Letter

Cite This: Nano Lett. 2018, 18, 6312−6317 pubs.acs.org/NanoLett

Intrinsic Electric Fields in Two-dimensional Materials Boost the

Solar-to-Hydrogen Efficiency for Photocatalytic Water Splitting
Cen-Feng Fu, Jiuyu Sun, Qiquan Luo, Xingxing Li, Wei Hu, and Jinlong Yang*
Hefei National Laboratory of Physical Science at the Microscale, Department of Chemical Physics, Synergetic Innovation Center of
Quantum Information & Quantum Physics, University of Science and Technology of China, Anhui 230026, China
*
S Supporting Information

ABSTRACT: Two-dimensional (2D) materials with the

See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

vertical intrinsic electric fields show great promise in inhibiting

the recombination of photogenerated carriers and widening light
absorption region for the photocatalytic applications. For the
first time, we investigated the potential feasibility of the
experimentally attainable 2D M2X3 (M = Al, Ga, In; X = S,
Downloaded via TU DELFT on May 23, 2023 at 10:48:29 (UTC).

Se, Te) family featuring out-of-plane ferroelectricity used in

photocatalytic water splitting. By using first-principles calcu-
lations, all the nine members of 2D M2X3 are verified to be
available photocatalysts for overall water splitting. The predicted
solar-to-hydrogen efficiency of Al2Te3, Ga2Se3, Ga2Te3, In2S3,
In2Se3, and In2Te3 are larger than 10%. Excitingly, In2Te3 is
manifested to be an infrared-light driven photocatalyst, and its
solar-to-hydrogen efficiency limit using the full solar spectrum even reaches up to 32.1%, which breaks the conventional
theoretical efficiency limit.
KEYWORDS: Solar-to-hydrogen efficiency, intrinsic electric field, two-dimensional materials, photocatalytic water splitting,
first-principles calculations

D eveloping clean and renewable hydrogen energy

resources is of particular importance to address great
challenges from worldwide energy and environment crises in
the contemporary era. For economical production of hydrogen
from photocatalytic water splitting, the solar-to-hydrogen
(STH) efficiency is required to be at least above 10%.1 In
theory, the photocatalysts available for water splitting must
possess a band gap of equal or larger than 1.23 eV, originating
from the difference between the redox potentials of H+/H2 and
H2O/O2. Assuming both light absorbance and quantum
efficiency can attain 100%, thus the theoretical limit of the
STH efficiency using the full solar spectrum is calculated to be
∼47%.2 In fact, the energy loss during the electron-transfer
process is not avoided, and the kinetic overpotentials are
demanded to drive the catalytic reactions. The authentic
energy required for photocatalytic water splitting is commonly
greater than 2.0 eV,3 and the corresponding theoretical STH
efficiency limit is decreased to ∼18%. In general, the
photocatalytic water splitting process is composed of three
pivotal steps: light harvesting, carrier separation and trans-
portation, and hydrogen evolution reaction (HER) as well as
oxygen evolution reaction (OER). Great efforts are devoted to
improving the efficiencies of these three steps.4−10 Albeit these
strategies are demonstrated to be effective in improving the
extremely low STH efficiency case, the experimentally reported
STH efficiency for photocatalytic water splitting is still hard to
exceed 10% so far.11−14 The STH efficiency is determined by
the product of the efficiencies of all three steps. Thus, the
successful enhancement of energy conversion efficiency calls
for the simultaneous improvement for the three steps of
photocatalytic water splitting.
A new mechanism for photocatalytic water splitting
originally proposed by our group reveals that the vertical
intrinsic electric field (EF) in the two-dimensional (2D)
material not only accelerates the carrier separation but also
breaks the conventional limitation of 1.23 eV for band gap of
photocatalysts, leading to enlarged light absorption, even to the
infrared region.15 Referring to this new mechanism, some 2D
materials with vertical EF have been theoretically proved to be
potential photocatalysts for water splitting, such as germanium
monochalcogenide,16 Sc2CO2,17 and Janus transition metal
dichalcogenides monolayers.18,19 However, the experimental
synthesis of these 2D materials is difficult to be achieved, and
the energy conversion efficiency, an ultimate index for
evaluating photocatalytic water splitting, has never been
explored on these 2D photocatalysts with intrinsic EF.
Recently, the theoretical computation predicted that 2D
M2X3 (M = Al, Ga, In; X = S, Se, Te) possess out-of-plane
ferroelectricity.20 Moreover, some members of 2D M2X3
groups have been successfully synthesized in experiment.21−24
Received: June 24, 2018
Revised: September 18, 2018
Published: September 21, 2018

