial
11996
and can be achieved by varying important parameters. As
written recently by Tahir and Khan et al., the etching time can
predominantly affect the growth of TiO2 on Ti3C2 MXene.49,95
It was suggested that increasing the etching time from 24 to 96
h resulted in more growth of TiO2 by which the highest
hydrogen generation was observed at 48 h of etching time.
Accordingly, Peng et al. revealed that the hybrid of Cu/TiO2@
Ti3C2Tx results in superior photocatalytic activity with
hydrogen generation of 860 μmol g−1 h−1.96 Owing to the
unique electronic properties of Ti3C2 MXene, they can serve as
hole mediators to provide efficient separation of the photo-
generated charges and assist in the photodeposition of Cu to
behave as a reduction cocatalyst. The photodeposition of the
Cu element in the composite of Cu/TiO2@Ti3C2Tx and the
differences in their morphological images can be discerned
through Figure 10b to get a clear understanding of the
formation of Cu/TiO2@Ti3C2Tx composites. As illustrated in
Figure 10c, with the absence of Ti3C2 MXene as hole mediator,
Cu2O cannot be reduced to elemental Cu as it exhibits a
normal type II band configuration whereby the reduction
reaction is most likely to happen at the TiO2 counterpart due
to the difference in the band potentials. Besides, the reduction
of Cu2O did not happen due to its higher CB energy than that
of TiO2, which restrained the reduction into elemental Cu. It is
worth mentioning that the work function exhibited by Ti3C2
MXene, which was calculated to be 3.4 eV, was the lowest
among the reported transitional metals. Therefore, Ti3C2
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Figure 11. (a) HRTEM images of MoS2/Ti3C2 [Reproduced with permission from ref 100. Copyright 2020 Elsevier]. (b) Schematic of the charge
transfer mechanism of MoS2/Ti3C2 in the R-Scheme system [Reproduced with permission from ref 101. Copyright 2020 Springer Nature]. (c)
Schematic illustration of the synthesis of MoxS@TiO2@Ti3C2 composite and (d) PL spectra of vacancy rich MoxS@TiO2@Ti3C2 composite (blue)
and MoS2@TiO2@Ti3C2 (red) [Reproduced with permission from ref 40. Copyright 2020 Elsevier].
MXene could capture the holes generated by TiO2 and leave
the electrons to be accumulated at the TiO2/Cu2O interfaces.
Thus, the accumulated electrons can be tunnelled from the CB
of TiO2 to the CB of Cu2O, where Cu2O can be reduced to
metallic Cu. The photocatalytic performances of Cu/TiO2@
Ti3C2Tx are superior to those of p−n TiO2/Cu2O, which
indicates that the reduction of Cu with the assistance of
Ti3C2Tx gravely affects photocatalytic hydrogen production.
Literature findings suggested that the oxidation of the metal
cocatalyst can lead to the induction period where the reaction
occurred at a slower rate with no hydrogen production. The
reaction started to accelerate after the induction period, where
hydrogen generation began. However, a recent study by Liu et
al. suggested that the induction period can be eliminated even
with the addition of metal cocatalyst, which can be achieved by
in situ formation of TiO2 on the nanoconfined Ti3C2/Ru
surface. This route was also more effective in increasing the
carrier dynamics than conventionally prepared TiO2−Ti3C2−
Ru through photodeposition.97 Ti3C2 MXene served as a
metallic conductor separating the semiconductor (TiO2) with
the cocatalyst (Ru). The increase in the distance between
oxidation and reduction reaction sites, through nanoconfined
Ti3C2/Ru observed in Figure 10d, outstandingly promoted the
catalytic reaction due to the hindered recombination of
photogenerated charges. Proficient separation of the photo-
generated charges was confirmed in Figure 10e, with a
reduction in the peak of TiO2−Ti3C2/Ru. No induction
period occurred due to the higher work function exhibited by
Ti3C2/Ru which facilitated the direct transfer of electrons to
the active center of Ru. Higher catalytic activity was also
observed by Zhuang et al. where they fabricated TiO2
nanofibers with Ti3C2 MXene through electrostatic self-
assembly with the enhancement in the hydrogen production
rate up to 6 979 μmol g−1 h−1 that is 3.8 times higher than the
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pristine TiO2 nanofibers.98 This positively linked with the
strong interfacial contact between TiO2 nanofibers with Ti3C2
MXene. Under light irradiation, the photogenerated electrons
migrated to Ti3C2 MXene nanosheets, leaving holes in TiO2
nanofibers. The Schottky junction formation prevented the
trapped electrons at Ti3C2 MXene from combining with the
holes in TiO2 nanofibers, thus prolonging the exciton lifetime.
