International Journal of Hydrogen Energy 66 (2024) 268–277

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International Journal of Hydrogen Energy

journal homepage: www.elsevier.com/locate/he

Janus PtSSe-based van der Waals heterostructures for direct Z-scheme

photocatalytic water splitting
Pooja Jamdagni a, *, Ashok Kumar b, Sunita Srivastava a, Ravindra Pandey c, K. Tankeshwar a, **
a
Department of Physics and Astrophysics, Central University of Haryana, Mahendragarh, 123031, India
b
Department of Physics, Central University of Punjab, Bathinda, 151401, India
c
Department of Physics, Michigan Technological University, Houghton, MI, 49931, USA

A R T I C L E I N F O A B S T R A C T

Handling Editor: Suleyman I. Allakhverdiev
The semiconductor photocatalysts based on van der Waals heterostructures (vdWHs) and direct Z-scheme
mechanism are viable candidates for water splitting using sunlight. In this study, we exploit the combined effects
of the inherent dipole in a Janus PtSSe monolayer and the intrinsic electric field present at the interface of Janus
PtSSe-based vdWHs for water splitting. These vdWHs exhibit type-II band edge position, narrow band gap and
intrinsic electric fields, establishing them as prototypical direct Z-scheme systems. Remarkably, the density
functional theory-based results find the potential drop of ~0.2–3.2 eV across the interface of vdWHs, promoting
the interlayer photogenerated carrier’s recombination while suppressing the intralayer charge transfer, which
leads to a direct Z-scheme charge transfer pathway with robust redox capabilities. In conjunction with redox
reactions, the built-in electric field at the interface generates sufficient driving force for the photogenerated
carrier’s separation. Also, these Janus PtSSe-based vdWHs possess exceptional abilities in capturing visible light
with high solar-to-hydrogen (STH) conversion efficiency. The results obtained from this study are important to
designing efficient direct Z-scheme photocatalysts for splitting water under sunlight and offer valuable insights
for potential commercial implementations.

1. Introduction water splitting [9]. Unfortunately, it is challenging for conventional

The continuous global population growth has resulted in the scarcity
of conventional fossil fuels and has worsened the energy crisis [1,2]. The
need of the hour is to find clean energy sources to replace depleting fossil
fuels. With the help of semiconductor photocatalysts and sunlight,
hydrogen can be produced by splitting water which is a sustainable and
environmentally friendly way to produce green energy [3]. Exploring
different semiconductor materials for high energy conversion efficiency
in photocatalytic water splitting has drawn significant research interest
[4–7]. In the water-splitting process using semiconductor materials,
photogenerated carriers are separated and moved to the photocatalyst
surface to drive the corresponding redox reactions without producing
any pollutants, making this process useful for practical application [8].
In general, high carrier mobility with low carrier recombination, broad
optical absorption, strong redox ability, large surface-to-volume ratio
and high solar-to-hydrogen (STH) conversion efficiency are the criteria
for choosing a highly efficient candidate material for photocatalytic
photocatalysts to satisfy all the above conditions. As a result, the hunt
for reliable and effective photocatalyst materials has gained significant
research attention [10–12].
Two-dimensional (2D) semiconductor materials have become
increasingly important for photocatalytic water splitting [13,14].
Various 2D compounds based on transition metals and chalcogen ele­
ments have been synthesized experimentally [15] and investigated
theoretically [16–19]. Also, their optoelectronic properties are tunable
with strains, electric fields and surface doping [20]. After the fabrication
of 2D Janus monolayers (MoSSe and WSSe) [21–23] and their hetero­
structures [24,25], the synthesis of 2D Janus PtSSe has also been suc­
cessfully achieved [26]. Unlike the traditional mirror symmetric 2D MX2
compounds, Janus PtSSe monolayer exhibits a structural asymmetry
with intrinsic dipoles that help in effective charge carrier separation in
the photocatalytic process [27]. Also, the characteristics such as high
carrier mobility, appropriate band edge position, good visible light
harvesting ability and high STH conversion efficiency make Janus

* Corresponding author.
** Corresponding author.
E-mail addresses: j.poojaa1228@gmail.com (P. Jamdagni), drtankeshwar@gmail.com (K. Tankeshwar).