© 2018 American Chemical Society 6312 DOI: 10.1021/acs.nanolett.8b02561

Nano Lett. 2018, 18, 6312−6317
Nano Letters Letter

In this work, the 2D M2X3 is investigated as potential parameters and total heights of M2X3 monolayers (listed in
photocatalyst for water splitting, by using first-principles Table S1) agree well with previous reports.20 The band
calculations. On the basis of the typical water splitting structures of all the nine 2D M2X3 predicted by HSE hybrid
photocatalysts criterion taking only one vacuum level into functional indicate that they are semiconductors with indirect
considerations, nearly all of these materials are not suitable for band gaps (Figure 2). The corresponding locations of the
photocatalytic overall water splitting. However, under the new valence band maximum (VBM) and the conduction band
mechanism, all nine members of the M2X3 family are proved to minimum (CBM) are illustrated in Figure 2. The direct and
be promising photocatalysts for overall water splitting. The indirect band gaps of these materials can be found in Table 1.
theoretical STH efficiencies of Al2Te3, Ga2Se3, Ga2Te3, In2S3, Interestingly, the band gaps tend to decrease, when the X
In2Se3, and In2Te3 are larger than 10%. Excitingly, In2Te3 is component varies from S to Te.
demonstrated to be an infrared-light driven photocatalyst for
overall water splitting, and the predicted STH efficiency using Table 1. Calculated Indirect HSE Band Gaps Egi(HSE),
the full solar spectrum can reach 32.1%, which breaks the Direct HSE Band Gaps Egd(HSE), the Differences between
theoretical limit of ∼18% for photocatalytic water splitting for the Vacuum Levels at the Two Surfaces ΔΦ, the Over-
the first time. Potential for Hydrogen Evolution Reaction χ(H2), and the
The stable 2D M2X3 monolayers show quintuple layer Over-Potential for Oxygen Evolution Reaction χ(O2) of
structures of X−M−X−M−X (Figure 1). The calculated lattice M2X3 Monolayersa
Egi(HSE) Egd(HSE) ΔΦ χ(H2) χ(O2)
Al2S3 2.94 3.41 2.35 1.72 2.34
Al2Se3 2.41 2.60 1.96 1.63 1.51
Al2Te3 1.51 1.91 1.43 1.27 0.43
Ga2S3 2.55 2.77 1.65 1.05 1.92
Ga2Se3 1.68 1.92 1.30 0.69 1.06
Ga2Te3 0.77 1.11 0.88 0.43 −0.01
In2S3 1.91 1.96 1.68 0.21 2.15
In2Se3 1.43 1.52 1.38 0.19 1.39
In2Te3 1.14 1.30 1.00 0.50 0.41
a
All the values are in eV.

Figure 1. Atomic structures of 2D M2X3 (M = Al, Ga, In; X = S, Se,

Te) materials. (a,b) Top and side views, respectively. The unit cell is
drawn with black solid lines. The black arrow in (b) indicates the
direction of the vertical electric field. The (001) and (00−1) surfaces
are shown in (b).
For conventional 2D materials without vertical EF, there is
only one vacuum level, and thus, the redox potentials of H+/H2
and H2O/O2 are the same on the two surfaces. Comparatively,
the intrinsic EF in the perpendicular direction leads to a
vacuum level difference (ΔΦ) on the two respective surfaces of

Figure 2. Band structures (left column) and band edge positions (right column) for M2X3 monolayers. The Fermi level is set to zero. The redox
potentials of H+/H2 and H2O/O2 are presented with green and blue lines, respectively. The VBM and CBM are shown with red points. The
definitions of χ(H2) and χ(O2) are shown in (a).