The presence of Ti3C2 MXene improved the electrical
conductivity and optical properties. This is in accordance
with the study done by Feng et al., indicating an improvement
in the photocatalytic performance of hydrogen production
from hydrazine and hydrazine borane.99
4.2.4. Design of Schottky-Based MoS2. The enhancement
in the hydrogen production rate was also observed in the
composite of MoS2/Ti3C2 MXene. Zhang et al. fabricated
MoS2 with Ti3C2 MXene through the hydrothermal method
and disclosed that MoS2/Ti3C2 exhibited outstanding photo-
catalytic performances with a 6144.7 μmol g−1 h−1 rate of
hydrogen generated, which was 2.3 times higher than those of
pristine MoS2.100 Through the HRTEM images in Figure 11a,
it can be observed that MoS2 and Ti3C2 formed close contact
with each other, which favored the electrical transfer between
MoS2 and Ti3C2 MXene. The excellent electrical properties of
Ti3C2 MXene allowed it to capture the electrons, preventing
the reverse injection of electrons back to MoS2. Therefore,
more protons can be converted into hydrogen with plenty of
electrons to participate in the reduction reaction, contributing
to a higher generation of hydrogen. Furthermore, more
efficient electron mobilization from MoS2 to the surface
Ti3C2 MXene, owed to stronger contact formation and a
shorter carrier transmission channel, also expedited the
reduction of protons toward hydrogen. Accordingly, Yao and
co-workers revealed that the incorporation of Ti3C2 MXene
boosted the photocatalytic performance of pure MoS2 from
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Figure 12. (a) Transient photocurrent response of pure Ti3C2, SnNb2O6, and Ti3C2 MXene/SnNb2O6 (TCS-5) [Reproduced with permission
from ref 109. Copyright 2021 Elsevier]. (b) DRS analysis of the pure ZnS and ZnS/Ti3C2 MXene [Reproduced with permission from ref 110.
Copyright 2021 Elsevier]. (c) SEM images of Ti3C2 MXene and (d) ZnS/Ti3C2 MXene [Reproduced with permission from ref 111. Copyright
2019 Elsevier]. (e) UV−vis absorption spectroscopy analysis of pure Ti3C2, CdLa2S4, and different ratios of CdLa2S4/Ti3C2 MXene [Reproduced
with permission from ref 112. Copyright 2020 Elsevier]. (f) Schematic illustration of the synthesis of Ti3C2 MXene@TiO2/ZnIn2S4 (M@T/ZIS)
through two-step hydrothermal treatment [Reproduced with permission from ref 113. Copyright 2020 Elsevier].

