Perspective

pubs.acs.org/JPCL

Computational Screening of 2D Materials for Photocatalysis

Arunima K. Singh,†,∥ Kiran Mathew,†,‡ Houlong L. Zhuang,†,§ and Richard G. Hennig*,†,‡
†
Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, United States
‡
Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611, United States

ABSTRACT: Two-dimensional (2D) materials exhibit a range of extraordi-

nary electronic, optical, and mechanical properties different from their bulk
counterparts with potential applications for 2D materials emerging in energy
storage and conversion technologies. In this Perspective, we summarize the
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recent developments in the field of solar water splitting using 2D materials and
review a computational screening approach to rapidly and efficiently discover
more 2D materials that possess properties suitable for solar water splitting.
Computational tools based on density-functional theory can predict the
intrinsic properties of potential photocatalyst such as their electronic
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properties, optical absorbance, and solubility in aqueous solutions. Computa-

tional tools enable the exploration of possible routes to enhance the photocatalytic activity of 2D materials by use of mechanical
strain, bias potential, doping, and pH. We discuss future research directions and needed method developments for the
computational design and optimization of 2D materials for photocatalysis.

S olar hydrogen production provides a potential solution to

the energy crisis caused by the depletion of fossil fuels and
the serious environment problems accompanying their
combustion.1−5 Production of hydrogen from photocatalytic
water splitting provides an alternative energy source, which
promises to be clean, environmentally friendly, low cost, and
renewable.

Production of hydrogen from

photocatalytic water splitting
provides an alternative energy
source, which promises to be
clean, environmentally friendly,
low cost, and renewable.
Since Fujishima and Honda1 discovered photocatalytic
splitting of water on TiO2 electrodes in 1972, over 130 semi-
conductor materials, including WO3, Bi2WO6, ZnO, Bi2O3, and
CdS, have been shown to function as photocatalyts for hydrogen
production (see Figure 1). 6−13 However, the practical
application of photocatalytic water splitting for hydrogen
production is limited by the inability to utilize visible light,
insufficient quantum efficiency, fast backward reaction, and poor
activation of catalysts, to name a few.14−17 Industrial reactors
have demonstrated solar-to-hydrogen conversion efficiencies
(the energy ratio of H2 produced by a reactor divided by the total
solar energy incident on the reactor) of 12%, with future
projections of 30%.18−20 Continuous search of remediation
methods has been ongoing to improve performance, increase
lifetime, and reduce costs to allow eventual large-scale
implementation. The use of sacrificial agents and dopants, of
composite semiconductors, and of morphological engineering
Figure 1. Schematic energy diagram and mechanism of photocatalytic
water splitting.
are just some of the numerous methods which have successfully
improved the efficiency of hydrogen production to current
levels.16,21,22 For instance, TiO2 nanotubes have solar-to-
hydrogen conversion efficiencies of up to 16%23 as opposed to
2.2%24 of bulk rutile TiO2.
Advantages of 2D Materials for Photocatalysis. The advent of
nanoscale materials with tunable shapes and dimensions presents
one of the most promising recent advancements in the field of
photocatalytic water splitting. Among various classes of nano-
materials, 2D materials stand out with two main intrinsic advan-
tages that can be utilized to enhance the photocatalytic efficiency
of water splitting. First, 2D materials maximize the surface area
per amount of material and, hence, exhibit a high specific surface
area available for photocatalytic reactions. Second, the 2D nature
Received: December 15, 2014
Accepted: February 26, 2015
Published: February 26, 2015