6313 DOI: 10.1021/acs.nanolett.8b02561

Nano Lett. 2018, 18, 6312−6317
Nano Letters
these 2D M2X3 monolayers (Figure S4). The redox potentials
of H+/H2 and H2O/O2 are determined by the relative
electrochemical potentials to the vacuum level, and thus, the
vacuum level difference on the two respective surfaces results
in the shifts of the redox potentials of H+/H2 and H2O/O2
between the two surfaces (the right column of Figure 2). Due
to the electrostatic potential difference of the two surfaces,
photogenerated electrons and holes aggregate on the (00−1)
and (001) surfaces, respectively. Correspondingly, the HER
and OER happen on the (00−1) and (001) surfaces,
respectively. Therefore, judging the activity of HER and
OER for photogenerated electrons and holes on the (00−1)
and (001) surfaces, respectively, is the key criteria for
evaluating photocatalysts for water splitting. It is important
to point out that if the vacuum level on the (00−1) surface is
singly considered, only Ga2S3 and In2S3 are potential
photocatalysts for overall water splitting. What is worse, the
sole consideration of the vacuum level on the (001) surface
results in all M2X3 monolayers unsuitable for photocatalytic
overall water splitting. Surprisingly, when both of the vacuum
levels on the two surfaces are taken into account (the right
column of Figure 2), all the M2X3 monolayers can serve as
promising photocatalysts for overall water splitting, except for
Ga2Te3. The overpotentials of HER (χ(H2)) and OER
(χ(O2)) represent the redox abilities of photogenerated
carriers and thus are important criteria for evaluating the
performance of photocatalysts during the water splitting
process. χ(H2) is the potential difference between the CBM
and redox potential of H+/H2, while χ(O2) is the potential
difference between the VBM and redox potential of H2O/O2
(Figure 2a). The detailed χ(H2) and χ(O2) are listed in Table
1. Except for χ(O2) of Ga2Te3 as well as χ(H2) of In2S3 and
In2Se3, all the χ(H2) and χ(O2) of the M2X3 monolayers are
larger than 0.4 eV, indicating high redox abilities for HER and
OER. For Ga2Te3, by adding an extra tensile force to cause 3%
strain, the band edge alignment becomes suitable for overall
water splitting (Figure S3), and the band gaps, χ(H2), and
χ(O2) are 0.88, 0.22, and 0.23 eV, respectively. It should be
specifically emphasized that In2Te3, with a quite small band
gap of 1.14 eV, can absorb infrared light to drive overall water
splitting.
As known, the photogenerated electrons and holes scattered
in different domains of one material benefits to decreasing
their recombination probability. The spatial distributions of the
valence band (VB) and the conduction band (CB) for In2S3
monolayer are exampled to indicate the efficient electron−hole
separation. As shown in Figure 3, most of the VB originates
from the top two layers of S, while most of the CB is
contributed by the down layers of S and In. When the X
component varies from S to Te, the CB gradually spreads to
the top surface owing to the weakened vertical intrinsic EF
(Figures S5 and S6).
The intrinsic EF existing in the material shifts the vacuum
levels on the two surfaces of 2D M2X3. Meanwhile, it will affect
the band positions of water molecules neighboring the two
respective surfaces, which is a crucial precondition for
achieving the new mechanism for photocatalytic water
splitting.15 This point is confirmed by calculating the electronic
properties of one water molecule or one water molecular layer
absorbed on the top and down surfaces of Ga2S3. The intrinsic
EF induces obvious shifts of the projected density of states for
the water adsorbed on the top and down surfaces, respectively,
in both systems of water molecules and water molecular layers
6314
Letter
Figure 3. (a) Distributions of VB and CB along the vertical direction
(z axis) for In2S3 monolayers. (b,c) Spatial distribution of CB and VB.
adsorbed on Ga2S3 (Figure S7). In Ga2S3 monolayer, the
direction of the intrinsic EF points from the down surface to
the top surface. As a result, the band levels of water molecules
on the top surface are significantly higher than those of water
molecules on the down surface.
The GW plus Bethe−Salpeter equation approach25−28 is
employed to predict the accurate optical absorption (Figure 4)
and excitonic nature of M2X3. Ascribed to the e−h interactions,
the optical absorption of all the M2X3 are strikingly improved,
and strongly bound exciton states below the onset of single-
particle transition continuum are observed. The increment of
band gap stemming from the quasi-particle (QP) correction
causes the blue-shift of absorption spectra, while the strong
excitonic effect results in the red-shift of absorption spectra.
Hence, the values of the first bright excitonic energies (optical
gap, EI) are comparable to those of direct band gaps predicted
by HSE hybrid functional (Egd(HSE)). The QP band gaps, EI,
and exciton binding energies (Eb) are listed in Table S2. The
linear scaling law between QP band gaps and Eb is observed
(Figure S8), which coincides well with previous works.29,30
However, the slope gained in this work is 0.14, which is smaller
than that reported in previous works. This indicates that the
vertical intrinsic EF in 2D material reduces exciton binding
energy, thereby benefiting the electron−hole separation.
Excitingly, the EI of Ga2Te3 (0.64 eV) and In2Te3 (1.18 eV)
are fairly small, and there is relatively strong absorption
intensity in the region below 1.60 eV for these two materials,
indicating they are capable of absorbing infrared light for
photocatalytic water splitting.
The improvement of energy conversion efficiency is the
ultimate target in the pursuit of solar energy utilization for
photocatalytic water splitting. Assuming the 100% efficiency of
the catalytic reaction, the efficiency upper limits of light
absorption, carrier utilization, and STH are predicted (Table
2). According to previous works,31 the efficiency of light
absorption is defined as
∞
∫E P(hω)d(hω)
g
ηabs = ∞
∫0 P(hω)d(hω)
DOI: 10.1021/acs.nanolett.8b02561
Nano Lett. 2018, 18, 6312−6317
Nano Letters Letter