65.4 to 380.2 μmol h−1 g−1.101 They also observed the charge
transfer mechanism in this system and proposed the new R-
Scheme mechanism as designated in Figure 11b. The charge
transfer mechanism in this system was marked by the
difference in the work function exhibited by MoS2 and Ti3C2
MXene. As discussed previously, the higher work function and
excellent electronic conductivity of Ti3C2 MXene assisted the
migration of charges from MoS2 toward Ti3C2 MXene. This
effectively extended the separation and excitation time of
photogenerated charges to undergo a redox reaction. On the
other hand, it was also reported that the active sites of MoS2
nevertheless could be tailored through defect engineering by
increasing the molybdenum vacancies in MoS2.102 The
addition of metal-like materials was also believed to improve
the active sites of the MoS2 composites. This was because low
catalytic active sites of MoS2 resulted in poor photocatalytic
activity in the pristine MoS2. According to Li et al., the
composites of MoxS@TiO2@Ti3C2 showed a remarkable
performance in photocatalytic hydrogen production with the
rate of hydrogen production as high as 10 505.8 μmol h−1
g−1.40 The profound increase in the performance of this
composite was due to the presence of MoxS and Ti3C2
functioning as dual cocatalysts. The molybdenum vacancies
obtained from the reduction of Mo4+ in MoS2 inherently
suppressed the thermal activation of excitons, depleted the
extra electrons, and improved the quantum efficiency. Besides,
hydrothermal treatment and oxidation of Ti3C2, as depicted in
Figure 11c, substantially converted Ti3C2 MXenes into TiO2@
Ti3C2 MXenes. This, on the other hand, improved the
electronic conductivity and the electron transfer in the
composite of MoxS@TiO2@Ti3C2. The formation of TiO2@
Ti3C2 MXenes improved the electronic coupling and enhanced
11998
the photocatalytic properties of the hybrid materials.49 The
synergistic effects of integrating vacancy-rich MoxS with
TiO2@Ti3C2 MXenes through two-step hydrothermal treat-
ment were shown through the reduction in the intensity peak
observed in the PL analysis in Figure 11d. The intensity peak
of MoxS@TiO2@Ti3C2, a vacancy-rich composite, was
observed to be lower compared to MoS2@TiO2@Ti3C2
which suggests a higher separation efficiency. Therefore,
integrating metallic conductive materials such as Ti3C2
MXenes was believed to increase the performance of the
MoS2. However, modifying the structural properties of MoS2
into a highly defective material could significantly improve the
stability and the electronic properties of the hybrid
composites.103
4.2.5. Design of Different Schottky-Based Semiconduc-
tors. The unique properties exhibited by Ti3C2 MXene render
them a notable place in photocatalytic water splitting. Highly
conductive Ti3C2 MXene is favored as a cocatalyst to be
integrated with different semiconductors such as g-C3N4, CdS,
TiO 2, MoS2, CdLa2S4, SnNb2O6, and ZnS to elevate
photocatalytic hydrogen production. The construction of
Schottky interfaces between Ti3C2 MXene and the semi-
conductor is the main contributor in enhancing the photo-
catalytic activity of the composites.90,104,105 The differences in
the work function between the Ti3C2 MXene and semi-
conductors facilitate electron migration. Generally, Ti3C2
MXene exhibits a higher work function than semiconductors
due to its metallic properties. Therefore, the photogenerated
electrons will migrate from lower Fermi level materials toward
higher ones, making Ti3C2 MXene an electron acceptor. The
close intimate contact between metal and semiconductor
builds a strong interfacial connection and will prevent the
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accumulated electrons from returning to the semiconductors
and recombining with holes.106,107
SnNb2O6 was denoted as a prominent photocatalyst for
water splitting as it exhibited a narrow bandgap energy of
approximately 2.40 eV with excellent solar absorption and
durable stability.108 Therefore, the addition of metallic
materials into SnNb2O6 was hypothetically believed to boost
the photocatalytic activity of the composite. Subsequently,
Wang et al. fabricated Ti3C2 MXene/SnNb2O6 to unravel the
role of highly conductive Ti3C2 MXene in enhancing
photocatalytic hydrogen production.109 They disclosed that
an improvement in the hydrogen generation rate (175.2 μmol
h−1 g−1) could be observed after incorporating few-layered
Ti3C2 MXene nanosheets into SnNb2O6, achieving an
enhancement twice that of pure SnNb2O6. It was even noted
that the SnNb2O6 based photocatalyst exhibited a low
quantum yield due to its internal features. However,
incorporating Ti3C2 MXene opened new routes to promote
the diversity of SnNb2O6 in photocatalytic application. The
improvement in the hydrogen production rate was positively
associated with the facile separation of the photogenerated
charges. The transient photocurrent response spectra indicated
the rapid recombination of the photogenerated charges
exhibited by pure Ti3C2 and SnNb2O6, as shown in Figure
12a. However, the increment in the photocurrent density of
Ti3C2 MXene/SnNb2O6 testified as to the enhancement in the
charge separation and transfer rate.109
In a different study of Schottky junctions in Ti3C2 MXene,
Liu et al. successfully fabricated ZnS nanoparticles on layered
Ti3C2 MXene sheets.110 The integration of Ti3C2 MXene
astoundingly shifted the absorption range of ZnS toward the
visible region. Aside from inhibiting the migration of
photogenerated electrons back to the ZnS and recombining
with holes, DRS analysis in Figure 12b indicates that
introducing Ti3C2 MXene enhanced the light utilization with
an observed bandgap of 2.9 eV. Optimizing the solar
absorption of the ZnS/Ti3C2 MXene composite elevated the
photocatalytic performances of the hybrid composite in which
the hydrogen production rate increases to 212 μmol h−1 g−1.
