1 s2.0 S0360319922044871 Main

international journal of hydrogen energy xxx (xxxx) xxx
Available online at www.sciencedirect.com
ScienceDirect
journal homepage: www.elsevier.com/locate/he
Photocatalytic hydrogen generation from overall

water splitting with direct Z-scheme driven by
two-dimensional InTe/Bismuthene heterostructure
Meng Ge, Chuan-Lu Yang*, Mei-Shan Wang, Xiao-Guang Ma

School of Physics and Optoelectronic Engineering, Ludong University, Yantai 264025, China
highlights graphical abstract
InTe/Bismuthene heterostructure
can drive hydrogen generation
from water splitting.
The maximum solar-to-hydrogen
efficiency can reach 16.17% under
þ9% strains.
InTe/Bismuthene heterojunction
raises efficiency compared to the
InTe monolayer.
The thermodynamic feasibility of
the HERs is confirmed with Gibbs
free energy changes.
article info abstract
Article history: The photocatalytic direct Z-scheme driven by two-dimensional (2D) heterostructure often
Received 17 July 2022 achieve high solar-to-hydrogen conversion efficiency (hSTH ). However, the favorable 2D
Received in revised form heterostructure is not easily identified. Here, we identify a 2D heterostructure with InTe
21 September 2022 and Bismuthene monolayers and confirm the most stable configurations. The band
Accepted 25 September 2022 alignments and built-in electric fields both turn out to satisfy the requirement of the direct
Available online xxx Z-scheme for hydrogen evolution reaction. In addition, the optical absorption, mobility,
hSTH and the change in Gibbs free energy is used to justify the photocatalytic performance.
Keywords: The maximum hSTH can reach 9.67% which is significantly higher than 4.22% of the InTe
Heterostructure monolayer. Moreover, the hSTH of the heterostructure can be raised to 16.17% under þ9%
Hydrogen evolution reaction biaxial strains, indicating that strains have a controlling effect on the hSTH s. The alterations
Z-scheme in Gibbs free energies of 1.72e2.12 eV assure the hydrogen evolution reactions are feasible
Built-in electric field in thermodynamics. Therefore, the present InTe/Bismuthene heterostructure has potential
Photocatalytic applications in driving photocatalytic hydrogen generation from overall water splitting
under the irradiation of sunlight.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
* Corresponding author.
E-mail address: [email protected] (C.-L. Yang).
https://doi.org/10.1016/j.ijhydene.2022.09.249
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Ge M et al., Photocatalytic hydrogen generation from overall water splitting with direct Z-scheme driven by
two-dimensional InTe/Bismuthene heterostructure, International Journal of Hydrogen Energy, https://doi.org/10.1016/
j.ijhydene.2022.09.249
2 international journal of hydrogen energy xxx (xxxx) xxx
In recent years, the monochalcogenides with honeycomb

Introduction structures based on the group III elements have been paid
attention to because of their layer-by-layer structures,
The excessive exploitation of fossil fuels has brought about together with some unique electronic, optical, and thermal
worsening environmental pollution, such as the earth's soil properties [29e31]. The bandgaps are 1e3 eV [32,33], and the
and water quality, as well as other natural environments, carrier mobility can reach 103 cm2/Vs [34]. The InTe monolayer
have been irreversibly damaged. At the same time, the carbon was theoretically reported to have high mobility [35]. For the
dioxide and other gases, which release in burning petroleum, experiment, Chattopadhyay et al. [36] used high-pressure x-
coal, and other energy sources, accelerate the process of the ray diffraction technique to study the crystal structure of InTe.
greenhouse effect. Therefore, the search for renewable clean Rajaji et al. [37] investigated the pressure-dependent behavior
energy has become a critical goal for researchers [1,2]. Fortu- of InTe through the Raman scattering measurements. More-
nately, hydrogen energy has turned out to be a favorable over, the InSe monolayer and few-layer structures have been
clean, and efficient energy source, although the effective prepared by mechanical exfoliation from the bulks [29] and
method to produce hydrogen is still lacking. Recently, sunlight chemical vapor transport methods [38]. They are widely used
photocatalytic hydrogen generation from water splitting in photodetectors in the visible to the near-infrared region
driven by semiconductors is believed as a clean and renew- with high photoresponsivity. The InTe monolayer is believed
able way to obtain hydrogen [3e5]. Therefore, it attracted re- to be fabricated shortly [39]. The Bi monolayer (Bismuthene) is
searchers' interest in finding suitable photocatalysts to a hexagonal honeycomb configuration and can be prepared by
efficiently drive hydrogen evolution reactions (HER) [6e8]. The molecular beam epitaxy [40], hot-pressing method [41],
optical absorption and overpotentials are the key factors for acoustic stripping method [42], and dry etching method [43] in
the solar-to-hydrogen conversion efficiency (hSTH ). For a pho- the environment of hydrogen. Owing to high carrier mobility,
tocatalyst of the monolayer with the same vacuum level on adjustable bandgap, and good thermoelectric performance,
both surfaces, the solar energy absorption and overpotentials Bismuthene has been extensively studied [44,45]. Degtyaeva
are limited to one another because bandgap equals the result et al. [46] used angle-dispersive x-ray diffraction techniques
of the potential for conduction band minimum (CBM) sub- with monochromatic synchrotron radiation to identify the
tracting its corresponding potential for valence band structure of Bi under high pressure. Zhao et al. [47] theoreti-
maximum (VBM). Moreover, the rapid photogenerated cally investigated the stability and the lattice dynamics of
electron-hole pair recombination is also difficult to suppress different high-pressure phases of Bi. Unfortunately, the band
[9,10]. The type-II heterostructure can promote spatial sepa- edges are not suitable for photocatalytic HER.