© 2015 American Chemical Society 1087 DOI: 10.1021/jz502646d

J. Phys. Chem. Lett. 2015, 6, 1087−1098
The Journal of Physical Chemistry Letters
2D materials stand out with two
main intrinsic advantages that
can be utilized to enhance the
photocatalytic efficiency of water
splitting.
of these materials minimizes the distance that photogene-
rated electrons and holes have to migrate before reaching the
solid/water interface, reducing the possibility of electron−hole
recombination and potentially enhancing the photocatalytic
performance.
Besides these intrinsic advantages, 2D materials present
a new class of materials that displays a wide range of electronic,
optical, and mechanical properties. Exploration of the space
of possible 2D materials will likely lead to new materials with
unexpected properties that can be useful for various
applications, including photocatalysis. Furthermore, a number
of 2D materials can be cleaved or exfoliated from bulk crystals
or synthesized by chemical vapor deposition or other thin-film
growth techniques, 25−29 which makes them attractive
candidates for investigations of their photocatalytic activity
for water splitting.
Several experimental studies have shown that the advantages
of 2D materials can indeed lead to an enhancement of the
photocatalytic activity compared to bulk materials. Recently, Xie
et al. synthesized freestanding single-layer SnS2, which generated
a high photocurrent density of 2.75 mA/cm2, over 70 times
higher than that of bulk SnS2 and an incident photon to
converted electron ratio (IPCE) of 38.7% at an irradiation
wavelength of 420 nm in contrast to only 2.33% for bulk SnS2.30
Another example is ZnSe with four atomic layers, which exhibits
a photocurrent density of 2.14 mA/cm2, about 200 times higher
than the value for bulk ZnSe and an IPCE of 42.5% compared to
0.25% of the bulk counterpart.31 Similar photocatalytic enhance-
ments through the reduction of the dimensionality have been
observed for other single and few-layer 2D materials such as SnO,
SnS, SnSe, CdS, and WS2.30,32−35
Key Goals of the Review Paper. In this paper, we review the
experimental, theoretical, and computational progress toward
the application of 2D materials as photocatalyst for water
splitting; for a general review of photocatalysis, cf. refs 1−5.
Although several 2D materials have already been identified as
suitable candidates for water splitting,30−35 the search for more
2D materials is ongoing. High-throughput computational
identification and screening of novel 2D materials for photo-
catalytic applications can help accelerate the scientific discovery
and technological advancement of materials design for photo-
catalysis.
This article emphasizes the role computational approaches
play in the discovery of 2D materials and the screening for
potential 2D photocatalyst to assist experimental efforts. We first
outline the desirable properties for a 2D material to be an
efficient photocatalyst for water splitting and suggest strategies
for enhancement of their photocatalytic activity. We then discuss
how density-functional calculations can establish their thermo-
dynamic and mechanical stability, determine their electronic
propertiesfor example, band gap, band edge positions, and
optical absorbanceand finally estimate their solubility in
aqueous solution. To enhance the photocatalytic activity, we
show how mechanical strain, pH, doping, and applied electrical
potential can be used to tune the relevant electronic properties of
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Perspective
these materials. Finally, we provide an outlook and discuss
possible future work for asserting and optimizing the photo-
catalytic activity of 2D materials.
Photocatalytic Water Splitting. One of the key properties for
photocatalytic water splitting is the electronic structure of the
photocatalyst, which controls the first steps of photocatalytic
water splitting. Incident light of sufficient energy excites an
electron across the optical band gap of the semiconducting
photocatalysts and generates an electron−hole pair. This exciton
then needs to diffuse to the solid/water interface and dissociate
into an unbound electron and hole. The excited electron then
drives the hydrogen reduction reaction generating hydrogen,
2H++ 2e− → H2, and the hole participates in the oxidation
reaction to generate oxygen, H2O + 2 h+ → 1/2 O2 + 2H+.
Required Properties of a Photocatalyst. For a 2D semiconductor
to facilitate photocatalytic water-splitting, at least four of the
following conditions must be satisfied:
1. Low formation energy. A low formation energy relative
to bulk material enables easy fabrication from their bulk
counterparts as well as extraction of suspended single-layer
flakes.
2. Sufficient band gap. The band gap must exceed the free
energy of water splitting of 1.23 eV and be smaller than
about 3 eV to enhance solar absorption.16
3. Band edges must straddle water redox potentials. The
conduction band minimum (CBm) energy is higher than
the reduction potential of H+/H2 and the valence band
maximum (VBM) energy is lower than the oxidation
potential of O2/H2O, that is, −4.44 and −5.67 eV,
respectively. All band edge energies in this article are
referenced with respect to the vacuum.16
4. Insoluble in water. The 2D semiconductor must be
insoluble in an aqueous solution.
In principle, any semiconductor that satisfies these
intrinsic materials requirements should display some
photocatalytic activity. However, there are several other
criteria the material must fulfill to become an efficient and
useful photocatalyst for practical applications:
5. Ability to utilize visible light. The material should capture
a significant fraction of the visible spectrum, as it accounts
for more than 40% of the solar energy compared to the
ultraviolet spectrum, which accounts for less than 5%.36
6. Small exciton binding energy. A small exciton binding
energy facilitates the splitting of excitons into free charge
carriers.
7. Low exciton recombination rate. Recombinations of the
photogenerated electron−hole pairs waste energy in the