The amelioration in the photocatalytic performances observed
by the hybrid of ZnS/Ti3C2 MXene is parallel to the study
done by Tie et al.111 The integration of ZnS with Ti3C2
MXene through in situ construction notably enhanced the
hydrogen production almost 4-fold higher than pristine ZnS. It
was noted that the introduction of Ti3C2 MXene promoted
particle nucleation, in which the change in the morphological
structure from sheet-like Ti3C2 MXene to a smooth micro-
sphere structure was observed through SEM analysis in Figure
12c,d. The alteration in the surface morphology by controlling
the optimal loading ratio of Ti3C2 MXene improved the
physical properties of the ZnS/Ti3C2 MXene. It was evident
that the composite of the ZnS/Ti3C2 MXene exhibited the
largest pore size of 15.96 nm, pore volume of 0.18 cm3 g−1, and
surface area of 84.72 m2 g−1 as proven by the BET analysis.
Correspondingly, photocatalytic hydrogen production im-
provement was also observed in the composite of CdLa2S4/
Ti3C2 MXene.112 Through UV−vis absorption spectroscopy
analysis presented in Figure 12e, the optical properties of
CdLa2S4/Ti3C2 MXene was observed to be exceptionally
improved. A discerned red shift was observed in the composite
CdLa2S4/Ti3C2 MXene, suggesting that the introduction of
Ti3C2 MXene substantially improved the solar absorption. This
was therefore maximizing the solar to energy conversion in
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which the hydrogen evolution rate astonishingly increased up
to 11 182.4 μmol h−1 g−1, 13.4 times higher than that of
pristine CdLa2S4. The enhancement in the optical properties of
the Ti3C2 MXene-based composite is in agreement with the
studies done previously. Additionally, the outstanding photo-
catalytic activity in the composite of CdLa2S4/Ti3C2 MXene
outperformed Pt/CdLa2S4. This clearly disclosed that Ti3C2
MXene exhibited better functionality than those of noble
metals. Therefore, the substitution of Ti3C2 MXene, which is
more cost-effective than noncommercial noble metals, moves
photocatalytic hydrogen production forward in the hopes of
becoming industrially applicable and commercially viable.
In another study, the fabrication of ternary composite of
Ti3C2 MXene@TiO2/ZnIn2S4 reported by Huang et al.
revealed excellent photocatalytic performances with hydrogen
generation up to 1185.8 μmol h−1 g−1.113 The construction of a
double heterojunction through two-step hydrothermal growth,
as depicted in Figure 12f, profoundly improved the charges
transfer between the semiconductors. Furthermore, the
construction of a type-II heterojunction between ZnIn2S4
and TiO2 and a Schottky junction between Ti3C2 and
semiconductors synergistically improved the overall photo-
catalytic activity. In this context, Ti3C2 MXene with excellent
metallic properties improved the light absorption while
confining the electron from traveling back to the semi-
conductors. On the other hand, the construction of ZnIn2S4/
TiO2 improved the separation of photogenerated charges and
facilitated the electron transfer between the semiconductors
toward Ti3C2 MXene.