ration and suppress recombination of charge carriers [11], In this work, we will construct 9 configurations of the two-
thus substantially improving the energy conversion efficiency dimensional (2D) InTe/Bismuthene heterostructure based on
of the heterostructures [12,13]. However, this mechanism various stacking ways while maintaining the lattice mismatch
weakens the redox ability of the charge carriers to some ratio. The three most stable configurations are identified by
extent because the CBM and VBM with small overpotentials calculating the formation energies. The thermodynamic sta-
are used for the HER and oxidation evolution reaction (OER). bility for the selected configurations will be assessed with the
The Z-scheme heterostructure can maintain both the strong Ab initio molecular dynamics (AIMD) [48,49] simulations. The
redox capability for driving photocatalytic reactions and the electronic and optical properties, mobility, hSTH , the Gibbs free
spatially separated reduction and oxidation active sites [14], energy, and strain engineering are explored to understand
which is an advantage over the type-II heterostructure. photocatalytic performance. The results show that the band
However, the traditional Z-scheme heterostructure has dis- arrangements of all the studied configurations match the
advantages such as the light shielding effect and feasibility standard of photocatalytic HER and OER, and the built-in
because of the solution system. Moreover, most redox medi- electric field between the inner surface of the hetero-
ators are unstable and tend to deactivate, which results in a structure supports the Z-scheme for overall water splitting.
decrease in the reaction rate [15,16]. The heterostructures Moreover, the optical absorptions of the monolayers sepa-
with direct Z-scheme photocatalytic have been considered as rated from the configurations show a relatively apparent ab-
a very favorable photocatalyst for solar-driven water cracking sorption in visible light. The maximum hSTH of 9.67% is
[12,14,16,17] because the direct Z-scheme leads to the carriers observed, and that of 16.17% can be achieved with þ9% biaxial
in the heterostructure migrating between the two monolayers strain. The changes in Gibbs free energies of 1.72e2.12 eV
directly without the solution system. Therefore, the direct Z- assure the HERs are feasible in thermodynamics. These re-
scheme can achieve large over-potentials and enhanced op- sults indicate that the InTe/Bismuthene heterostructure is a
tical absorption in the high irradiance region of solar light, potential material for driving photocatalytic direct Z-scheme
which are necessary to achieve high hSTH [18]. Wang et al. [19] for HER.
prepared a direct Z-scheme ZnO/CdS heterostructure and
improved its hydrogen production efficiency. The H2 release
rate of direct Z-scheme black phosphorus/Bi2WO6 is as high as Computational method
21,042 mol g1, which is 9.15 times that of the Bi2WO6 mono-
layer [20]. In addition, some heterostructures with excellent The Heyd-Scuseria-Ernzerhof hybrid functional (HSE06)
photocatalytic properties and high hSTH are theoretically and [50,51] is employed to obtain the energy stable structures and
experimentally reported [21e28]. compute the electronic properties, which is completed with
international journal of hydrogen energy xxx (xxxx) xxx 3
the Vienna ab initio simulation package (VASP) [52,53]. The van Where EHet, EInTe, and EBismuthene represent the total energy
der Waals interactions are computed by density functional of the InTe/Bismuthene heterostructure, the InTe monolayer,
dispersion correction (DFT-D4) [54]. The plane-wave basis sets and Bismuthene, respectively. The obtained Ef, the interlayer
for the valence electrons and projector-augmented-wave distance between the two monolayer dil, and lattice constants
pseudopotential [55,56] are adopted in all calculations. A (a, b) are presented in Table. S1. The negative Efs are observed
vacuum space of about 25 A was added along with the z-di- for all nine configurations, which means that the structures
rection to prevent interactions between the neighbor hetero- are stable in energy. The TB, TBx, and TBy configurations, as
structures. The 4 8 1 G-centered grid k-mash is used to be shown in Fig. 1, hold the three largest absolute values of Ef. So,
sampled within the first Brillouin zone, and 500 eV of cutoff they are selected for the following discussions. Then, their
energy is selected. The convergent thresholds of 105 eV and thermal stabilities are confirmed with the results of the AIMD
0.01 eV/
A are adopted for energy and force in the geometrical simulations in Fig. S3.
optimization, respectively. The Nose-Hoover [48,49] thermo- The carrier mobilities of the monolayers are calculated
stat method, the supercells of 4 2 1 for the presently according to the deformation theory having described in the
considered structures of the InTe/Bismuthene hetero- Supplementary Materials, and the obtained outcomes are
structure, and the canonical ensemble (NVT) are used to shown in Figs. S4-S5 and Table. S2. For Bismuthene, the
perform the AIMD simulations to assure thermal stability. The electron mobilities can reach ~104 cm2V1s in both the x and y
present 10-ps runs of AIMDs are carried out at 400 K, and two directions. These values show approximately 10/100 times
fs of the time interval are used. The computational method larger than those of holes in the same directions, respectively.
and detail for mobility, and the STH conversion efficiency of For the InTe monolayer, the electron mobility in the y-direc-
HER are presented in the Supplementary Materials. tion approaches 1.26 104 cm2V1s, which is much larger
than the hole in the same direction. Therefore, the mobilities
of electron and hole demonstrate significant differences for
Results and discussions both the InTe monolayer and Bismuthene, indicating that the
spatial charge separation of electron-hole pairs and the effi-
Geometrical structures, electronic/optical characters for the cient photoelectronic performance are possible. Unfortu-
InTe monolayer, Bismuthene, and their heterostructure nately, no experimental carrier mobility has been found for
the two monolayers. The result can be used as a helpful
The bulk structures corresponding to the two monolayers are reference for the experimental measurement by the optical
calculated and compared with the experimental data [36,57] to pump terahertz probes [59] or transient current techniques
confirm the reliability of the present calculational method. [60] that have been developed for the measurement of carrier
The optimized lattice constants are 3.77 and 3.20 A for the mobility.