Figure 4. Optical absorption spectrum for M2X3 monolayers calculated by GW. A Gaussian broadening of 0.05 eV is adopted.

Table 2. Energy Conversion Efficiency of Light Absorption the activation energy issue.10 The previous experiments
(ηabs), Carrier Utilization (ηcu), STH (ηSTH), and Corrected reported that the overpotentials of OER cocatalysts for IrOx,
STH (η′STH) NiFeOx, CoFeOx, NiCoOx, etc., are below 0.5 eV32 and that of
HER cocatalyst for Pt is below 0.1 eV.33 Considering the
ηabs (%) ηcu (%) ηSTH (%) ηSTH
′ (%)
energy loss during carrier migration between different
Al2S3 7.2 37.8 2.7 2.6 materials, the required overpotentials for HER and OER are
Al2Se3 20.9 43.6 9.1 8.0 assumed to be 0.2 and 0.6 eV, respectively. Then, E is
Al2Te3 61.1 46.6 28.4 21.4

l E , (χ (H ) ≥ 0.2, χ (O ) ≥ 0.6)
determined by
o
o
o
Ga2S3 16.5 42.0 6.9 6.4

o
o
o
o
o
Ga2Se3 52.2 54.5 28.4 21.9

o
g 2 2

o Eg + 0.2 − χ (H2), (χ (H2) < 0.2, χ (O2) ≥ 0.6)

E=o
Ga2Te3a
m
89.1 51.9 46.2 34.7

o
o
o
o Eg + 0.6 − χ (O2), (χ (H2) ≥ 0.2, χ (O2) < 0.6)
In2S3 40.9 43.9 17.9 14.4