form of heat or light.
8. Low rate of backward reaction. The backward reaction of
hydrogen and oxygen to produce water is an energetically
favorable process that should be kinetically suppressed.
Additionally, the reaction kinetics should be favorable for a
fast forward reaction.
9. Passivation of edges. The edges of the material must be
passivated to minimize reactions with ions in the solution.
10. Stable suspension in water. To take advantage of the large
surface area and short exciton diffusion length, the 2D
material must be dispersed in water and resistant to
agglomeration.
11. High corrosion resistance. The material should be inert
to the various ions and other chemical species generated
during the water splitting process.
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12. Cost efficient. The use of low cost materials and
processing will make solar hydrogen production more
competitive.
13. Environment friendly. Abundant and environmentally
friendly materials are necessary for sustainable energy
production.
High-throughput computational
identification and screening of
novel 2D materials for photo-
catalytic applications can help
accelerate the scientific discovery
and technological advancement
of materials design for photo-
catalysis.
Figure 2 illustrates the screening process of 2D materials to be
suitable for photocatalytic water splitting. The four key intrinsic
Figure 2. Discovery and design of 2D materials for photocatalytic water
splitting can be accelerated by computational prescreening for suitable
materials prior to their experimental fabrication, characterization, and
testing. Computational methods allow prescreening for 2D materials by
accurately and rapidly identifying 2D materials that are thermodynami-
cally stable, insoluble in water, exhibit a band gap larger than 1.23 eV,
and display band edges that straddle the redox potentials of water.
materials properties, the first four criterialow formation
energy, sufficient band gap, appropriate band edge positions,
and low solubility in watercan be accurately and efficiently
computed using density functional theory (DFT). Among the
remaining listed criteria, criteria 5 and 6 can be computed
accurately using higher order computational techniques but are
computationally expensive. The most challenging criteria to
assess are 7, 8, 10, and 11, and the remainder can be determined
trivially using databases and handbooks. In the following, each
criteria is addressed in further detail.
Thermodynamic Stability. The most fundamental property of any
material is its thermodynamic stability and the search for efficient
photocatalytic materials must start from an analysis of the
materials’ stability. 2D materials are always metastable and not
true thermodynamic ground states, as the omnipresent
dispersion interaction always lowers the energy when two layers
are brought together. Hence, even in the absence of other
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Perspective
competing 3D phases, the dispersion energy would stabilize a
bulk layered compound over individual layers. Nevertheless, 2D
materials can be either kinetically stable by themselves, for
example, free-standing graphene,46 BN,47 or MoS2,48 or can be
stabilized by the presence of solvents, adsorbates, or substrates,
for example, AlN, GaN, 2D silica glass, and silicene.49−52
The thermodynamic stability of a 2D material is simply given
by the difference in free energy of the 2D material and the lowest
value for any mixture of bulk materials that has the same
composition as the 2D material. The free energy can be approxi-
mated by the energy of the system and the thermodynamic
stability by the formation energy
E2D E
ΔEf = − 3D
N2D N3D (1)
where E2D and E3D are the energies of the single-layer and bulk
(or mixture of bulk) materials, respectively, and N2D and N3D
denote the numbers of atoms in the respective unit cells.
Figure 3 illustrates the formation energy of several experi-
mentally synthesized (blue bars) and experimentally unsynthe-
sized but theoretically predicted 2D materials (red bars). To be a
feasible photocatalyst, the 2D materials should be stable in an
aqueous solution and, thus, stable as free-standing or suspended
nanosheets. 2D materials with weak van-der-Waals-bonded
layered bulk counterparts generally have low formation energies,
within 200 meV/atom,38,39,41,43,53 and, thus, have been extracted
as free-standing or suspended single-layer flakes. Some examples
are graphene,54 GaSe,55 MoS2,56 SnS2,33 MoSe2,57 WSe2,57,58
BN,57,59 NbTe2,57 and SnSe.33
In contrast, 2D materials with formation energies exceeding
about 200 meV/atom, such as silicene,38 2D oxides,44 and 2D
group III−V materials,45 are unlikely to be synthesized unless a
suitable stabilizing substrate can be found.50,53 It is furthermore
unlikely to achieve freestanding flakes or suspended flakes of 2D
materials with high formation energies.43,50,53,60 Figure 3 shows
that only a few of the high formation energy materials, shaded
yellow region, have been synthesized on substrates, for example,
ZnO,61 silicene,62 and AlN,49 and additionally have not been
extracted in a free-standing or suspended state.
Electronic Structure. The screening of a 2D material for its
potential as a photocatalyst requires the prediction of its
electronic properties, specifically of the band gap and band
edge positions. The most popular method for electronic
structure calculations is density functional theory (DFT),
which can provide an excellent balance between accuracy and
computational cost.64 The accuracy of DFT depends on the
approximation for the exchange-correlation functional. Band
gaps from local and semilocal approximations to the exchange-
correlation functional, such as the LDA and PBE functionals,65
underestimate the fundamental band gap because of the lack of
derivative discontinuity of the functional with respect to the
number of electrons and no clear physical meaning of the
unoccupied orbitals.65
One of the most effective ways to circumvent this band gap
problem of DFT is the use of computationally more expensive