InTe monolayer and Bismuthene with space group Pm3 m (No. The optical absorptions of the InTe monolayers and Bis-
221), which are in agreement with the experimentally re- muthene are calculated by using the geometrical structures
ported data of 3.61 [36] and 3.18 [57] A, respectively. The separated from the heterostructure [23], because the mono-
optimized geometrical structures of the InTe monolayer and layers in the heterostructure will be deformed to some extent
Bismuthene are demonstrated in Fig. S1, respectively. The in comparison with those of the isolated ones. The optical
obtained lattice parameter of 4.24 A for the InTe monolayer absorption aðuÞ of the InTe monolayer and Bismuthene can be
equals the calculational datum of Zo lyomi et al. [35], while computed by Ref. [61]:
that of 4.21
A for Bismuthene is close to the theoretical 4.26
A rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
of Mozvashi et al. [58] Therefore, the lattice mismatch ratio of aðuÞ ¼ 2u ε21 ðuÞ þ ε22 ðuÞ ε1 ðuÞ (2)
the InTe monolayer and Bismuthene is only 0.7%, indicating
that the two monolayers are suitable for constructing Here the imaginary part ε2 ðuÞ of dielectric function will be
heterostructure. calculated by using the following expression [62]:
To examine the possible configurations of the hetero- Z
4p2 X 2 2
structure consisting of the InTe monolayer and Bismuthene in ε2 ðuÞ ¼ Mc;y ðkÞ dðεck εyk huÞd3 k (3)
different stacking ways, we construct nine configurations by m2 u2 c;y BZ ð2pÞ
3
overturning each monolayer along with the x and y axes and 2

The momentum matrix element Mc;y ðkÞ is computed by
go across the center of the conventional cell of the monolayer,
employing HSE06. The real part ε1 is deduced from ε1 by
which can keep the lattice mismatch ratio unchanged. The
KramerseKronig transformation [63].
monolayers, together with the overturned counterparts, are
The obtained aðuÞ are illustrated in Fig. 2. The monolayers,
denoted as T, Tx, Ty, B, Bx, and By, respectively. As a result,
which are separated from the InTe/Bismuthene hetero-
the possible stacking configurations of TB, TBx, TBy, TxB,
structure, demonstrate obvious absorptions within the visible
TxBx, TxBy, TyB, TyBx, and TyBy are built and subjected to
light/UV range, which indicates that the heterostructure can
relaxation calculations. The fully relaxed structures are illus-
capture solar energy. In addition to that, the aðuÞ of the InTe
trated in Fig. S2. The stabilities of the configurations are
monolayer and Bismuthene are not significantly altered in
evaluated by calculating formation energy (Ef) using the
different configurations, which indicates that all the consid-
equation
ered configurations can respond to the sunlight well, which is
a valuable prerequisite for the realization of photocatalytic
Ef ¼ EHet-EInTe-EBismuthene (1) water splitting.
Fig. 1 e The top and side views of the three most stable configurations of the InTe/Bismuthene heterostructure. (a) Stacking
with the usual structures of the InTe monolayer and Bismuthene (TB), (b) the Bismuthene overturned along with the x-axis
(TBx), and (c) the Bismuthene overturned along with the y-axis (TBy).
Fig. 2 e The optical absorptions of the Bismuthene and InTe monolayers. Both the individual monolayers and the ones are
separated from the heterostructure are considered.
Overall water splitting of the InTe/Bismuthene agreement with the theoretical 0.99 eV obtained by Zhang
heterostructure and effect of strain et al. [65]. Then, the band alignments and total projected
densities of state for the presently considered configurations
The band alignments and total densities of state for the isolate are calculated by employing HSE06 and illustrated in Fig. 3 and
InTe monolayer/Bismuthene are computed by using HSE06 Fig. S7-8, respectively. The CBMs/VBMs of the InTe monolayer
and presented in Fig. S6, respectively. By the way, an indirect and Bismuthene are projected from the band alignments of
bandgap of 1.96 eV by HSE06 can be obtained for the InTe the heterostructure and collected in Table. S3. The results
monolayer if the geometrical structure is optimized by PBE. demonstrate that all the configurations of TB, TBx, and TBy
This value approximately equals the previously reported have a staggered arrangement of band alignment. The CBM of
1.94 eV [64]. However, all the present optimizations of the heterostructure is attributed to the InTe monolayer, while
geometrical structures are performed by HSE06 to obtain more the VBM is located at Bismuthene. The bandgaps of these
accurate results. The VBM is situated in a section between G three configurations are 0.86, 0.77, and 0.64 eV, which are
and Y. At the same time, one can find that the CBM is situated smaller than those of the separate monolayers. However, the
at G. Therefore, the monolayer has an indirect bandgap of bandgaps of Bismuthene demonstrate an apparent increase,
2.49 eV. The Bismuthene has a direct bandgap of 1.03 eV since while those of the InTe monolayer only decrease a little in
its CBM and VBM are located at the G point, which is in good comparison with the bandgap of the individual ones.