o
o
o
o
o
In2Se3 65.5 58.8 38.5 26.9

o
o
n g
In2Te3 79.8 54.5 43.4 32.1
a E + 0.8 − χ (H2) − χ (O2), (χ (H2) < 0.2, χ (O2) < 0.6)
Band structure of Ga2Te3 monolayer with 3% strain is used.
Then, the STH efficiency is defined as
where P(hω) is the AM1.5G solar energy flux at the photon ηSTH = ηabs × ηcu
energy hω and Eg is the band gap of materials. The integral
from 0 to ∞ in the denominator represents the total power The intrinsic EF does positive work for the electron−hole
density of incident simulative sunlight (AM1.5G), while the separation during the process of photocatalytic water splitting.
integral from Eg to ∞ in the numerator represents the power Therefore, this part of work should be added into the total
density that can be absorbed by materials. The efficiency of energy, and then the corrected STH efficiency of photo-
carrier utilization is defined as catalytic water splitting for 2D material with vertical intrinsic
∞ P(hω) EF is calculated as
ΔG ∫ hω
d(hω) ∞
E
ηcu = ∞ ∫0 P(hω)d(hω)
∫E P(hω)d(hω) ′ = ηSTH ×
ηSTH ∞ ∞ P(hω)
g
∫0 P(hω)d(hω) + ΔΦ ∫E hω
d(hω)
where ΔG is the potential difference of 1.23 eV for water
g