https://doi.org/10.1016/j.ijhydene.2024.04.118
Received 7 January 2024; Received in revised form 1 April 2024; Accepted 9 April 2024
Available online 13 April 2024
0360-3199/© 2024 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.
P. Jamdagni et al.
monolayers viable candidate material for photocatalytic applications
[27,28].
The performance of 2D materials in the photocatalytic process shows
improvement compared to their bulk counterpart due to their high
specific surface area and more exposed active sites to participate in the
photocatalytic reaction [29,30]. However, due to redox reactions on the
same surface of the 2D semiconductor photocatalyst, the charge carrier’s
recombination increases, which lowers the photocatalytic efficiency of
the 2D photocatalyst [31,32]. Therefore, numerous strategies such as
element doping [33,34], surface defects engineering [35] and con­
structing van der Waals heterostructures (vdWHs) [36,37] have been
suggested to increase the photocatalytic effectiveness of 2D photo­
catalysts. Among them, the construction of type-II vdWH with staggered
band alignments shows great promise as the VBM and CBM consist of
different semiconductors that lead to the occurrence of hydrogen evo­
lution reaction (HER) and oxygen evolution reaction (OER) processes on
different surfaces of vdWH [38–40]. The intrinsic spatial separation of
photogenerated carriers in type-II vdWHs increases the photocatalytic
efficiency [41,42]. However, type-II vdWHs often have low redox abil­
ities, so they don’t provide enough driving force for HER and OER
processes. Note that the wide optical absorption calls for a small
bandgap, whereas the strong redox ability of water is associated with a
wide bandgap of semiconductor photocatalysts. So, it is challenging for
type-II vdWHs to have both a robust redox ability and a broad absorp­
tion of sunlight [43].
To overcome the problems with type-II vdWHs, a suitable direct Z-
scheme vdWHs have been proposed as an alternative [44]. Although the
staggered band structure layout of type-II and direct Z-scheme vdWHs
are identical, the carrier transport mechanisms are entirely different. In
direct Z-scheme vdWH, electrons from the CBM of the water oxidation
surface recombine with the holes from the VBM of the water reduction
surface of the photocatalyst without using any redox mediator, thereby
only leaving spatially separated holes (electrons) in the VBM (CBM) of
water oxidation (reduction) surface of photocatalyst [45]. In addition,
the narrow gap semiconductors can be employed to construct a
Z-scheme vdWH to enlarge the photoabsorption range up to the infrared
region for water splitting [46].
Various 2D heterostructures for direct Z-scheme photocatalysis have
been realized in experiments [47–51]. Also, using first-principles cal­
culations, researchers have investigated various direct Z-scheme vdW
heterostructures as water-splitting photocatalysts such as GeS/WS2
[52], C3N/WS2 [53], MS2(M = Pt, Zr, Hf, Sn)/As [54–56], GeC/BSe
[57], GeSe/HfS2 [58], GaSe/ZrS2 [59], PtS2/g-C3N4 [60], WTe2/InSe
[61], GaN/BS [62], GeC/HfS2 [63], MOSSe/WSeTe [64], h-BNC/WSSe
[65], CdO/PtSSe [66], SnC/HfSSe [67] and SCCl2/ML (ML = MoTe2,
Hf2CO2) [68] indicating that the direct Z-scheme photocatalyts based on
2D semiconductors are promising for the efficient water splitting.
In this work, we systematically investigated 2D Janus PtSSe-based
vdWHs using density functional theory. We first identify various
possible 2D monolayers suitable for forming commensurate hetero­
structure with Janus PtSSe. After analyzing their electronic properties,
taking lattice mismatch of <1.5% and determining the most stable
stacking configurations among various possible stacking patterns, we
have chosen 8 heterostructures (PtSSe/As, PtSeS/As, PtSSe/H-HfSe2,
PtSSe/H–SnS2, PtSSe/H–ZrSe2, PtSSe/T-ZrS2, PtSSe/T-HfS2, PtSSe/T-
SnS2) having type-II bands alignments for the further study. The ther­
modynamical stability of the energetically most stable heterostructure
configuration is confirmed using AIMD simulations. Then, a thorough
investigation of these vdWHs for Z-scheme photocatalytic water split­
ting is conducted.
2. Computational details
All the results presented are based on the Vienna ab initio simulation