Fig. 3 e The band structures for the TB, TBx, and TBy configurations of the InTe/Bismuthene heterostructure by HSE06. The
Fermi level is set to zero.
The vacuum levels are evaluated with the asymptotic The results in Fig. 5 have illustrated an electron accu-
values of electrostatic potential in the vacuum space. Based mulation in the inner surface of the InTe monolayer, indi-
on the outcomes from Fig. S9, the redox potentials of the band cating that electrons transfer from the Bismuthene to the
edges for each configuration are determined by subtracting InTe monolayer in three configurations. Moreover, the
the vacuum levels from the CBMs/VBMs by HSE06. Then, the electron transfer can also be illustrated visually, as shown in
photocatalytic Z-schemes for overall water splitting are con- Fig. S10. The quantitative charge transfer between the
structed. As shown in Fig. 4, the potential of the CBM on the monolayers in the InTe/Bismuthene heterostructure is
Bismuthene is over the reduction potential of HER, while the evaluated by Bader charge analysis [66e68]. The results
one of the VBM on the InTe monolayer exceeds the oxidation show that the charge transfer amounts from Bismuthene to
potential of OER for all three configurations. Therefore, the the InTe monolayer in the configurations of TB, TBx, and
present configurations of the InTe/Bismuthene hetero- TBy are 0.07, 0.07, and 0.05 |e|, respectively, which confirms
structure match the conditions of the overall water splitting to the conclusion by the average difference in charge density.
generate hydrogen with the Z-scheme. Nevertheless, a satis- It is worth noting that a work function (F) difference be-
factory built-in electric field direction between the inner tween two semiconductor photocatalysts is the pre-
interface of heterostructure is needed to complete the Z- requisite for inducing charge redistribution and the forma-
scheme's electron transfer between the monolayers. We use tion of a built-in electric field, which remarkably affects the
the average difference in charge density (Dr ) along with the z- photogenerated charge carrier separation and transfer pro-
axis to recognize the built-in electric field direction for the cess [11,69]. The F of the InTe monolayer and Bismuthene
InTe/Bismuthene heterostructure. If the in-plane average are 5.71 and 4.04 eV, respectively. When the two monolayers
electron density of the InTe/Bismuthene heterostructure and come into contact to form the InTe/Bismuthene hetero-
the InTe monolayer and Bismuthene are stood for by rHet , structure, the electrons will transfer from Bismuthene to
rInTe , and rBi , one can obtain: InTe until the Fermi level is in equilibrium. These charge
transfers induce built-in electric fields in the space between
Dr ¼ rHet rInTe rBismuthene (4)
Bismuthene and the InTe monolayer, and the direction is
Fig. 4 e The type II band alignments of Z-schemes for the three configurations of the InTe/Bismuthene heterostructure.
Fig. 5 e The curves of plane-integrated electron density difference along with the z-direction for the TB, TBx, and TBy
configurations. Dotted lines mark the edges of the two monolayers.
from the inner interface of the Bismuthene to that of the biaxial strains. However, the band edges demonstrate
InTe monolayer. In addition to that, the built-in electric field different changes with the strains. For the TB configuration,
can propel the photogenerated electrons to move from the both CBM and VBM are lifted by the compressive strains but
InTe monolayer to Bismuthene to recombine the photo- lowered by the tensile strains, which changes the bandgaps
generated holes in the Bismuthene. Therefore, the consid- and overpotentials of HER and OER, as shown in Tables. S4-S6.
ered configurations of the InTe/Bismuthene heterostructure As a result, the hSTH of the configuration decreases under the
can support the mechanism of the Z-scheme for photo- compressive strains but increases under the tensile ones and
catalytic overall water splitting. reaches a maximum of 16.17% under the biaxial tensile strain
To assess the hydrogen production efficiencies for the Z- of 9%. For the TBx and TBy configurations, the strain effect on
schemes, we calculate the hSTH for the three configurations of hSTH are less obvious, although the compressive strains still
the InTe/Bismuthene heterostructure, based on the compu- decrease, and the tensile ones increase the hSTH s. Corre-
tational method [70] in Supplementary Materials. The calcu- spondingly, the maximum hSTH s of the TBx and TBy configu-
lations are for the maximum conversion efficiency with the rations is 12.07% and 13.93% under 4% and 2% biaxial tensile
irradiance of the sun, the bandgap of the monolayers, and the strains, respectively. Obviously, the TB configuration can
overpotentials of CBM and VBM, which premises that all the reach hSTH higher than the other two configurations under
photogenerated carriers satisfy the requirements of overall heavy tensile strains, although its hSTH is the lowest one
water splitting can complete HER and OER. Here, the over- without strain. These outcomes also mean that the
potentials for HER and OER are the CBM and VBM referring to compressive strain should be avoided to pursue higher hSTH
the redox potential of photocatalytic water splitting for for the InTe/Bismuthene heterostructure. In fact, we have also
hydrogen production and oxygen evolution reactions, considered the photocatalytic overall water splitting for both
respectively. It should be noticed that the optical absorptions monolayers. The potential of 4.24 eV for the VBM of Bismu-
simultaneously occur on the two monolayers. As a result, the thene does not meet OER, although that of 3.22 eV for the