hybrid functionals such as Heyd−Scuseria−Ernzerhof
(HSE)66,67 and PBE0,68 which incorporate a fraction of exact
exchange and generally provide better agreement with
experimental band gaps. Another powerful technique is that of
many-body perturbation theory such as the GW quasiparticle
approximation.69 The GW approximation is a theoretically
justified approach to calculate the quasiparticle band structure
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The Journal of Physical Chemistry Letters
Figure 3. Formation energies of some experimentally synthesized (blue bars) and theoretically predicted but experimentally unsynthesized 2D materials
(red bars) are shown in this figure. The materials in the yellow shaded region, with ΔEf > 0.2 eV/atom, have only been extracted as single-layer or few-layer
nanosheets on suitable substrates and are yet to be obtained in a free-standing or suspended form. Formation energies of graphene computed using
quantum Monte Carlo simulations;37 BN38 and silicene38 were using the LDA exchange correlation functional; GaSe,39 CrS2,40 MoS2,41 MoSe2,41 WSe2,41
NbTe2,41 SnS2,42 SnS,43 and PbO43 using a van der Waals functional; CdO,44 CaO,44 ZnO,44 GaSb,45 InAs,45 GaN,45 and AlN45 using a GGA functional.
including electron−electron interactions. The GW approxima-
tion provides excellent results for the band gaps of 3D
materials;70,71 for 2D materials the limited amount of experi-
mental data of fundamental gaps has hampered comparisons.
Hybrid functionals and the GW method predict the funda-
mental band gap and to determine the optical band gap of a
2D material, excitonic effects must be included. Most 3D semi-
conductors exhibit very small exciton binding energies, and
therefore, the distinction between optical and electronic band
gaps is frequently ignored. However, in 2D materials and some
organic semiconductors, the difference can be significant. In
these materials, the high exciton binding energy is due to the
reduced Coulomb screening. The Bethe−Salpeter equation
(BSE) can be used to estimate the optical band gap and exciton
binding energies. For instance, an optical band gap for MoS2 of
1.84 eV is obtained if the GW electronic band gap of 2.8 eV is
corrected by the BSE exciton binding energy of 0.96 eV,72−74
which is in good agreement with the experimentally observed
optical band gap of 1.9 eV.48
The four key intrinsic materials
properties, the first four criteria
low formation energy, sufficient
band gap, appropriate band edge
positions, and low solubility in
watercan be accurately and
efficiently computed using den-
sity functional theory.
The intrinsic band-edge positions of 2D materials can be
obtained by DFT methods through alignment of the electrostatic
potential in the vacuum region.39 However, similar to the band
gap energies, the band alignments heavily depend on the
exchange-correlation functional. Hybrid functionals generally
provide an improved accuracy over semilocal functionals. The
DFT band-edge positions, ECBm/VBMDFT, can be corrected with
the quasiparticle GW energy contributions, δECBm/VBM, to
provide more accurate exchange-correlation functional inde-
pendent band-edge positions75−78
QP DFT
ECBm/VBM = ECBm/VBM + δECBm/VBM
Perspective
Aqueous Solution Stability. 2D materials that satisfy the band gap
and band-edge position requirements can be used in practice
only if they are stable in aqueous solutions. Although materials
already synthesized can straightforwardly be tested for this in the
laboratory, as yet, hypothetical materials’ stability in aqueous
solution, or in other words, their solubility in water, can be com-
puted using the approach of Zhuang et al.39,41 They compute the
enthalpy of solvation of relevant 2D materials and use the fact
that the solubility of any material decreases exponentially with
increasing enthalpy of solvation. The comparison of the enthalpy
of solvation to that of any poorly soluble materials, such as HgS
with a solubility of 1.27 × 10−27 mol/100 g of water, provides an
indication of their solubility.
When a solid compound AB(s) dissolves in water, the
equilibrium concentrations of the dissolved ions is established by
the solvation reaction
A nBm(s) ⇌ n Ap +(aq) + mBq −(aq) (3)
p+ q−
Here, A (aq) and B (aq) represent A and B ions in an aqueous
solution, respectively. Charge balance requires that np = mq. The
solubility product, Ksp, of this solvation reaction is given by the
Gibbs energy of solvation, ΔGsolv, or the enthalpy of solvation,
ΔHsolv, if the entropy of solvation is assumed to be small.
The enthalpy of solvation, ΔHsolv, can be computed efficiently
by decomposing the reaction 3 into two steps. First, the solid
compound is separated into isolated atoms in the gas phase, A(g)
and B(g)
A nBm(s) ⇌ n A(g) + mB(g) (4)
The enthalpy change of reaction 4, that is, the cohesive energy of
the AB compound, ΔEcoh, can be calculated efficiently using any
solid state DFT code.
In the subsequent second reaction
n A(g) + m B(g) ⇌ n Ap +(aq) + m Bq −(aq) (5)
the gas atoms are ionized and solvated in water. To calculate the
enthalpy of hydration, ΔHhyd, for this reaction, the energy of the
isolated atoms and of the hydrated ions can be efficiently
computed using the quantum chemistry codes for molecular and
atomic species such as Gaussian09.79 Here, it is important to
converge the hydration energy with respect to the number of
explicit water molecules used to augment an implicit solvation
model for the description of solvation in water.80 Furthermore,
(2) the charges of the dissolved species, p+ and q−, are given by the
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Figure 4. Band-edge positions of 2D materials compared to redox potentials of water, (a) group-III monochalcogenides, adapted with permission from
ref 39, copyright 2013 American Chemical Society, (b) transition-metal dichalcogenides, adapted with permission from ref 41, copyright 2013 American
Chemical Society, and (c) metal phosphide trichalcogenides relative to the vacuum level, reprinted with permission from ref 63, copyright 2014, AIP
Publishing LLC.