Package (VASP) [69] using a projector-augmented wave (PAW)
approach. The state-of-the-art density functional theory (DFT) is
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International Journal of Hydrogen Energy 66 (2024) 268–277
implemented in VASP to perform electronic structure calculations with
the help of Perdew, Burke, and Ernzerhof’s (PBE) version of generalized
gradient approximation (GGA) [69]. Due to the inherent drawback of
underestimating electronic band gaps by PBE functional, the
Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional method [70] was
employed to calculate a more accurate bandstructure and optical ab­
sorption spectrum. The weak interlayer vdW interactions in vdWHs are
considered using Grimme’s DFT-D3 method [71]. A dipole correction is
used perpendicularly throughout the calculations [72]. An energy
cut-off of 500 eV is used for the wavefunctions expanded using plane
waves. A reciprocal space is sampled with 20 × 20 × 1 k-points within
the Monkhorst-Pack scheme. A vacuum distance of 15 Å is used along
the perpendicular direction to remove the superficial interactions due to
periodic images. The vdWHs were relaxed using the conjugated gradient
approach and force criteria less than 0.01 eV/Å on each atom. The AIMD
simulations are performed at 300K using the Nose algorithm for 5 ps
with a time step of 1 fs in a larger 3 × 3 supercell.
3. Results and discussions
3.1. Properties of monolayers
Firstly, we examine the pristine 2D Janus PtSSe monolayer in a 1T
phase where Pt atoms are bonded to six surrounding chalcogens in an
octahedral arrangement (Fig. 1a). The calculated value lattice constant
(a=b=3.64 Å) of the Janus PtSSe monolayer is consistent with the
existing literature [27]. Note that the mechanical and thermodynamical
stability of Janus PtSSe monolayer is confirmed in the previous studies
[27,36,73]. Also, the computed electronic band structure using hybrid
HSE06 functional shows that of Janus PtSSe monolayer is an indirect
band gap semiconductor (Eg=2.33 eV) with VBM and CBM lying at
Г-point and along Г-M direction, respectively (Fig. 1b), which is also in
agreement with the existing results in literature [33]. The contribution
of VBM is mainly given by the strongly hybridized chalcogen (S and Se)
orbitals, whereas CBM shows the main contribution from metal (Pt)
atoms.
The electrostatic potential difference of 0.76 eV is calculated be­
tween the S and Se surfaces, which leads to the intrinsic electric field of
0.93 eV/Å in the Janus PtSSe monolayer. The intrinsic electric field in
the Janus PtSSe monolayer has been calculated as a slope of the line
between the minimum of the planar average potential (Fig. 1c) of the
outermost Se and S atoms. Note that, in previous studies, the intrinsic
electric field of 0.82 eV/Å and 0.87 eV/Å has been calculated for Janus
α-Te2S [74] and Janus β-PtSSe [75] monolayers, respectively. This
feature is important for carrier separation and hence the performance of
Janus PtSSe monolayer for efficient water splitting. Note that the Janus
PtSSe monolayer has suitable alignments of bands to act as a
water-splitting photocatalyst (Fig. 1c). The characteristics of Janus
PtSSe monolayer, such as vacuum level difference between the two
surfaces, occurrence of HER and OER processes on different surfaces and
a sizable energy difference of 0.56 eV between the CBM and reduction
potential of water and 1.30 eV between the VBM and oxidation potential
of water make it a potential candidate material for water splitting.
Next, we consider possible monolayers that can make commensurate
heterostructures with Janus PtSSe. The electronic band structure
calculated using hybrid HSE06 functional reveals all the monolayers as
semiconductors with indirect band gaps ranging from 0.54 eV to 3.23 eV
(Fig. S1). Note that these monolayers have been reported to be ther­
modynamically stable in free-standing form in the literature [13,17,19,
31,76]. Only a few monolayers (β-As, GaS, GaSe, T-PtS2 and T-PtSe2)
exhibit the proper band alignments, which engulf the water redox po­
tential levels and are hence suited for photocatalytic water splitting
(Fig. S2).
P. Jamdagni et al. International Journal of Hydrogen Energy 66 (2024) 268–277