larger one of the two bandgaps projected from the hetero- CBM is suitable for HER. So, the overall water splitting cannot
structure will dominate the photoexcited performance. Ac- be driven by Bismuthene to produce hydrogen. However, the
cording to the bandgaps of each monolayer projected from the HER and OER can be driven by the InTe monolayer because its
band alignment of heterostructure in Table S3, the larger one potentials of CBM and VBM simultaneously satisfy the HER/
is attributed to the InTe monolayer for all the considered OER conditions. Unfortunately, the hSTH of this monolayer can
configurations. So, these bandgaps are used in the calcula- only reach 4.22%, which is significantly lower than those of
tions of hSTH . The method has been used for estimating the the InTe/Bismuthene heterostructure. Therefore, the InTe/
STH conversion efficiencies for many monolayers [71,72], Bismuthene heterostructure can more efficiently drive the
heterostructures [23,27,73,74], and nanosheets [75]. By using overall water splitting reaction. Moreover, the InTe/Bismu-
the overpotentials and bandgaps in Tables. S4-S6, the hSTH of thene heterostructure has superior performance in the
the three configurations of the InTe/Bismuthene hetero- transferring and separation of the charges. As shown in the
structure are obtained. As demonstrated in Tables. S4-S6, the above section for the work function, the F of the InTe mono-
largest hSTH of 9.67% is attributed to TBy configurations, and layer is larger than that of Bismuthene. When the two
the smaller ones with the TB configuration can reach 6.56%. monolayers come into contact to form the heterostructure,
The tables indicate that the hSTH s of the configurations are the electrons will transfer from Bismuthene to InTe until the
mainly dominated by the hcu that is affected by the difference Fermi level reaches equilibrium. As a result, the InTe layer
between oxidation and reduction. becomes negatively charged due to the gain of electrons, while
The strain engineering on the electronic structure char- Bismuthene becomes positively charged by losing electrons.
acter and hSTH are also investigated. Fig. 6 illustrates that the Therefore, a built-in electric field directed from Bismuthene to
band edges under the considered biaxial strains remain to InTe is generated at the interface, which facilitates to transfer
straddle the redox potentials of the HER and OER reactions, the photo-generated electrons from the InTe monolayer to
indicating that all three configurations can drive HER under Bismuthene and to recombine the hole. This recombination
Fig. 6 e The effects of biaxial strains on the potentials for HER (the CBM of the InTe monolayer) and for OER(the VBM of
Bismuthene) of the direct Z-scheme driven by the InTe/Bismuthene heterostructure.
will suppress the recombination of the photogenerated pairs monolayer, the STH conversion efficiency hSTH is promoted
of each monolayer and prolong the lifetime of the electron for because the bandgap decreases, but the overpotentials are
HER and the hole for OER. Meanwhile, the photo-generated retained when the heterostructure is constructed. The largest
holes in Bismuthene are propelled into the InTe monolayer hSTH can reach 9.67%, and a higher one of 16.17% is possible
and join the OER there. As a result, photocatalytic perfor- under 9% biaxial tensile strain, although all the compressive
mance is promoted and excellent hSTH is obtained. strains will reduce the hSTH of the considered configurations.
The alterations of the Gibbs free energy in the range of
The Gibbs free energy alterations (DGH s) in HERs 2.05e2.12 eV, which is smaller than those of some photo-
catalysts realized by the experiment, indicate the present
The Gibbs free energy alterations (DGH s) in HERs are calcu- HERs with Z-scheme driven by the considered configurations
lated to understand the thermodynamic feasibility of the re- of the InTe/Bismuthene heterostructure are thermodynami-
actions according to the computational approach in cally feasible. The present results suggest that the InTe/Bis-
Supplementary Materials. For the three configurations of the muthene heterostructure could have potential applications in
InTe/Bismuthene heterostructure, we considered the solar photocatalytic overall water splitting to manufacture
adsorption sites on Bismuthene because the HER with the Z- hydrogen.
scheme occurs on the monolayer. The fully relaxed structures
for the H adsorbed on the heterostructure are demonstrated in
Fig. S11, and the adsorption energy DEH s for each site are listed Declaration of competing interest
in Tables. S7-S9. The obtained outcomes in Fig. S10 show that
the DGH s of the HERs driven by the three configurations are in The authors declare that they have no known competing
the range of 2.05e2.12 eV. When two hydrogen atoms are financial interests or personal relationships that could have
adsorbed at the equivalent sites for the Tafel step [76] to appeared to influence the work reported in this paper.
produce H2, the DGH for each site on the TB configuration can
decrease to 1.72 eV. The present DGH s are close to the theo-
retical 1.88 eV of the Re1xMoxSe2 alloy [77] and smaller than
Acknowledgments
that of the N-doped Ni3S2 (2.7 eV) [78] that have been achieved
experimentally, implying that the HERs driven by the InTe/
This work was supported by the National Natural Science
Bismuthene heterostructure is not easy but feasible.
Foundation of China under Grant Nos. NSFC-11874192.
Conclusion
Appendix A. Supplementary data
In conclusion, we have constructed the direct Z-schemes from
Supplementary data to this article can be found online at
hydrogen generation from photocatalytic HER/OER driven by
https://doi.org/10.1016/j.ijhydene.2022.09.249.