values that minimize the enthalpy of hydration, ΔHhyd. In a

similar manner, one can take into account the energy for ion
association, that is, a solvated cation−anion pair. A more rigorous
treatment of solvation is possible by replacing the implicit
solvation model80,81 with ab initio molecular dynamics
simulations that can capture dynamic solvent effects.82
Finally, the enthalpy of solvation, ΔHsolv, is given by the sum of
ΔEcoh and ΔHhyd. Using this approach, Zhuang et al. have shown
that single-layer GaS, GaSe, GaTe, InS, InSe, InTe, MoS2, WS2,
PtS2, and PtSe2 are suitable for photocatalytic water splitting as
they not only satisfy the band gap energy and band-edge position
requirements shown in Figure 4a and b but are also insoluble in
water as shown in Figure 5.39,41
Optical Absorption. The efficiency of photocatalytic water
splitting materials is dependent on their ability to capture a
significant fraction of sunlight. It is preferable to capture the
visible part of the spectrum as it accounts for more than 40% of
the solar energy; in comparison, the ultraviolet part of the
Figure 5. Solvation enthalpy of single-layer metal chalcogenides and
spectrum accounts for less than 5%.36 The optical absorption
dichalcogenides in water. Predicted enthalpy of solvation, ΔHsolv, (a) for
function is given by the imaginary part of the dielectric function transition metal dichalcogenides in comparison with HgS, adapted with
and can be computed using DFT or the GW approximation. permission from ref 41, copyright 2013 American Chemical Society, and
However, to obtain an accurate dielectric function and optical (b) for the single-layer monochalcogenides, adapted with permission
absorption spectrum, one has to include excitonic effects and from ref 39, copyright 2013 American Chemical Society. The high
solve the BSE. As input to the BSE, the quasiparticle energies are solvation enthalpies indicate that the single-layer monochalcogenides
usually obtained from GW calculations and the wave functions are insoluble in water.
from standard DFT.83,84 A large optical absorption for a
candidate 2D material indicates that it could exhibit a high below 3.2 eV of the BSE spectrum. The first peak at an energy of
efficiency for photocatalytic water splitting. 2.75 eV corresponds to the direct optical band gap of SnS2 and
The optical absorption spectrum of 2D materials, such as agrees well with the experimental optical gap of 2.55 eV
SnS242 and MoS2,73,85 are dominated by excitonic states that are measured by UV−visible transmission spectroscopy.86 Further,
well described by the BSE. The BSE spectrum provides a good the second peak at 2.92 eV is due to another exciton, and finally,
approximation for the exciton energies and the optical band gap the third peak corresponds to the direct quasiparticle band gap of
of 2D materials. For example, Figure 6 shows the imaginary part 3.16 eV obtained with the G0W0 method. The exciton binding
of the permittivity for SnS2 calculated from the BSE and the energy of SnS2 is the energy difference between the first and third
random phase approximation (RPA), respectively. In contrast peak. The BSE value of 0.41 eV is close to the value for bulk SnS2
with the RPA, which lacks a description of electron−hole pairs, of 0.4 eV,87 and also is comparable to the exciton binding energy
three absorption peaks are observed in the low-energy region of single-layer MoS2, 0.96 eV,74 and WS2, 0.6 eV.73
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Figure 6. Imaginary part of the permittivity of single-layer SnS2
calculated with the BSE and RPA scheme. The inset shows a closeup
of the first three BSE peaks. To compensate for the band gap
underestimation using the PBE functional in the RPA calculation, we
shift the spectra by 1.0 eV, which is the difference between the HSE06
and PBE band gaps. Reprinted figure with permission from ref 42.
Copyright 2013 by the American Physical Society.
Future Computational Screening. Modeling of exciton diffusion
and recombination, kinetics of electron transfer reactions, charge
trapping, and corrosion of 2D materials in electrolytes can be
pursued in the future to understand the fundamental processes
that control stability and efficiency of 2D photocatalyst and to
identify better materials for photocatalysis.
Exciton Dynamics and Electron Transfer Reactions. The theoretical
description of photoinduced electron dynamics is a challenging
task, as it requires in principle the solution of the time-dependent
Schrödinger equation for the many-body system, which has so
far only been achieved for small molecules.88,89 Nonetheless, this
nonadiabatic problem can be investigated by mean-field classical
molecular dynamics,90−92 using the so-called Ehrenfest dynam-
ics93−96 for the nuclei, which is self-consistently coupled with
time-dependent DFT for the description of the electronic
degrees of freedom. Such an approach has been employed
previously to study electron transfer, relaxation dynamics,
multiple exciton generation, electron−phonon coupling, wet
electron systems, and so forth. For a detailed description of this
approach, a discussion of its capabilities and limitations, and of
various applications, see refs 90−93, 97, 98, and references
within. For solar energy conversion applications, such a tech-
nique allows to estimate relaxation times and employ them as a
Figure 7. Illustration of stability of SnO in water. (a) Pourbaix diagram showing the range of stability for the bulk phases Sn, SnO, and SnO2. (b) Stability
of 2D SnO in water against dissolved species.
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Perspective
means to identify materials that increase electron−hole re-
combination times. Such a modeling is feasible and should be
performed for 2D materials to study the effect of dimensionality
on exciton dynamics. However, the high computational expense
of this approach currently makes it impractical for high-
throughput screening of materials.
Corrosion and Pourbaix Diagrams. The immersion of 2D materials
in an aqueous solution can lead to dissolution of atoms, surface
damages, formation of secondary phases like oxides, nitrates,
hydroxides, and so forth. Such corrosive chemical reactions can be
