Computational Search for Two-Dimensional Photocatalysts V. Wang1G. Tang2Y. C. Liu1Y. Y. Liang3H. Mizuseki4Y. Kawazoe567J. Nara8and W. T. Geng9y 1Department of Applied Physics Xian University of Technology Xian 710054 China

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Computational Search for Two-Dimensional Photocatalysts

V. Wang,1, ∗G. Tang,2Y. C. Liu,1Y. Y. Liang,3H. Mizuseki,4Y. Kawazoe,5, 6, 7 J. Nara,8and W. T. Geng9, †

1Department of Applied Physics, Xi’an University of Technology, Xi’an 710054, China

2Advanced Research Institute of Multidisciplinary Science,

Beijing Institute of Technology, Beijing 100081, China

3Department of Physics, Shanghai Normal University, Shanghai 200234, China

4Korea Institute of Science and Technology (KIST), Seoul 02792, Republic of Korea

5New Industry Creation Hatchery Center, Tohoku University, Sendai, Miyagi 980-8579, Japan

6Department of Physics and Nanotechnology, SRM Institute of

Science and Technology, Kattankulathur,Tamil Nadu-603203, India

7Department of Physics, Suranaree University of Technology, Nakhon, Ratchasima, Thailand

8National Institute for Materials Science, Tsukuba 305-0044, Japan

9School of Materials Science and Engineering, Hainan University, Haikou 570228, China

(Dated: October 11, 2022)

To overcome current serious energy and environmental issues, photocatalytic water splitting holds

great promise because it requires only solar energy as an energy input to produce hydrogen. Two-

dimensional (2D) semiconductors and heterostructures possess several inherent advantages which

are more suitable for boosting solar energy than their bulk counterparts. In this work, by per-

forming high-throughput ﬁrst-principles calculations combined with a semiempirical van der Waals

dispersion correction, we ﬁrst provided the periodic table of band alignment type for van der Waals

heterostructures when packing any two of the 260 semiconductor monolayers obtained from our

2D semiconductor database (2DSdb) (https://materialsdb.cn/2dsdb/index.html). Based on the

rules of thumb for photocatalytic water splitting, we have further screened dozens of potential semi-

conductors and thousands of heterostructures which are promising for photocatalytic water splitting.

The resulting database would provide a useful guidance for experimentalists to design suitable 2D

vdWHs and photocatalysts according to desired applications.

I. INTRODUCTION

Exploiting photocatalytic water splitting (PWS) for

hydrogen production oﬀers a potential solution to the en-

ergy crisis caused by the approaching exhaustion of fos-

sil fuels and the serious environmental problems.1The

discovery of PWS on TiO2electrode by Fujishima and

Honda in 1972 has opened a new epoch in harness-

ing solar energy.2Many potential semiconductor pho-

tocatalysts have been extensively investigated and vari-

ous photocatalysis,3including WO3,4Bi2WO6,5Bi2O3,6

C3N4,7and CdS,8have been developed. However, the

practical application of PWS for hydrogen production is

limited by several technical issues such as the inability to

utilize visible light, insuﬃcient quantum eﬃciency, fast

backward reaction, and poor activation of catalysts.9–12

In bulk materials, photoexcited carriers must move to

the surfaces of photocatalysts to participate in the redox

reaction with the absorbed water molecules. Due to the

long and complex migration path, a large number of pho-

toinduced electrons and holes may recombine, resulting

in poor photocatalytic eﬃciency.12 Continuous search of

eﬃcient and environment-friendly photocatalysts for hy-

drogen production is therefore very urgent.