Therefore, throughout the literature analysis on different
Ti3C2 MXene-based composites, several observations on Ti3C2
MXene can be made as follows: (1) Ti3C2 MXene having a
bandgap close to zero exhibits metallic properties and does not
possess semiconductor properties; therefore, it is unable to
generate electrons and holes on its own. (2) The formation of
Ti3C2 MXene with OH terminal group acts as a center for
forming the high-activity photocatalyst. (3) Formation of
hydrophilic functional surface groups (−O, −OH) provides a
rapid reactant diffusion. (4) Modulating the surface termi-
nation of Ti3C2 MXene can be achieved through different
synthesis routes and reaction conditions, which is due to the
notable feature that Ti3C2 MXene with different termination
groups exhibits different photochemical properties. (5) The
presence of −O termination provides a potent bridging effect
for coupling with other semiconductors without the assistance
of surface-active agents. Therefore, the literature analysis
suggests that Ti3C2 MXene indeed plays an eminent role as an
induced Schottky barrier cocatalyst in promoting photo-
catalytic hydrogen production in various semiconductors.
Ti3C2 MXene exhibits excellent electrical properties that
endow it with the capability of trapping electrons, providing
efficient carrier separation. The surface functionalized groups
exhibited by Ti3C2 MXene could also contribute to an
enhanced photocatalytic reaction by tailoring the stability
and electronic and photochemical properties of MXene-based
materials. In addition, incorporating metallic Ti3C2 MXene
could alternatively provide similar results, even better than
those of noble metals. Even though the addition of noble
metals such Pt is noticed to substantially boost the photo-
catalytic performances of most of the reported composites,
drawbacks in employing noble metals are mainly due to their
high prices and limited availability. Therefore, it is not prudent
to employ noble metals, especially in industrial-scale photo-
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Figure 13. Overview of different morphological structures of MXenes.
catalytic processes, to generate hydrogen, as it is not
economical. Alternatives in finding new metallic materials
such as MXenes shed light on the future of hydrogen
generation through photoinduced water splitting. Table S2
summarizes the catalytic activity of hydrogen production by
Ti3C2 MXene as a cocatalyst with a comparison to those by
noble metals. Clearly, Ti3C2 MXene was indeed the best
substitution for the noble metals as it exhibited higher catalytic
efficiency in most of the composites.
Furthermore, the incorporation of Ti3C2 MXenes substan-
tially improves the specific area of the composites and provides
abundant catalytic active sites, subsequently expediting the
catalytic performance. Most of the reported Ti3C2 MXene-
based composites suggest that a larger specific surface area is
observed through BET analysis after incorporating Ti3C2
MXene compared to that found in their pure form.
Interestingly, the increase in the specific area is also on trend
with the photocatalytic performances. Controlling the loading
of Ti3C2 MXene also is important to avoid light-shielding
effects and to prevent the aggregation of Ti3C2 MXene on the
catalyst surfaces. However, in some reported composites, such
as in SnNb2O6/Ti3C2 MXene, the finding suggested that only a
slight increase in the BET surface area can be observed,
signifying that surface area is not the primary indicator for
generating higher hydrogen yield. It was also noted that the
incorporation of Ti3C2 MXene hardly affected the surface area
of the SnNb2O6-based composite, explaining that the excellent
photocatalytic performance was instead attributed to the
nature of Ti3C2 MXene to improve the carrier dynamics. In
the composite of g-C3N4/Ti3C2 MXene, the Schottky barrier
induced by Ti3C2 MXene was revealed to minimize the
electrostatic potential barrier, driving the charge transport and
confining charges to prevent backward reversal. On the other
hand, the oxidation of sulfide elements in CdS linked to
photocorrosion resulted in poor stability and lower catalytic
activity of the photocatalyst. Adding 2D Ti3C2 MXene as a
cocatalyst not only served as efficient support to CdS but could
also prevent photocorrosion and improve the stability of CdS
as stable catalytic activity was observed after longer exposure to
light. The poor catalytic efficiency observed in pure MoS2 was
due to lesser active sites, only present at the edges of the MoS2
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layers, constraining the catalytic activity. Findings suggested
that owing to the unique 2D Ti3C2 MXene sheets, more
exposed active sites can be generated in the composite of
MoS2/Ti3C2 MXene, which hastened the redox reaction and
accelerated the hydrogen yield. It was mentioned that Ti3C2
MXene is a metallic material, and tailoring the surface
functionalization of Ti3C2 MXene cannot alter the optoelec-
tronic properties of Ti3C2, unlike other MXene families. This
showed that Ti3C2 MXene cannot serve as a semiconductor
and is incapable of generating electrons and holes. However,
Ti3C2 MXene can be converted into a TiO2 semiconductor
due to the oxidation of the Ti group of Ti3C2. The Ti group
served as the source of titanium which promoted photo-
catalytic activity. Therefore, TiO2 can be grown on Ti3C2
MXene to profoundly promote photocatalytic performance
toward hydrogen generation by controlling parameters like the
etchant time, temperature, and reaction environment.