studied using Pourbaix diagrams, which represent aqueous phase
electrochemical equilibria.99 Pourbaix diagrams graphically
illustrate the stability boundaries for dominant solution or pre-
cipitate species as a function of pH and applied electrical potential.
They are particularly useful for defining the conditions for selective
precipitation and for passivation of materials.
To calculate a Pourbaix diagram requires not only the free
energies of the solid phases and of the solvated ions but also a
knowledge of all competing solid phases and solvated species that
the chemical components and solvent can form. The
determination of all possible phases and solvated species and
the calculation of their free energies is a difficult and time-
consuming task. A few software packages are available, such as
Thermo-Calc and the Material Project Pourbaix App,100,101 that
compute Pourbaix diagrams from available experimental and
computational data. These tools can be applied to estimate the
electrochemical stability of 2D materials by adjusting the free
energy of the bulk material to that of the 2D counterpart using
the formation energy, ΔEf , given in eq 1.
Figure 7a shows the calculated Pourbaix diagram of Sn and the
stability range for the bulk phases of Sn and its two oxides, SnO
and SnO2 relative to the dissolved species. The Pourbaix diagram
is calculated from the combination of the experimental Gibbs
energies of the dissolved ionic species with the calculated
formation energies of the bulk phases by adjusting the chemical
potential of Sn such that the calculated energy of SnO matches
the experimental Gibbs energy.101,102 Figure 7b shows the
stability of the 2D SnO relative to the dissolved species by
removing the bulk phases from the analysis. The results show
that 2D SnO is stable against corrosion in water for a range of
pH values from 6 to 8 at negative potentials. Such stability
analysis can provide useful information about the intrinsic
corrosion stability of 2D materials.
Pourbaix diagrams provide a useful and intuitive way to predict
the equilibrium stability of systems in solutions as a function of
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pH and the applied electrical potential. However, it is important
to note that several effects that are not included in the Pourbaix
diagram can strongly affect a materials’ stability and solubility in a
realistic electrolyte environment. First, other species that are
present in the aqueous solution can adsorb on materials surfaces,
modify passivation layers, associate with dissolved ions, and so
forth, which affects the Gibbs free energies and stability. For
example, ligands can change the stability of nanocrystal surfaces
and certain species such as chloride ions can destroy passivating
layers.103,104 The presence of multiple ions, ligands, and solvent
molecules makes it challenging to determine the lowest energy
configurations. To overcome this complexity, combinations of
simplified interaction models, for example, electrostatic or
empirical energy models,105,106 and structure search algorithms,
for example, genetic algorithms, particle-swarm optimization,
minima-hopping, and so forth,107−110 have the potential to
quickly screen configurations and identify low-energy candidates.
Furthermore, kinetic effects that are not accounted for in
Pourbaix diagrams can in practice prevent certain reactions and
stabilize species that are shown as unstable. The reaction
overpotential, the additional potential above the equilibrium
potential required for a reaction to occur, depends significantly
on the choice of the solvent and its composition.111 Photo-
generated holes and electrons on the surfaces could also induce
formation of reactive intermediates on the surface. The stability
of such species and the amount of photocurrent generated
depend on the type and the quantity of chemical species present
in the solution that could react with the reactive species on the
surface.112
To determine what species are present in the solution and to
understand how local variations of the interface potential affect
the presence of a particular species, it is important to consider the
interactions between the interface and the solution and its
constituents simultaneously. Implicit solvation models can
provide an efficient description of the effects of solvent on
surfaces, adsorption energies, and reaction energy barriers. A
first-principles computational treatment of the effect of photo-
generated holes and electrons on the stability of adsorbed species
and reactions on surfaces requires the study of charged systems in
the presence of solvents. Study of charged 2D slabs is
problematic in a typical DFT framework due to the usage of
periodic boundary conditions and the lack of a proper
electrostatic reference potential in such a periodic array of
charges.113,114 One way to address the problem is to couple the
DFT calculations to an implicit solvation model that is based on
the Poisson−Boltzmann equation. The solution of the Poisson−
Boltzmann equation provide a unique reference for the
electrostatic potential even in charged systems due to the
shielding provided by the ions in the solution.115 Though it is an
implicit approach to treat the solution effects, most of the surface
chemistry can be captured by introducing one or two layers of
explicit solvent molecules and adsorbants on the surface and
filling the rest with the implicit solvent.
In general, a comprehensive and realistic treatment of complex
interface phenomena that occur in 2D photocatalytic systems
requires that configurational, kinetic, and environmental effects
are properly accounted for. To that end, it is important to extend
computational methods for structure prediction107−110 to 2D
materials, surfaces, and adsorbates and to complement the
computational schemes with the emerging efficient techniques to
describe solvation effects.81,116,117
Enhancement of Photocatalytic Activity. Engineering of the band
gap, band edges, and optical spectra of materials has been
1093
Perspective
demonstrated by application of external sources such as
mechanical strain, application of chemical, and electrical bias
and doping.39,41,118 Computational tools such as DFT and GW
calculations can efficiently identify which of these strategies best