InTe/Bismuthene heterostructure. Nine configurations of the
heterostructure were constructed, and the three most stable
ones were screened out according to their formation energy. references
The band alignment, charge transfer, and built-in electric
fields endorse the direct Z-scheme for the photocatalytic
overall water splitting to produce hydrogen. The obvious [1] Kubacka A, Ferna ndez-Garcı́a M, Colo
n G. Advanced
different mobilities for the photogenerated electron and hole, nanoarchitectures for solar photocatalytic applications.
and absorptions in the visible light region indicate that effi- Chem Rev 2012;112:1555e614.
cient photoelectronic performance of the InTe monolayer and [2] Fu J, Yu J, Jiang C, Cheng B. g-C3N4-Based heterostructured
Bismuthene are feasible. Compared with the isolate InTe photocatalysts. Adv Energy Mater 2018;8:1701503.
[3] Turner JA. Sustainable hydrogen production. Science driven by the Sb2S3 monolayer and RuI2/Sb2S3
2004;305:972e4. heterostructure with solar light. J Power Sources
[4] Armaroli N, Balzani V. The hydrogen issue. ChemSusChem 2022;532:231352.
2011;4:21e36. [26] Li P, Lin Y, Ma M, Wang Q, Zhang M, Li J, et al. Effect of
[5] Ball M, Wietschel M. The future of hydrogen-opportunities pressure on photocatalytic water splitting performance of Z-
and challenges. Int J Hydrogen Energy 2009;34:615e27. scheme RP/CH3NH3PbI3 perovskite heterostructure. Int J
[6] Holladay JD, Hu J, King DL, Wang Y. An overview of hydrogen Hydrogen Energy 2022;47:8091e104.
production technologies. Catal Today 2009;139:244e60. [27] Zhang CF, Yang CL, Wang MS, Ma XG. Z-Scheme
[7] Chen X, Shen S, Guo L, Mao SS. Semiconductor-based photocatalytic solar-energy-to-hydrogen conversion driven
photocatalytic hydrogen generation. Chem Rev by the HfS2/SiSe heterostructure. J Mater Chem C
2010;110:6503e70. 2022;10:5474e81.
[8] Liao CH, Huang CW, Wu JCS. Hydrogen production from [28] Wang Y, Yang C, Zhang Y, Guo L, Wang Y, Gao G, et al.
semiconductor-based photocatalysis via water splitting. Nanoarchitectonics of CdS/ZnSnO3 heterostructures for Z-
Catalysts 2012;2:490e516. Scheme mediated directional transfer of photo-generated
[9] Kudo A, Miseki Y. Heterogeneous photocatalyst materials for charges with enhanced photocatalytic performance. Int J
water splitting. Chem Soc Rev 2009;38:253e78. Hydrogen Energy 2022;47:9566e78.
[10] Meng A, Zhang L, Cheng B, Yu J. Dual cocatalysts in TiO2 [29] Lei S, Ge L, Najmaei S, George A, Kappera R, Lou J, et al.
photocatalysis. Adv Mater 2019;31:e1807660. Evolution of the electronic band structure and efficient
[11] Bai S, Jiang J, Zhang Q, Xiong Y. Steering charge kinetics in photo-detection in atomic layers of InSe. ACS Nano
photocatalysis: intersection of materials syntheses, 2014;8:1263e72.
characterization techniques and theoretical simulations. [30] Mudd GW, Svatek SA, Hague L, Makarovsky O,
Chem Soc Rev 2015;44:2893e939. Kudrynskyi ZR, Mellor CJ, et al. High broad-band
[12] Low J, Yu J, Jaroniec M, Wageh S, Al-Ghamdi AA. photoresponsivity of mechanically formed InSe-graphene
Heterojunction photocatalysts. Adv Mater 2017;29:1601694. van der Waals heterostructures. Adv Mater
[13] Wang B, Zhang J, Huang F. Enhanced visible light 2015;27:3760e6.
photocatalytic H2 evolution of metal-free g-C3N4/SiC [31] Mudd GW, Svatek SA, Ren T, Patane A, Makarovsky O,
heterostructured photocatalysts. Appl Surf Sci Eaves L, et al. Tuning the bandgap of exfoliated InSe
2017;391:449e56. nanosheets by quantum confinement. Adv Mater
[14] Low J, Jiang C, Cheng B, Wageh S, Al-Ghamdi AA, Yu J. A 2013;25:5714e8.
review of direct Z-scheme photocatalysts. Small Methods [32] Late DJ, Liu B, Luo J, Yan A, Matte HS, Grayson M, et al. GaS
2017;1:1700080. and GaSe ultrathin layer transistors. Adv Mater
[15] Maeda K. Z-scheme water splitting using two different 2012;24:3549e54.
semiconductor photocatalysts. ACS Catal 2013;3:1486e503. [33] Schwarz S, Dufferwiel S, Walker PM, Withers F,
[16] Zhou P, Yu J, Jaroniec M. All-solid-state Z-scheme Trichet AA, Sich M, et al. Two-dimensional metal-
photocatalytic systems. Adv Mater 2014;26:4920e35. chalcogenide films in tunable optical microcavities. Nano
[17] Li X, Shen R, Ma S, Chen X, Xie J. Graphene-based Lett 2014;14:7003e8.
heterojunction photocatalysts. Appl Surf Sci [34] Feng W, Zheng W, Cao W, Hu P. Back gated multilayer InSe
2018;430:53e107. transistors with enhanced carrier mobilities via the
[18] Fu CF, Sun J, Luo Q, Li X, Hu W, Yang J. Intrinsic electric fields suppression of carrier scattering from a dielectric interface.
in two-dimensional materials boost the solar-to-hydrogen Adv Mater 2014;26:6587e93.