4.3. Effects of the Morphological Design on the Ti3C2
MXene-Based Schottky Junction. The efficiency of the
photocatalyst in photocatalytic water splitting strongly depends
on its morphological and architectural features. It is denoted
that the structural features at the nano-/microscales and
reasonable control of the crystal morphological could improve
the photocatalytic performance of the photocatalyst.114
Generally, Ti3C2 MXene can be formed into various
dimensions such as 0D, 1D, 2D, and 3D as demonstrated in
Figure 13. Ti3C2 MXene originally existed in the form of 2D
sheets; this can be achieved via etching of MAX phases.
However, the development of Ti3C2 MXene in 0D and 1D
forms is exploited only in a limited manner due to the difficulty
in controlling its morphological structure with optimal catalytic
efficiency. However, the advances of Ti3C2 MXene in its 0D
and 1D forms may bring great benefits for improvements in
carriers dynamics. Additionally, Ti3C2 MXene is normally used
as a support to increase the structural and photostability of the
composites. Therefore, the readily available 2D sheets of Ti3C2
MXene, which possesses a larger surface area, could be an
efficiently supporting site to hamper the aggregation and
agglomeration of photocatalysts with higher surface energy.
Unfortunately, the Ti3C2 MXene nanosheets also suffered from
restacking, reducing the exposure of catalytic active sites and
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ACS Applied Energy Materials
minimizing the efficiency of Ti3C2 MXene. Therefore,
modulating the morphology of Ti3C2 MXene into various
dimensions could improve the catalytic properties of Ti3C2
MXene and enhance the contact area between Ti3C2 MXene
and other semiconductors.
Tuning of Ti3C2 MXene nanosheets into quantum dots was
ascribed to providing more efficient contact with other
semiconductor materials as observed in composite QD
Ti3C2/Cu2O nanowires which exhibited stronger contact
formation than that with 2D Ti3C2 sheets. Besides, the
stability of Cu2O nanowires was greatly increased with the
addition of quantum dot (QD) Ti3C2 MXene denoted to cover
and protect the porous surfaces of Cu2O nanowires to preserve
them from easy oxidation.115 In addition, it was suggested that
highly conductive quantum dot Ti3C2 MXene exhibited Fermi
levels less negative than the CB of Cu2O, wherein the Fermi
level energy of the Ti3C2 MXene nanosheet was observed to be
more positive, which was not conducive for the promotion of
the catalytic reaction. Correspondingly, Li et al. suggested that
quantum dot Ti3C2 MXene exhibited excellent solvent
solubility and abundant active edge sites, which was beneficial
for the efficient catalytic reaction.116 They revealed that
fabricating g-C3N4 with Ti3C2 QD astoundingly enhanced the
photocatalytic hydrogen production with 5111.8 μmol g−1 h−1
hydrogen yield, which is 3 and 10 times higher than those of
Pt/g-C3N4 and Ti3C2 MXene sheet/g-C3N4, respectively. The
higher catalytic activity in Ti3C2 QDs was ascribed to their
nanosized shape, which was in the range of 2−25 nm,
allocating more active and adsorption sites to promote the
photocatalytic reaction. Besides, stronger contact formation
between Ti3C2 QD with g-C3N4 facilitated the migration of
electrons to the Ti3C2 QD surface, and a higher potential
barrier of Ti3C2 QD provided spatial separation through
Schottky barrier effects. Generally, QD semiconductors were
smaller in size and often associated with quantum confinement
effects where their molecules were tightly confining electron−
hole pairs in all dimensions, leading to the band transition from
continuous to discrete energy levels. Mainly, due to the
metallic nature of Ti3C2 QDs with zero bandgap energy, the
quantum confinement did not occur in Ti3C2 MXene.