tune the band gap, band edges, and absorbency of a promising
2D material for photocatalysis.
Strain. One of the methods of adjusting the band gap and band-
edge positions of a semiconductor is the application of mechani-
cal strain. Figure 8 shows that application of 5% compressive
Figure 8. Band edge positions of single-layer α-TiNBr at strains of 0%
and 5%, as well as pure and 12.5% Ti-doped single-layer α-MNI (M =
Zr, Hf). The energy scale is indicated by the vacuum level (left Y-axis) in
electron volts as a reference. The CBm (blue color) and VBM (red
color) are presented along with the potentials in electronvolts. The
redox potentials (magenta dashed line) of water splitting are shown for
comparison. Adapted from ref 118 with permission from The Royal
Society of Chemistry.
strain to single-layer α-TiNBr shifts the CBm above the H+/H2
energy, rendering it useful in spontaneous photocatalytic water
splitting. Surprisingly, the majority of 2D materials have
significantly softer elastic constants in comparison to their bulk
3D counterpart, which assists application of strains without
inducing breakage of materials.53 Notably, small strains can shift
band edge positions and band gaps by a significant amount.38,39,42
Experimentally controlled tensile and compressive uniaxial
strains of up to 2.2% have been imparted to single-layer or few-
layer flakes of graphene and MoS2 by bending of flakes deposited
(or suspended) on flexible substrates.119−122 Recently, Shioya
et al.123 demonstrated that two different techniques, recrystalliza-
tion of metal contacts and condensation polymerization of
organic films, can be used to impart biaxial and in-plane isotropic
compressive strains to graphene in a controlled manner. Neither
of these techniques require bending of substrates and can be
applied to other 2D materials to achieve controlled strains of
as much as 10%. Under experimental conditions the presence of
unintended strains, impurities, and defects can cause similar
effects; thus, it is advisible to investigate photocatalytic activity
for a range of bias voltages.
Chemical Bias. Modifications of the electrolyte such as changing
the pH can tune the reduction and oxidation potentials of water.
This is known as chemical biasing.22,124 Each unit of pH dif-
ference between two electrolytes provides a chemical bias of the
water redox potentials of 59 meV;125 the pH dependent reduc-
tion potential of water is EredH+/H2 = −4.44 eV+ pH·0.059 eV and the
oxidation potential is EOoxd2/H2O = −5.67 eV+ pH·0.059 eV. Adjusting
the pH of the solution can tune the alignment of the energy levels
between the 2D material and the solvent to optimize the system
for photocatalysis. For example, increasing the pH shifts both
DOI: 10.1021/jz502646d
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The Journal of Physical Chemistry Letters
energy levels of H+/H2 and O2/H2O potentials upward, as
illustrated in Figure 4b, making MoSe2 and WSe2 possible
photocatalysts. However, care must be taken before exploring this
avenue because the hydroxyl groups attached on the semi-
conductor surface can lead to the modification of their band edges
and band gaps counteracting the increase of the voltage with pH.4
The use of chemical additives is another promising approach
to tune the band-edge positions of 2D materials at a fixed
electrolyte pH. Adsorbed species affect the electronic structure of
the surface, for example, band edges, band gap, density of states,
and so forth. For instance, chemical functionalization of GaAs
with positively charged porphyrins leads to a shift in GaAs band-
edge positions.126 Moreover, chemical additives can potentially
enhance the photocatalytic activity of semiconductor photo-
catalysts by inhibiting charge recombinations, by improving the
photoresponse to visible light through formation of impurity
energy levels, and by suppression of backward reactions.16
Reference 16 elaborates the detailed mechanism, advantages, and
limitations of using chemical additives for enhancing the
photocatalytic activity of TiO2.
Electrical Bias. Misaligned band edges (where one or both of the
band edges do not straddle the redox potentials of water)
necessitate an external applied bias. Although biasing works well,
it can have many drawbacks. For instance, an electrical bias
potential decreases the efficiency for water splitting.4 If a part of
the output of water splitting is assumed to provide energy to an
external power source for electrical biasing, the water splitting
efficiency, η, of the photocatalyst can be defined as
j(1.23V − Vbias)
η=
Plight (6)
where Vbias is the applied bias potential, j the measured current
density, Plight the power density from the light source, and 1.23 V
is the free energy of water splitting. This shows that the bias
potential must be significantly smaller than 1.23 V in order for
the photocatalysts to exhibit a significant positive energy output.
Single-layer SnS2 is an example for a 2D material requiring a
bias potential. Photocatalytic water splitting was achieved for this
material in a 0.5 M Na2SO4 electrolyte (equivalent to pH = 6.6)
at an applied bias of −1 V.30 In agreement, HSE06 calculations
show that indeed, while the VBM energy, −7.42 eV, of SnS2 is
well below that of the oxidation potential of water, EOoxd2/H2O,pH=6.6 =
−5.28 eV, the CBm energy, −4.90 eV, of SnS2 is below that
reduction potential of water, EHred2+ /H2,pH=6.6 = − 4.05 eV.42 In
agreement with experimental results, an additional bias potential
of 0.9 V is required to shift the CBm above the reduction
potential of water, thus making it photocatalytically active for
water splitting.
Predicted 2D Photocatalysts. On the basis of computational studies
investigating the band gap and band edge criterion, scores of 2D
materials have been predicted to be capable of spontaneous water
splitting. Figure 4 illustrates the band edge alignment for several
families of 2D materials. Figure 4a shows the prediction by
Zhuang et al. that the single layer group-III monochalcogenides,
GaS, GaSe, GaTe, InS, InSe, and InTe are suitable candidates for
spontaneous photocatalytic water splitting.118
Another class of 2D materials that has received a lot of
attention for its potential in photocatalysis are the transition-