efficiency for photocatalytic water splitting. Nano Lett [35] Zo lyomi V, Drummond ND, Fal'ko VI. Electrons and phonons
2018;18:6312e7. in single layers of hexagonal indium chalcogenides fromab
[19] Wang X, Liu G, Chen ZG, Li F, Wang L, Lu GQ, et al. Enhanced initiocalculations. Phys Rev B 2014;89:205416.
photocatalytic hydrogen evolution by prolonging the lifetime [36] Chattopadhyay T, Santandrea R, Von Schnering H.
of carriers in ZnO/CdS heterostructures. Chem Commun Temperature and pressure dependence of the crystal
2009:3452e4. structure of InTe: a new high pressure phase of InTe. J Phys
[20] Hu J, Chen D, Mo Z, Li N, Xu Q, Li H, et al. Z-scheme 2D/2D Chem Solid 1985;46:351e6.
heterojunction of black phosphorus/monolayer Bi2WO6 [37] Rajaji V, Pal K, Sarma SC, Joseph B, Peter SC, Waghmare UV,
nanosheets with enhanced photocatalytic activities. Angew et al. Pressure induced band inversion, electronic and
Chem Int Ed Engl 2019;58:2073e7. structural phase transitions in InTe: a combined
[21] Chu S, Hu Y, Zhang J, Cui Z, Shi J, Wang Y, et al. Constructing experimental and theoretical study. Phys Rev B
direct Z-scheme CuO/PI heterojunction for photocatalytic 2018;97:1551158.
hydrogen evolution from water under solar driven. Int J [38] Ho CH. Thickness-dependent carrier transport and optically
Hydrogen Energy 2021;46:9064e76. enhanced transconductance gain in III-VI multilayer InSe. 2D
[22] Bao J, Zhu B, Zhang F, Chen X, Guo H, Qiu J, et al. Sc2CF2/Janus Mater 2016;3:25019.
MoSSe heterostructure: a potential Z-scheme photocatalyst [39] Demirci S, Avazlı N, Durgun E, Cahangirov S. Structural and
with ultra-high solar-to-hydrogen efficiency. Int J Hydrogen electronic properties of monolayer group III
Energy 2021;46:39830e43. monochalcogenides. Phys Rev B 2017;95:115409.
[23] Yin QK, Yang CL, Wang MS, Ma XG. Two-dimensional [40] Sun HH, Wang MX, Zhu F, Wang GY, Ma HY, Xu ZA, et al.
heterostructures of AuSe/SnS for the photocatalytic Coexistence of topological edge state and superconductivity
hydrogen evolution reaction with a Z-scheme. J Mater Chem in bismuth ultrathin film. Nano Lett 2017;17:3035e9.
C 2021;9:12231e8. [41] Hussain N, Liang T, Zhang Q, Anwar T, Huang Y, Lang J, et al.
[24] Sun S, Ren D, Yang M, Cui J, Yang Q, Liang S. In-situ Ultrathin Bi nanosheets with superior photoluminescence.
construction of direct Z-scheme sea-urchin-like ZnS/SnO2 Small 2017;13:1701349.
heterojunctions for boosted photocatalytic hydrogen [42] Lu L, Liang Z, Wu L, Chen Y, Song Y, Dhanabalan SC, et al.
production. Int J Hydrogen Energy 2022;47:9201e8. Few-layer bismuthene: sonochemical exfoliation, nonlinear
[25] Wang F, Yang CL, Wang MS, Ma XG. Photocatalytic hydrogen optics and applications for ultrafast photonics with
evolution reaction with high solar-to-hydrogen efficiency enhanced stability. Laser Photon Rev 2018;12:1700221.
[43] Reis F, Li G, Dudy L, Bauernfeind M, Glass S, Hanke W, et al. [62] Read AJ, Needs RJ. Calculation of optical matrix elements
Bismuthene on a SiC substrate: a candidate for a high- with nonlocal pseudopotentials. Phys Rev B 1991;44:13071e3.
temperature quantum spin Hall material. Science [63] Melrose D, Stoneham R. Generalised Kramers-Kronig
2017;357:287e90. formula for spatially dispersive media. J Phys 1977;10:L17.
[44] Zhang S, Xie M, Li F, Yan Z, Li Y, Kan E, et al. Semiconducting [64] Rawat A, Ahammed R, Dimple Jena N, Mohanta MK, De
group 15 monolayers: a broad range of band gaps and high Sarkar A. Solar energy harvesting in type II van der Waals
carrier mobilities. Angew Chem Int Ed Engl 2016;55:1666e9. heterostructures of semiconducting group III
[45] Xiao S, Wei D, Jin X. Bi(111) thin film with insulating interior monochalcogenide monolayers. J Phys Chem C
but metallic surfaces. Phys Rev Lett 2012;109:166805. 2019;123:12666e75.
[46] Degtyareva O, McMahon MI, Nelmes RJ. Crystal structure of [65] Zhang S, Guo S, Chen Z, Wang Y, Gao H, Gomez HJ, et al.
the high pressure phase of bismuth Bi-III. Mater Sci Forum Recent progress in 2D group-VA semiconductors: from
2001;378e381:469e75. theory to experiment. Chem Soc Rev 2018;47:982e1021.
[47] Zhao Y, Cle ment S, Haines J, Viennois R. Lattice dynamics [66] Henkelman G, Arnaldsson A, Jo nsson H. A fast and robust
study of elemental bismuth under high pressure. J Phys algorithm for Bader decomposition of charge density.