However, in this context, the term QD could be ascribed to
the size of the Ti3C2 MXene at the nanoscale range as QDs are
nanomaterials comprised of metals, insulators, semiconductors,
and organic materials, which was discerned based on their tiny
morphology.117 In regards to Ti3C2 MXene QDs, the
photocatalytic activity of 1D Ti3C2 MXene has not been
reported yet so far. Among the reported 1D MXene materials,
some examples are present in other MXene families, such as
nanotube Sc2C and Ti2CO2. However, studies are mostly
focused on computational analysis, and so far, they have not
been experimentally implemented.118 However, Pang et al.
successfully fabricated a fluoride-free Nb2CTx nanowire via
hydrolysis and HF-free E-etching method. They disclosed that
MXene in 1D forms exhibited higher stability with the oriented
charge transfer pathway, minimizing the transfer resistance.
The study showed that 1D MXene exhibited a great potential
in paving the way toward improving the catalytic properties of
MXene materials.119
In the context of hierarchical Ti3C2 MXene consisting of
semiconductors with multidimensional domains, this is often
regarded as the best strategy to prevent the aggregation of
particulate photocatalysts and enhance the quantum efficiency
owing to its unique and structurally formed shape. Interest-
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ingly, the synergistic effects between the multidimensional
materials lead to a substantial increase in the photocatalytic
performance as they exhibit higher surface area and are more
accessible to solar absorption. As noticed in Ti3C2−TiO2
nanoflowers, the 3D porous nanoflowerlike structure was
equipped with abundant active sites and exhibited excellent
light scattering ability.120 These features were ascribed to the
fact that varying the reaction temperature of Ti3C2 to TiO2
conversion could affect the formation of the nanoflower shape,
which is linked to variation in the surface area. The highest
surface area exhibited by Ti3C2−TiO2 under thermal treatment
at 500 °C resulted in the highest hydrogen yield of 783.11
μmol g−1h−1 owing to better contact between the water
molecules with the catalyst surface. Increasing the temperature
was observed to alter the width of the petals and shorten the
length of the belts which contributed to improving redox
activity due to the shorter carrier transmission pathway.
Accordingly, higher catalytic activity was observed in
hierarchical cauliflowerlike CdS-Ti3C2 MXene with 14 342
μmol g−1 h−1 hydrogen production and quantum efficiency of
40.1% at 420 nm.17 The higher light-harvesting capability with
the promotional effects of the Schottky barrier by Ti3C2
MXene promoted higher charge separation with more
generation of electrons and holes to participate in the catalytic
reaction. Besides, more exposure of surface active sites with
respect to the 3D hierarchical structure was one of the
contributing factors for improved catalytic activity.
5.0. CONCLUSION AND FUTURE PROSPECTS
Photocatalytic hydrogen generation through the utilization of
Ti3C2 MXene photocatalyst offers novel alternatives to provide
clean, sustainable, and renewable energy sources. Enormous
effort has been devoted to improving the solar to energy
conversion of these photocatalysts. The employment of Ti3C2
MXene as a cocatalyst to derive hydrogen generation has been
regarded as a promising maneuver due to the unique structural
and excellent electrical properties of Ti3C2 MXene, which
endow it with a special ability to induce the Schottky barrier
for capturing the electrons. It is very important to understand
Ti3C2 MXene by examinging the basic characteristics of
MXene materials, such as the control of surface functionaliza-
tion groups, the stability of MXene in the water environment
and in atmospheric conditions, and, also, the stability toward
heat treatment. It is also important to mention that electronic
and electrical properties could play parts in improving the
efficiency of MXene materials. In various Ti3C2 MXene based
composites, it can be postulated that the incorporation of
Ti3C2 MXene could improve the properties of the semi-
conductor materials in countless ways, which is by serving as
efficient support materials, reducing the potential barriers,
improving the carriers dynamics, and acting as electron
trappers. Schottky heterojunction formation by hybrid Ti3C2
MXene is strongly associated with the metallic properties
exhibited by the Ti3C2 MXene. In this context, Ti3C2 MXene
serves as an electron trapper, prolonging the exciton lifetime
and thus increasing the photocatalytic performance. The highly
abundant and cost-effective Ti3C2 MXene is considered to be
the best alternative to substitute for expensive and non-
commercial noble metals. Some studies even reported that the
integration of Ti3C2 MXene could generate a substantial
amount of hydrogen that surpasses those with noble metal
integration. However, challenges can also be addressed while
designing MXene materials which can be noticed in controlling
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ACS Applied Energy Materials
the surface functionalization groups of Ti3C2 MXene. Studies
have shown that the electronic properties of MXene materials
also depend on the type of functional groups present (Tx),
which can be tailored either during the etching process of
MAX or through the intercalating agents used. However, the
presence of different termination groups prepared through
different synthesis methods is still vexed as to what extent the
reaction parameters could tailor the formation and distribution
of the functional groups. Besides, limited studies are available
to attest to the role of Ti3C2 MXene with mixed functional
groups and their behavior toward the photocatalytic reaction.