metal dichalcogenides.40,41,127−131 Figure 4b, illustrates that the
band edge positions of the single-layer transition-metal
dichalcogenides CrS2, MoS2, WS2, PtS2, and PtSe2 make them
suitable for photocatalytic splitting of water.40,41 Further, studies
1094
Perspective
on the electronic structure of vacancies and edges of MoS2 show
that these defects can provide catalytically active sites.128−130
Recently, Liu et al. predicted that single-layer metal−
phosphorus-trichalcogenides, MPX3 (M = Zn, Mg, Ag0.5Sc0.5,
Ag0.5In0.5 and X = S, Se) exhibit the intrinsic electronic properties
suitable for spontaneous photocatalytic water splitting, see
Figure 4c.63 Single layer α-MNX (M = Zr, Hf; X = Cl,Br,I) and
β-MNX (M = Zr, Hf; X = Cl, Br) have been shown to be yet
another class of 2D materials suitable for photocatalytic water
splitting.118 Furthermore, single-layer bismuth oxyhalides
including BiOCl, BiOBr, and BiOI are suggested to exhibit
photocatalytic activity for water splitting.132
Another 2D material, 2D oxosulfide, (N2H4)2Mn3Sb4S8(μ3−
OH)2, is predicted to result in continuous hydrogen evolution
under visible-light irradiation.133 Also, CdS nanosheets with
thickness of about 4 nm exhibit efficient photocatalytic activity
with hydrogen production rate of 41.4 mmol h−1 g−1, about six
times higher than CdS nanosheet based aggregates. However,
they have a small IPCE of 1.38% which was improved to 9.62%
by loading with PdS.34
Finally, the 2D group-IV monochalcogenides, MX (M = Ge,
Sn, Pb; X = O, S, Se, Te), have been predicted to be suitable for
photocatalytic water splitting but require a bias potential.43 In
agreement with these results, Liang et al. have experimentally
demonstrated that 7 atomic layer thick SnO sheets display
photocatalytic water splitting under bias potentials of −0.2 to
−1 V.35 In their work, they also elucidate the effect of layer
thickness on the IPCE where 7 atomic layer, 12 atomic layer,
and bulk SnO sheets displayed IPCE of 20.1%, 10.7%, and 4.2%,
respectively.
Summary and Future Outlook. We described a computational
strategy to predict and explore 2D materials for photocatalytic
water splitting. We suggest possible techniques for their catalytic
activity enhancement. The high-throughput computational
screening of materials is a powerful tool to rapidly predict
promising candidates and eliminate unlikely materials candi-
dates, allowing for more efficient use of experimental resources
and accelerating possible applications of 2D photocatalysts.
Current ab initio methods, such as density functional theory and
the GW approximation, combine the accuracy to reduce false
positive and negatives with the speed required for a high-
throughput approach. This strategy can be applied to many more
2D materials and a repository or database from these predictions
will accelerate the innovation of photocatalytic water splitting
materials.
We see the future challenges for the computational screening
of materials for photocatalytic applications mostly in the area of
the description of solvation and kinetics. The active development
of implicit solvation models and their implementation into
widely used software packages is expected to lead to an efficient
description of the effect of the electrolyte on electronic
properties and stability, including corrosion. A challenge for
solvation models and computational studies of corrosion is to
overcome the complexity of the interaction and chemical
reactions between solvated species and the 2D materials. With
regards to kinetics, computational methods that describe
nonadiabatic dynamics and can assess the rate of electron
transfer reactions and exciton dynamics are still being developed
and not yet routinely applied or available in community codes.
The enormous progress in the fields of 2D materials and
computational methods suggests that many of those challenges
will be tackled in the near future.
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J. Phys. Chem. Lett. 2015, 6, 1087−1098
The Journal of Physical Chemistry Letters
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: rhennig@ufl.edu.
Present Address
∥
(A.K.S.) Material Measurement Laboratory, National Institute
of Standards and Technology, Gaithersburg, Maryland 20899,
United States.
§ Nanostructures: Controllable Synthesis, Growth Mechanism, and Their
(H.L.Z.) Center for Nanophase Materials Sciences, Oak Ridge
National Laboratory, Bethel Valley Road, Oak Ridge, Tennessee
37831, United States.
Notes
The authors declare no competing financial interest.
Biographies
Arunima K. Singh is a postdoctoral researcher at the National Institute
of Standards and Technology. She received her Ph.D. in Materials
Science and Engineering in 2014 from Cornell University under the
supervision of Richard G. Hennig. Her research focuses on accelerating
2D materials discovery, synthesis and application using first-principles
computation.
Kiran Mathew is a Ph.D. student at Cornell University. His research
focuses on multiscale modelling and the development of solvation
models.
Houlong L. Zhuang is a postdoctoral researcher at Oak Ridge National
Laboratory. He received his Ph.D. in Materials Science and Engineering
in 2014 from Cornell University under the supervision of Richard G.
Hennig. His research focuses on computational discovery and design of
novel 2D materials for energy applications.
Richard G. Hennig received his Diploma in Physics at the University of
Göttingen in 1997 and his Ph.D. in Physics from Washington University
in St. Louis in 2000. After working as a postdoctoral researcher and
research scientist at Ohio State University, he joined the faculty of the
Department of Materials Science and Engineering at Cornell University
in 2006 as an Assistant Professor. In 2014, he moved to the University of
Florida as an Associate Professor.
■
ACKNOWLEDGMENTS
This work was supported by the NSF through the Cornell Center
for Materials Research under Award No. DMR-1120296 and the
CAREER award No. DMR-1056587. This research used
computational resources of the Texas Advanced Computing
Center under Contract No. TG-DMR050028N.
■
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1098 DOI: 10.1021/jz502646d

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