splitting and E is the energy of photons that can actually be
utilized for water splitting. The integral from E to ∞ in the
numerator is the effective photocurrent density. Determining
the extra energy needed to overcome the barriers of HER and
OER is important for calculating STH efficiency. Current
calculations show that the barrier of OER is relatively large
(Figures S11 and S12). In experiments, introducing cocatalysts
has been demonstrated to be an efficient route in addressing
6315
where ΔΦ is the vacuum level difference on the two respective
surfaces of these 2D M2X3, and the second term in the
denominator represents the work done by the vertical intrinsic
EF. Here, the band gaps, χ(H2), and χ(O2) predicted by HSE
hybrid functional are used to calculate these energy conversion
efficiencies (Table 2). The light absorption efficiency is
strongly dependent on the band gap. The band gaps of the
Al2Te3, Ga2Se3, Ga2Te3, In2S3, In2Se3, and In2Te3 materials are
DOI: 10.1021/acs.nanolett.8b02561
Nano Lett. 2018, 18, 6312−6317
Nano Letters
smaller than 2.0 eV, and thus, their energy conversion
efficiencies of light absorption are above 40%. Due to the
suitable values of χ(H2) and χ(O2), the energy conversion
efficiencies of carrier utilization for all the M2X3 materials are
higher than 35%. The high efficiencies of both light absorption
and carrier utilization lead to high STH efficiency. Except for
Al2S3, Al2Se3, and Ga2S3, the corrected STH efficiencies of
M2X3 are larger than 10%, which is a critical value for solar
hydrogen generation to be an economically viable resource.
The quite small band gaps (≤1.51 eV), Al2Te3, Ga2Se3,
Ga2Te3, In2Se3, and In2Te3 give the corrected STH efficiencies
above 21%, which are larger than the conventional theoretical
limit of ∼18% and are comparable to or larger than the best
STH efficiency for solar water splitting by photovoltaic-
electrolysis reported in experiment.34 It should be strongly
recommended that the corrected STH conversion efficiencies
of Ga2Te3 and In2Te3 using the full solar spectrum even
achieve 34.7% and 32.1%, respectively, because of their ability
to absorb infrared light for driving overall water splitting. The
quantum and other forms of efficiencies of the 2D M2X3 group
are also investigated and presented in the Supporting
Information.
It should be mentioned that the protons and hydroxyl ions
will gradually accumulate on the two respective surfaces during
the process of photocatalytic water splitting, which results in
the decrease of intrinsic EF. Finally, the intrinsic EF will
vanish, and the normal photocatalytic water splitting will
continue without the support of an intrinsic EF. To recover the
intrinsic EF, the residual protons and hydroxyl ions should be
removed from the surfaces. This can be realized by several
means, such as applying a pulsed electric field or sonication
treatment, or adding a sacrificial reagent.15
In conclusion, the first-principles calculations are performed
to explore the potential applications of 2D M2X3 materials as
photocatalysts for water splitting. All nine members of the
M2X3 family are proved to be promising photocatalysts for
overall water splitting. The predicted STH efficiencies of
sunlight for Al2Te3, Ga2Se3, Ga2Te3, In2S3, In2Se3, and In2Te3
are larger than 10%. Excitingly, In2Te3 is demonstrated to be
infrared-light driven photocatalyst, and its theoretical limit of
STH efficiency using the full solar spectrum even achieves
32.1%. These results provide convincing theoretical proof that
experimentally attainable 2D M2X3 materials with vertical
intrinsic EF are highly efficient photocatalysts for overall water
splitting. Furthermore, we believe that exploring 2D materials
with intrinsic EF is a bright route to get access to highly
efficient photocatalysts for practical hydrogen production