Therefore, future perspective research approaches have been
elucidated to provide insight into the future study of Ti3C2
MXene in the photocatalysis process:
• The experimental study of different termination groups
of Ti3C2 MXene should be maximized. This is to provide
a clear picture of the significance of each termination
group in contributing to stable and robust photocatalytic
activity. For instance, which termination group is the
most suitable to promote the photocatalytic reaction for
hydrogen generation and otherwise?
• In addition, the study of mixed functional groups of
Ti3C2 MXene should be focused both experimentally
and theoretically. This is because knowledge of MXene
materials should be established to customize the design
of MXene to drive specific catalytic reactions.
• Ti3C2 MXene as an electron mediator has not been
widely explored when compared to reduced graphene
oxide (rGO). This is hypothetically due to the thick
layer of Ti3C2 MXene which inhibits the contact
formation between different materials. However, en-
gineering modifications can be performed to tailor the
thickness of the Ti3C2 MXene layer to utilize it as an
electron mediator in a Z-scheme system which could be
a novel route for substantially improving photocatalytic
water splitting.
• A deeper understanding of the Ti3C2 MXene-based
materials can be further enhanced through the operando
characterization technique to gain fundamental knowl-
edge of the relationship between the molecular structure
and activity of Ti3C2 MXene with their selectivity.121
This technique would enable extensive studies to be
conducted on the stability of Ti3C2 MXene under
various reaction conditions, understanding the nature of
the catalytic sites with the reaction mechanism of Ti3C2
MXene, which is beneficial to improving the role of
Ti3C2 MXene in the photocatalysis field.
• The beneficial advantages exhibited by monolayer Ti3C2
MXene are proven to enhance the photocatalytic
performances of the MXene-based photocatalysts. The
study of atomic defects and their impact on the
structural arrangement and properties of Ti3C2 MXene
provide a fundamental understanding for the develop-
ment of monolayer Ti3C2 MXene in the energy
conversion field. However, the position and the presence
of active sites of the monolayer Ti3C2 MXene should be
critically examined since they are crucial to determining
the exact position of the catalytic sites to reveal the role
of Ti3C2 MXene in future developments.
• To tackle the morphological study of Ti3C2 MXene,
especially in forming a hierarchical structure with
multidimensional domains, parameters such as composi-
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tional ratio, the Fermi level of the semiconductor
photocatalyst, and the control of temperature should
be given attention with regard to controling the
morphology of Ti3C2 MXene while attaining a higher
photocatalytic performance.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.1c02241.
Figures S1 and S2, schematics of MXene formation, and
Tables S1 and S2, hydrogen generation data for different
MXenes (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Muhammad Tahir − School of Chemical and Energy
Engineering, Universiti Teknologi Malaysia, 81310 Johor
Bahru, Johor, Malaysia; Chemical and Petroleum
Engineering Department, UAE University, Al Ain, United
Arab Emirates; orcid.org/0000-0002-2937-5645;
Email: m.tahir@utm.my, bttahir@yahoo.com
Author
Areen Sherryna − School of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, 81310 Johor Bahru, Johor,
Malaysia
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.1c02241
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to extend their most profound
appreciation to the Ministry of Higher Education (MOHE)
for financial support under the Fundamental Research Grant
Scheme (FRGS, Vot No R.J130000.7851.5F384).
■
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