Two-dimensional (2D) semiconductors have many ad-

vantages which can be used to improve the photocat-

alytic eﬃciency for water splitting as discussed in sev-

eral reviews and the references therein.13–18 Compared

with their bulk counterparts, 2D materials can pro-

vide a more eﬃcient redox reaction due to the abun-

dant reactive sites, improved electron-hole separation,

fast mobility of charge carriers, short diﬀusion length

for photo-generated electrons and holes, which causes

lower electron-hole recombination rate and better quan-

tum eﬃciency.13,17 Thus, the search and design of 2D

photocatalysts for water splitting has been a hot topic

in both experimental and theoretical studies.13,17 Cur-

rently, a variety of 2D materials have been veriﬁed to

be promising photocatalysts for water splitting veriﬁed

by experiments or ﬁrst-principles calculations, including

MoS2,19 g-C3N4,20 SnS2,21 FePS3,22 single layer group-

III monochalcogenides,23 Transition metal phosphorus.24

Owing to the quantum conﬁnement eﬀect, 2D photocat-

alysts can be further modulated through band gap en-

gineering by varying the chemical and/or physical con-

ditions, including layer thickness, stacking order, dop-

ing, defect engineering, strain, external electric ﬁeld,

etc.17,25,26

However, 2D materials also face some problems while

serving as photocatalysts.25,27 For example, photogen-

erated carriers accumulated in monolayers are easy to

recombine. Moreover, some 2D semiconductors are not

stable in air or aqueous solution, leading to the decrease

of the photocatalytic activity. In parallel with the eﬀorts

on synthesis of new 2D monolayer photocatalysts, an-

other strategy has been gaining strength over the past few

years. By stacking together diﬀerent 2D materials on top

of each other, various artiﬁcial van der Waals heterostruc-

tures (vdWHs) can be formed.28,29 Compared with the

conventional bulk semiconductor-based heterostructures,

vdWHs do not demand crystal lattice matching, allow-

arXiv:2210.04423v1 [cond-mat.mtrl-sci] 10 Oct 2022

ing to build artiﬁcial vdWHs with desired functionalities

by picking and stacking atomic layers of arbitrary com-

positions. The vdWHs not only preserve the excellent

properties of the original single layers due to the weak

vdW interaction, but also bear additional features. The

construction of vdWHs is an eﬀective method to further

improve the photocatalytic performance as discussed in

several reviews.13,14,16,18,30 Especially, in type-II hetero-

junctions, the lowest energy states of holes and electrons

are on diﬀerent sides of the heterojunctions, which en-

sures the eﬀective separation of photogenerated electrons

and holes, thereby suppressing the recombination of pho-

togenerated electrons and holes.31,32

Up to now, the electronic and optical properties and

photocatalytic applications of many vdWHs have been

predicted through ﬁrst-principles calculations, provid-

ing strong support for experimental synthesis and com-

mercial applications.31,33 In our previous study, we per-

formed high-throughput ﬁrst-principles calculations to

build a 2D semiconductor database (2DSdb) which in-

cluding more than 260 2D semiconductors.34 In spite of

the rapid development of high-throughput computational

2D crystals databases publicly also available at present,

such as MC2D,35 C2DB36, 2DMatPedia37 and JARVIS-

DFT38, systematic high-throughput predictions of band

alignment in vdWHs are still rather incomplete and in-

vestigations of 2D vdWHs applied in photocatalysis are

strongly called for.

In this work, combining the high-throughput ﬁrst-

principles calculations with a semiempirical vdW dis-

persion correction, the periodic table of heterostructure

types including around 34000 possible vdWHs is obtained

based on Anderson’s rule. Furthermore, dozens of poten-

tial semiconductors and thousands of vdWHs for PWS

applications have been further screened based on the

rules of thumb for PWS. The remainder of this paper is

organized as follows. In Sec. II, methodology and com-

putational details are described. The details of screen-

ing criteria are discussed in Sec. III. Sec. IV presents

high-throughput computational screening of 2d semicon-

ductors and heterostructures potential for photocatalytic

water splitting. Finally, a short summary is given in Sec.