Fig. 1. (a) PtSSe monolayer crystal structure’s top and side views (colour code: Pt-grey, S-yellow, Se-light green), (b) atom-resolved electronic structure along K-Г-M-
K direction of 2D Brillouin zone, using hybrid HSE06 theory and (c) electrostatic potential profile of PtSSe monolayer. Band edge positions with respect to water
redox potential for water splitting at pH = 0 are shown in (c). Δφ represents the difference between the vacuum levels on the two surfaces of the Janus monolayer.
(For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

3.2. Geometrical structure and stability of vdWHs
The lattice parameters of various monolayers forming Janus PtSSe
heterostructures are given in Table S1. In the unit cell of Janus PtSSe
monolayer, the lattice mismatch of these monolayers varies from 0.2%
to 4.3 %. The extent of lattice mismatch between layers and types of
heterostructure are very important factors in designing efficient photo­
catalysts. Following the criteria of minimum lattice mismatch (<1.5%)
and type-II bands alignments for efficient photocatalysts, we consider
PtSSe/As, PtSeS/As, PtSSe/H-HfSe2, PtSSe/H–SnS2, PtSSe/H–ZrSe2,
PtSSe/T-ZrS2, PtSSe/T-HfS2 and PtSSe/T-SnS2 heterostructures for the
further investigation.
These heterostructures’ possible stacking configurations are consid­
ered based on the relative positions of the Janus monolayer (PtSSe) and
other monolayers making up the vertical heterostructures. There are 10
different stacking arrangements for the heterostructures of Janus
monolayer and As (Fig. S3). The calculated binding energy determines
the most stable stacking configuration: Eb = Eheterostructure − (Emonolayer1 +
Emonolayer2 ). The interlayer binding energy (Eb) and distance (d0) of the
relaxed stacking configurations are given in Table S2. The hetero­
structures made up of Janus monolayer and H-phase monolayers (H-
HfSe2, H–SnS2, and H–ZrSe2) have 8 possible stacking configurations
(Fig. S4, Table S3), while the heterostructures containing Janus mono­
layer and T-phase monolayers (T-ZrS2, T-HfS2, and T-SnS2) have 4
possible stacking configurations (Fig. S5, Table S4). The calculated
interlayer binding energy of vdWHs with the most stable configurations
is ~ − 20 meV/Å2 - ~ − 83 meV/Å2. The negative value of the binding
energy demonstrates these heterostructures to be energetically stable.
Note that the calculated binding energy magnitude of heterostructures
considered in the study is nearly the same as that for typical van der
Waals structures such as graphite (− 12 meV/Å2) [77] and MoS2 (− 26
meV/Å2) [78], indicating that vdW forces are responsible for interlayer
interactions in the heterostructures.
Additionally, we assess the thermodynamic stability of the energet­
ically most stable configuration of different heterostructures using AIMD
simulation at 300 K for 5000 fs. Fig. S6 displays the temperature, total
energy, and structural modifications of different heterostructure con­
figurations during the AIMD simulation. These heterostructures are not
immediately disrupted, demonstrating their high thermodynamic sta­
bility. Therefore, these heterostructure configurations are chosen for the
subsequent calculations and investigations.
3.3. Electronic structure of vdWHs
Now, we examine the projected band structure of various vdWHs
obtained using the hybrid HSE06 theory in Fig. 2. The monolayer fea­
tures are preserved in the heterostructures along with the semiconductor
nature of all the heterostructures considered in the study. All the vdWHs
are semiconductors with an indirect band gap ranging from 0.64 eV to
1.60 eV. The VBM and CBM of vdWHs are given by different layers of

