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

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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 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
the contemporary era. For economical production of hydrogen photocatalytic water splitting.
from photocatalytic water splitting, the solar-to-hydrogen A new mechanism for photocatalytic water splitting
(STH) efficiency is required to be at least above 10%.1 In originally proposed by our group reveals that the vertical
theory, the photocatalysts available for water splitting must intrinsic electric field (EF) in the two-dimensional (2D)
possess a band gap of equal or larger than 1.23 eV, originating material not only accelerates the carrier separation but also
from the difference between the redox potentials of H+/H2 and breaks the conventional limitation of 1.23 eV for band gap of
H2O/O2. Assuming both light absorbance and quantum photocatalysts, leading to enlarged light absorption, even to the
efficiency can attain 100%, thus the theoretical limit of the infrared region.15 Referring to this new mechanism, some 2D
STH efficiency using the full solar spectrum is calculated to be materials with vertical EF have been theoretically proved to be
∼47%.2 In fact, the energy loss during the electron-transfer potential photocatalysts for water splitting, such as germanium
process is not avoided, and the kinetic overpotentials are monochalcogenide,16 Sc2CO2,17 and Janus transition metal
demanded to drive the catalytic reactions. The authentic dichalcogenides monolayers.18,19 However, the experimental
energy required for photocatalytic water splitting is commonly synthesis of these 2D materials is difficult to be achieved, and
greater than 2.0 eV,3 and the corresponding theoretical STH the energy conversion efficiency, an ultimate index for
efficiency limit is decreased to ∼18%. In general, the evaluating photocatalytic water splitting, has never been
photocatalytic water splitting process is composed of three explored on these 2D photocatalysts with intrinsic EF.
pivotal steps: light harvesting, carrier separation and trans- Recently, the theoretical computation predicted that 2D
portation, and hydrogen evolution reaction (HER) as well as M2X3 (M = Al, Ga, In; X = S, Se, Te) possess out-of-plane
oxygen evolution reaction (OER). Great efforts are devoted to ferroelectricity.20 Moreover, some members of 2D M2X3
improving the efficiencies of these three steps.4−10 Albeit these groups have been successfully synthesized in experiment.21−24
strategies are demonstrated to be effective in improving the
extremely low STH efficiency case, the experimentally reported Received: June 24, 2018
STH efficiency for photocatalytic water splitting is still hard to Revised: September 18, 2018
exceed 10% so far.11−14 The STH efficiency is determined by 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 For conventional 2D materials without vertical EF, there is
drawn with black solid lines. The black arrow in (b) indicates the only one vacuum level, and thus, the redox potentials of H+/H2
direction of the vertical electric field. The (001) and (00−1) surfaces and H2O/O2 are the same on the two surfaces. Comparatively,
are shown in (b). 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 Letter

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

the water adsorbed on the top and down surfaces, respectively, ηabs = ∞
in both systems of water molecules and water molecular layers
∫0 P(hω)d(hω)

6314 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 where ΔΦ is the vacuum level difference on the two respective
utilized for water splitting. The integral from E to ∞ in the surfaces of these 2D M2X3, and the second term in the
numerator is the effective photocurrent density. Determining denominator represents the work done by the vertical intrinsic
the extra energy needed to overcome the barriers of HER and EF. Here, the band gaps, χ(H2), and χ(O2) predicted by HSE
OER is important for calculating STH efficiency. Current hybrid functional are used to calculate these energy conversion
calculations show that the barrier of OER is relatively large efficiencies (Table 2). The light absorption efficiency is
(Figures S11 and S12). In experiments, introducing cocatalysts strongly dependent on the band gap. The band gaps of the
has been demonstrated to be an efficient route in addressing Al2Te3, Ga2Se3, Ga2Te3, In2S3, In2Se3, and In2Te3 materials are
6315 DOI: 10.1021/acs.nanolett.8b02561
Nano Lett. 2018, 18, 6312−6317
Nano Letters Letter

smaller than 2.0 eV, and thus, their energy conversion ORCID
efficiencies of light absorption are above 40%. Due to the Jiuyu Sun: 0000-0001-6957-8626
suitable values of χ(H2) and χ(O2), the energy conversion Jinlong Yang: 0000-0002-5651-5340
efficiencies of carrier utilization for all the M2X3 materials are
Notes
higher than 35%. The high efficiencies of both light absorption
The authors declare no competing financial interest.

■
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 ACKNOWLEDGMENTS
hydrogen generation to be an economically viable resource. This work was partially supported by the National Natural
The quite small band gaps (≤1.51 eV), Al2Te3, Ga2Se3, Science Foundation of China (Grant No. 21688102 and No.
Ga2Te3, In2Se3, and In2Te3 give the corrected STH efficiencies 21503204), by the National Key Research & Development
above 21%, which are larger than the conventional theoretical Program of China (Grant No. 2016YFA0200604), by Anhui
limit of ∼18% and are comparable to or larger than the best Initiative in Quantum Information Technologies (Grant No.
STH efficiency for solar water splitting by photovoltaic- AHY090400), and by the China Postdoctoral Science
electrolysis reported in experiment.34 It should be strongly Foundation (Grant No. 2018M632534). The numerical
recommended that the corrected STH conversion efficiencies calculations have been done on the supercomputing system
of Ga2Te3 and In2Te3 using the full solar spectrum even in the USTC-SCC and CAS-SCC.

■
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6317 DOI: 10.1021/acs.nanolett.8b02561

Nano Lett. 2018, 18, 6312−6317