applications.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.nano-
lett.8b02561.
Computational details, cohesive energies, electronic
properties, carrier mobility, and quantum as well as
other forms of efficiencies (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jlyang@ustc.edu.cn.
6316
Letter
ORCID
Jiuyu Sun: 0000-0001-6957-8626
Jinlong Yang: 0000-0002-5651-5340
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was partially supported by the National Natural
Science Foundation of China (Grant No. 21688102 and No.
21503204), by the National Key Research & Development
Program of China (Grant No. 2016YFA0200604), by Anhui
Initiative in Quantum Information Technologies (Grant No.
AHY090400), and by the China Postdoctoral Science
Foundation (Grant No. 2018M632534). The numerical
calculations have been done on the supercomputing system
in the USTC-SCC and CAS-SCC.
■
REFERENCES
(1) Cox, C. R.; Lee, J. Z.; Nocera, D. G.; Buonassisi, T. Ten-Percent
Solar-to-Fuel Conversion with Nonprecious Materials. Proc. Natl.
Acad. Sci. U. S. A. 2014, 111 (39), 14057−14061.
(2) Maeda, K.; Domen, K. Photocatalytic Water Splitting: Recent
Progress and Future Challenges. J. Phys. Chem. Lett. 2010, 1 (18),
2655−2661.
(3) Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.;
Mi, Q.; Santori, E. A.; Lewis, N. S. Solar Water Splitting Cells. Chem.
Rev. 2010, 110 (11), 6446−6473.
(4) Zou, Z.; Ye, J.; Sayama, K.; Arakawa, H. Direct Splitting of Water
under Visible Light Irradiation with an Oxide Semiconductor
Photocatalyst. Nature 2001, 414, 625.
(5) Gai, Y.; Li, J.; Li, S.-S.; Xia, J.-B.; Wei, S.-H. Design of Narrow-
Gap TiO2: A Passivated Codoping Approach for Enhanced
Photoelectrochemical Activity. Phys. Rev. Lett. 2009, 102 (3), 36402.
(6) Zhu, W.; Qiu, X.; Iancu, V.; Chen, X.-Q.; Pan, H.; Wang, W.;
Dimitrijevic, N. M.; Rajh, T.; Meyer, H. M.; Paranthaman, M. P.; et al.
Band Gap Narrowing of Titanium Oxide Semiconductors by
Noncompensated Anion-Cation Codoping for Enhanced Visible-
Light Photoactivity. Phys. Rev. Lett. 2009, 103 (22), 226401.
(7) Yin, W.-J.; Wei, S.-H.; Al-Jassim, M. M.; Yan, Y. Double-Hole-
Mediated Coupling of Dopants and Its Impact on Band Gap
Engineering in TiO2. Phys. Rev. Lett. 2011, 106 (6), 66801.
(8) Kudo, A.; Miseki, Y. Heterogeneous Photocatalyst Materials for
Water Splitting. Chem. Soc. Rev. 2009, 38 (1), 253−278.
(9) Fu, C.-F.; Luo, Q.; Li, X.; Yang, J. Two-Dimensional van Der
Waals Nanocomposites as Z-Scheme Type Photocatalysts for
Hydrogen Production from Overall Water Splitting. J. Mater. Chem.
A 2016, 4 (48), 18892−18898.
(10) Yang, J.; Wang, D.; Han, H.; Li, C. Roles of Cocatalysts in
Photocatalysis and Photoelectrocatalysis. Acc. Chem. Res. 2013, 46
(8), 1900−1909.
(11) Liao, L.; Zhang, Q.; Su, Z.; Zhao, Z.; Wang, Y.; Li, Y.; Lu, X.;
Wei, D.; Feng, G.; Yu, Q.; et al. Efficient Solar Water-Splitting Using a
Nanocrystalline CoO Photocatalyst. Nat. Nanotechnol. 2014, 9, 69.
(12) Liu, J.; Liu, Y.; Liu, N.; Han, Y.; Zhang, X.; Huang, H.; Lifshitz,
Y.; Lee, S.-T.; Zhong, J.; Kang, Z. Metal-Free Efficient Photocatalyst
for Stable Visible Water Splitting via a Two-Electron Pathway. Science
2015, 347 (6225), 970−974.
(13) Wang, Q.; Hisatomi, T.; Jia, Q.; Tokudome, H.; Zhong, M.;
Wang, C.; Pan, Z.; Takata, T.; Nakabayashi, M.; Shibata, N.; et al.
Scalable Water Splitting on Particulate Photocatalyst Sheets with a
Solar-to-Hydrogen Energy Conversion Efficiency Exceeding 1%. Nat.
Mater. 2016, 15, 611.
(14) Goto, Y.; Hisatomi, T.; Wang, Q.; Higashi, T.; Ishikiriyama, K.;
Maeda, T.; Sakata, Y.; Okunaka, S.; Tokudome, H.; Katayama, M.;
et al. A Particulate Photocatalyst Water-Splitting Panel for Large-Scale
Solar Hydrogen Generation. Joule 2018, 2 (3), 509−520.
DOI: 10.1021/acs.nanolett.8b02561
Nano Lett. 2018, 18, 6312−6317
Nano Letters Letter