Chem C 2020;124:26659e69. Comput Mater Sci 2006;36:354e60.
[48] Nose S. A unified formulation of the constant temperature [67] Sanville E, Kenny SD, Smith R, Henkelman G. Improved grid-
molecular dynamics methods. J Chem Phys 1984;81:511e9. based algorithm for Bader charge allocation. J Comput Chem
[49] Hoover WG. Canonical dynamics: equilibrium phase-space 2007;28:899e908.
distributions. Phys Rev 1985;31:1695e7. [68] Tang W, Sanville E, Henkelman G. A grid-based Bader
[50] Heyd J, Scuseria GE, Ernzerhof M. Hybrid functionals based analysis algorithm without lattice bias. J Phys Condens
on a screened Coulomb potential. J Chem Phys Matter 2009;21:84204.
2003;118:8207e15. [69] Liu J, Cheng B, Yu J. A new understanding of the
[51] Perdew JP, Burke K, Ernzerhof M. Generalized gradient photocatalytic mechanism of the direct Z-scheme g-C3N4/
approximation made simple. Phys Rev Lett TiO2 heterostructure. Phys Chem Chem Phys
1996;77:3865e8. 2016;18:31175e83.
[52] Kresse G, Furthmüller J. Efficient iterative schemes for ab [70] Fu CF, Sun J, Luo Q, Li X, Hu W, Yang J. Intrinsic electric fields
initio total-energy calculations using a plane-wave basis set. in two-dimensional materials boost the solar-to-hydrogen
Phys Rev B 1996;54:11169e86. efficiency for photocatalytic water splitting. Nano Lett
[53] Kresse G, Furthmüller J. Efficiency of ab-initio total energy 2018;18:6312e7.
calculations for metals and semiconductors using a plane- [71] Qiao NH, Yang CL, Wang MS, Ma XG. Two-dimensional
wave basis set. Comput Mater Sci 1996;6:15e50. TeX(X¼C, Si, Ge) monolayers with strong intrinsic electric
[54] Grimme S, Antony J, Ehrlich S, Krieg H. A consistent and field for efficiency hydrogen evolution reaction. Surface
accurate ab initio parametrization of density functional Interfac 2022;31:102011.
dispersion correction (DFT-D) for the 94 elements H-Pu. J [72] Ju L, Shang J, Tang X, Kou L. Tunable photocatalytic water
Chem Phys 2010;132:154104. splitting by the ferroelectric switch in a 2D AgBiP2Se6
[55] Kresse G, Joubert D. From ultrasoft pseudopotentials to the monolayer. J Am Chem Soc 2020;142:1492e500.
projector augmented-wave method. Phys Rev B [73] Fan Y, Wang J, Zhao M. Spontaneous full photocatalytic
1999;59:1758e75. water splitting on 2D MoSe2/SnSe2 and WSe2/SnSe2 vdW
€ chl PE. Projector augmented-wave method. Phys Rev B
[56] Blo heterostructures. Nanoscale 2019;11:14836e43.
1994;50:17953e79. [74] Ren K, Tang W, Sun M, Cai Y, Cheng Y, Zhang G. A direct Z-
[57] Jaggi R. Structure and properties of the high pressure scheme PtS2/arsenene van der Waals heterostructure with
modification Bi II. Helv Phys Acta 1964;37:618e9. high photocatalytic water splitting efficiency. Nanoscale
[58] Mozvashi SM, Vishkayi SI, Tagani MB. Antimonene/ 2020;12:17281e9.
bismuthene vertical Van-der Waals heterostructure: a [75] Liu M, Yang CL, Wang MS, Ma XG. Halogen edge-passivated
computational study. Phys Met 2020;118:113914. antimonene nanoribbons for photocatalytic hydrogen
[59] Johnston MB, Herz LM. Hybrid perovskites for photovoltaics: evolution reaction with high solar-to-hydrogen conversion. J
charge-carrier recombination, diffusion, and radiative Phys Chem C 2021;125:21341e51.
efficiencies. Acc Chem Res 2016;49:146e54. [76] Nørskov JK, Bligaard T, Logadottir A, Kitchin J, Chen JG,
[60] Eremin V, Strokan N, Verbitskaya E, Li Z. Development of Pandelov S, et al. Trends in the exchange current for
transient current and charge techniques for the hydrogen evolution. J Electrochem Soc 2005;152:J23.
measurement of effective net concentration of ionized [77] Kwak IH, Kwon IS, Debela TT, Abbas HG, Park YC, Seo J, et al.
charges (Neff) in the space charge region of pn junction Phase evolution of Re1-xMoxSe2 alloy nanosheets and their
detectors. Nucl Instrum Methods Phys Res A enhanced catalytic activity toward hydrogen evolution
1996;372:388e98. reaction. ACS Nano 2020;14:11995e2005.
[61] Saha S, Sinha T, Mookerjee A. Electronic structure, chemical [78] Chen P, Zhou T, Zhang M, Tong Y, Zhong C, Zhang N, et al. 3D
bonding, and optical properties of paraelectric BaTiO3. Phys nitrogen-anion-decorated nickel sulfides for highly efficient
Rev B 2000;62:8828. overall water splitting. Adv Mater 2017;29:1701584.

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international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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Photocatalytic hydrogen generation from overall

Meng Ge, Chuan-Lu Yang*, Mei-Shan Wang, Xiao-Guang Ma

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article info abstract

In recent years, the monochalcogenides with honeycomb

overturning each monolayer along with the x and y axes and 2

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