II. METHODOLOGY

A. Density Functional Calculations

Our total energy calculations were performed using

the Vienna Ab initio Simulation Package (VASP).39,40

The electron-ion interaction was described using pro-

jector augmented wave (PAW) method41,42 and the ex-

change and correlation (XC) were treated with GGA

in the Perdew Burke Ernzerhof (PBE) form43. Part of

electronic structure calculations were also performed us-

ing the standard screening parameter of Heyd-Scuseria-

Ernzerhof (HSE06) hybrid functional,44–49 upon the

PBE-calculated equilibrium geometries. A cutoﬀ energy

of 400 eV was adopted for the plane wave basis set, which

yields total energy convergence better than 1 meV/atom.

In addition, the non-bonding vdW interaction is incorpo-

rated by employing a semi-empirical correction scheme

of Grimme’s DFT-D2 method in this study, which has

been successful in describing the geometries of various

layered materials.50,51 In the slab model of 2D systems,

periodic slabs were separated by a vacuum layer of 20

Å in zdirection to avoid mirror interactions. The Bril-

louin zone was sampled by the k-point mesh following the

Monkhorst-Pack scheme,52 with a reciprocal space reso-

lution of 2π×0.03 Å−1. On geometry optimization, both

the shapes and internal structural parameters of pristine

unit-cells were fully relaxed until the residual force on

each atom is less than 0.01 eV/Å. To screen the novel

2D hotocatalysts, we used the VASPKIT package53 as a

high-throughput interface to pre-process the input ﬁles

and post-process the data obtained by using VASP code.

III. RESULTS AND DISCUSSIONS

A. 2D van der Waals Heterojunctions

We begin our discussion by determining the band align-

ments of vdWHs when packing any two of the 260 semi-

conductors obtained from our previous study.34 Accord-

ing to the alignments of the CBM and VBM in the con-

stituent layers, vdWHs can be classiﬁed into three types:

type I (straddling gap), type II (staggered gap), or type

III (broken gap), as illustrated in Fig. 3(a), respectively.

In type I heterojunctions, both VBM and CBM of two in-

dependent component semiconductors are located at the

same side of the heterointerface. This is beneﬁcial for

spatially conﬁning electrons and holes so that eﬃcient re-

combination can be achievable, rendering them potential

applications in optoelectronic devices such as lightemit-

ting diodes (LEDs).54 In type II heterojunctions, the

CBM and VBM are located in diﬀerent components with

electrons accumulating in the layer with the lower CBM

and holes accumulating in the other layer with the higher

VBM. Diﬀerent from type I band alignment, the separa-

tion of electrons and holes on diﬀerent layers can increase

carrier lifetime, which is desirable for photocatalysis and

unipolar electronic device applications including photo-

voltaics and photodetection applications55–59 In type III

heterojunctions, the VBM of one semiconductor is higher

than the CBM of the other, making the whole system

overall heterojunction metallic. Such a property could

have great potential in tunnel ﬁeld-eﬀect transistors and

wavelength photodetectors.60,61

The high-throughput design of vdWHs has gained sig-

niﬁcant attention because vdWHs have unique physical

properties and potential applications mentioned above.

Rasmussen et al. theoretically predicted the band align-

ments of 51 semiconducting TMDs and TMOs mono-

layers using GW0 calculations.62 Latterly, äzçelik et

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ComputationalSearchforTwo-DimensionalPhotocatalystsV.Wang,1,G.Tang,2Y.C.Liu,1Y.Y.Liang,3H.Mizuseki,4Y.Kawazoe,5,6,7J.Nara,8andW.T.Geng9,y1DepartmentofAppliedPhysics,Xi'anUniversityofTechnology,Xi'an710054,China2AdvancedResearchInstituteofMultidisciplinaryScience,BeijingInstituteofTechnology,Beijing...

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Computational Search for Two-Dimensional Photocatalysts V. Wang1G. Tang2Y. C. Liu1Y. Y. Liang3H. Mizuseki4Y. Kawazoe567J. Nara8and W. T. Geng9y 1Department of Applied Physics Xian University of Technology Xian 710054 China

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