(15) Li, X.; Li, Z.; Yang, J. Proposed Photosynthesis Method for Combining Experiment and Theory. Angew. Chem., Int. Ed. 2015,
Producing Hydrogen from Dissociated Water Molecules Using 54 (1), 52−65.
Incident Near-Infrared Light. Phys. Rev. Lett. 2014, 112 (1), 018301. (34) Jia, J.; Seitz, L. C.; Benck, J. D.; Huo, Y.; Chen, Y.; Ng, J. W. D.;
(16) Ji, Y.; Yang, M.; Dong, H.; Hou, T.; Wang, L.; Li, Y. Two- Bilir, T.; Harris, J. S.; Jaramillo, T. F. Solar Water Splitting by
Dimensional Germanium Monochalcogenide Photocatalyst for Water Photovoltaic-Electrolysis with a Solar-to-Hydrogen Efficiency over
Splitting under Ultraviolet, Visible to near-Infrared Light. Nanoscale 30%. Nat. Commun. 2016, 7, 13237.
2017, 9 (25), 8608−8615.
(17) Fu, C.-F.; Li, X.; Luo, Q.; Yang, J. Two-Dimensional Multilayer
M2CO2 (M = Sc, Zr, Hf) as Photocatalysts for Hydrogen Production
from Water Splitting: A First Principles Study. J. Mater. Chem. A
2017, 5 (47), 24972−24980.
(18) Ma, X.; Wu, X.; Wang, H.; Wang, Y. A Janus MoSSe
Monolayer: A Potential Wide Solar-Spectrum Water-Splitting Photo-
catalyst with a Low Carrier Recombination Rate. J. Mater. Chem. A
2018, 6 (5), 2295−2301.
(19) Ji, Y.; Yang, M.; Lin, H.; Hou, T.; Wang, L.; Li, Y.; Lee, S.-T.
Janus Structures of Transition Metal Dichalcogenides as the
Heterojunction Photocatalysts for Water Splitting. J. Phys. Chem. C
2018, 122 (5), 3123−3129.
(20) Ding, W.; Zhu, J.; Wang, Z.; Gao, Y.; Xiao, D.; Gu, Y.; Zhang,
Z.; Zhu, W. Prediction of Intrinsic Two-Dimensional Ferroelectrics in
In2Se3 and Other III2-VI3 van Der Waals Materials. Nat. Commun.
2017, 8, 14956.
(21) Zhou, J.; Zeng, Q.; Lv, D.; Sun, L.; Niu, L.; Fu, W.; Liu, F.;
Shen, Z.; Jin, C.; Liu, Z. Controlled Synthesis of High-Quality
Monolayered α-In2Se3 via Physical Vapor Deposition. Nano Lett.
2015, 15 (10), 6400−6405.
(22) Almeida, G.; Dogan, S.; Bertoni, G.; Giannini, C.; Gaspari, R.;
Perissinotto, S.; Krahne, R.; Ghosh, S.; Manna, L. Colloidal
Monolayer β-In2Se3 Nanosheets with High Photoresponsivity. J.
Am. Chem. Soc. 2017, 139 (8), 3005−3011.
(23) Zhou, Y.; Wu, D.; Zhu, Y.; Cho, Y.; He, Q.; Yang, X.; Herrera,
K.; Chu, Z.; Han, Y.; Downer, M. C.; et al. Out-of-Plane
Piezoelectricity and Ferroelectricity in Layered α-In2Se3 Nanoflakes.
Nano Lett. 2017, 17 (9), 5508−5513.
(24) Xiao, J.; Zhu, H.; Wang, Y.; Feng, W.; Hu, Y.; Dasgupta, A.;
Han, Y.; Wang, Y.; Muller, D. A.; Martin, L. W.; et al. Intrinsic Two-
Dimensional Ferroelectricity with Dipole Locking. Phys. Rev. Lett.
2018, 120 (22), 227601.
(25) Hybertsen, M. S.; Louie, S. G. Electron Correlation in
Semiconductors and Insulators: Band Gaps and Quasiparticle
Energies. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 34 (8),
5390−5413.
(26) Benedict, L. X.; Shirley, E. L.; Bohn, R. B. Optical Absorption
of Insulators and the Electron-Hole Interaction: An Ab Initio
Calculation. Phys. Rev. Lett. 1998, 80 (20), 4514−4517.
(27) Albrecht, S.; Reining, L.; Del Sole, R.; Onida, G. Ab Initio
Calculation of Excitonic Effects in the Optical Spectra of Semi-
conductors. Phys. Rev. Lett. 1998, 80 (20), 4510−4513.
(28) Rohlfing, M.; Louie, S. G. Electron-Hole Excitations in
Semiconductors and Insulators. Phys. Rev. Lett. 1998, 81 (11),
2312−2315.
(29) Choi, J.-H.; Cui, P.; Lan, H.; Zhang, Z. Linear Scaling of the
Exciton Binding Energy versus the Band Gap of Two-Dimensional
Materials. Phys. Rev. Lett. 2015, 115 (6), 66403.
(30) Jiang, Z.; Liu, Z.; Li, Y.; Duan, W. Scaling Universality between
Band Gap and Exciton Binding Energy of Two-Dimensional
Semiconductors. Phys. Rev. Lett. 2017, 118 (26), 266401.
(31) Chen, Z.; Jaramillo, T. F.; Deutsch, T. G.; Kleiman-
Shwarsctein, A.; Forman, A. J.; Gaillard, N.; Garland, R.; Takanabe,
K.; Heske, C.; Sunkara, M.; et al. Accelerating Materials Development
for Photoelectrochemical Hydrogen Production: Standards for
Methods, Definitions, and Reporting Protocols. J. Mater. Res. 2010,
25 (1), 3−16.
(32) McCrory, C. C. L.; Jung, S.; Peters, J. C.; Jaramillo, T. F.
Benchmarking Heterogeneous Electrocatalysts for the Oxygen
Evolution Reaction. J. Am. Chem. Soc. 2013, 135 (45), 16977−16987.
(33) Zheng, Y.; Jiao, Y.; Jaroniec, M.; Qiao, S. Z. Advancing the
Electrochemistry of the Hydrogen-Evolution Reaction through

6317 DOI: 10.1021/acs.nanolett.8b02561

Nano Lett. 2018, 18, 6312−6317