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Fig. 2. The projected electronic band structure of various Janus vdWHs using
hybrid HSE06 theory. The indirect band value of each heterostructure is also
shown. Fermi level is set at 0 eV.
heterostructures, indicating the type-II band arrangements with small
energy band gap (~0.6–1.6 eV), which is much smaller than the indi­
vidual layer band gap (~1.5–2.3 eV). The small inter-layer band gap
benefits the recombination of the inter-layer carriers between the CBM
of one layer and the VBM of the other in vdWHs, which greatly enhances
the efficiency of photocatalyst for splitting of water by enhancing redox
ability on the respective surfaces of the vdWHs.
Additionally, we have calculated the effective masses of electrons
(me*) and holes (mh*) of vdWHs (Table S5). The difference between me*
and mh* results in different carrier mobility (μ = eτ/m*) and, hence, the
carrier’s diffusion lengths that help in effective separation of charge
carriers [75]. Note that the diffusion length is related to the carrier’s
mobility as Lp=(μkbτ/e)1/2 = kbτ2/m*)1/2 [79]. Also, the effective mass
anisotropy (Rm* = mh*/me*) can be used to quantitatively estimate the
relative diffusion length. The deviation of calculated Rm* values from
unity suggests lower recombination of photogenerated carriers on each
surface of heterostructures that may improve their photocatalytic
water-splitting efficiency.
3.4. Direct Z-scheme characteristics of vdWHs
Now, we examine the charge transfer pathways across the interface
of vdWHs within the direct Z-scheme mechanism. Because of the dif­
ference in the work function (Φ) of the two monolayers forming vdWH,
the charge at the heterostructure interface gets redistributed. Note that
the work function is calculated as a difference between the values of the
vacuum level and Fermi level. Table S1 shows the work function of
various monolayers forming heterostructures. As guided by Anderson’s
rule, the electrons from the monolayer with a lower work function move
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International Journal of Hydrogen Energy 66 (2024) 268–277
to the monolayer with a higher work function until the Fermi level is
aligned [80]. So, the monolayers in the heterostructure become posi­
tively and negatively charged, and the built-in electric field gets
generated at the heterostructure’s interface. Also, the built-in electric
field raises a band bending near the heterostructure interface (Fig. 3).
When the incident light irradiates the vdWHs, both layers of heter­
ostructures can generate photogenerated electron-hole pairs. These
photogenerated charge carriers can generally transfer in hetero­
structures through three pathways (Fig. 3): i) interlayer charge transfer,
i.e., electrons(hole) transfer between the Layer-1 and Layer-2 through
Path-1 ii) the electrons of the Layer-I combine with the holes of Layer-2
through Path-2, and iii) interlayer electron-hole recombination, i.e.,
holes of Layer-1 combine with the electrons of Layer-2 through Path-3.
The charge transfer mechanism through Path II is strongly prohibited
because of the large spatial separation of charge carriers (Fig. 3). The
carrier transfer mechanism for the other two pathways happens
concurrently and competes with each other. However, the built-in
electric field and decent band alignments i.e. the close positioning of
the VBM of one layer with the CBM of another layer in heterostructure
make interlayer carrier recombination more favourable at the interface
of the studied vdWHs (Fig. 4). Hence, these vdWHs accord with the
characteristics of direct Z-scheme carrier migration. The qualitative
estimation of photogenerated carrier dynamics requires more sophisti­
cated investigations using non-adiabatic molecular dynamics (NAMD)
simulations [81].
More importantly, the alignments of bands of the vdWHs taken into
account in the study bestride the standard redox potential of water at pH
= 0. HER and OER processes are suggested to occur on the different
surfaces of vdWH (Fig. 4). Also, carriers with a longer lifetime and
robust redox ability are preserved on the respective surfaces of the
vdWHs. Therefore, both the robust redox ability and the good spatial
separation of charge carriers occur simultaneously, which effectively
improves the water-splitting performance of direct Z-scheme vdWHs.
To get further insight into the mechanism of charge transfer across
the interface of heterostructures, we obtain the charge density difference
(Δρ) along the Z-axis as Δρ = ρheterostructure − (ρmonolayer1 − ρmonolayer2 ) as
shown in Fig. 5. It is evident from the Δρ profiles that the charge
accumulation (yellow regions) and charge depletion (cyan region) occur
across the heterostructure interface, which leads to the polarized het­
erostructure interface and, hence, the production of built-in electric
field. The built-in electric field drives carrier movement at the hetero­
structure interface, which is important to designing a direct Z-scheme
Fig. 3. The various photogenerated charge transfer pathways of Janus vdWHs.
EC, EV and Evac represent the conduction band minimum, valence band
maximum and vacuum level energy, respectively.
P. Jamdagni et al. International Journal of Hydrogen Energy 66 (2024) 268–277

Fig. 4. The band alignments and direct Z-scheme mechanism of various Janus vdWHs at HSE06 level of theory at pH = 0. Vacuum potential (Evac) is set at 0 eV.

Fig. 5. Top and side views and electrostatic potential profile of various Janus vdWHs. Charge density difference profiles are projected along the z-direction of
electrostatic potential. The isosurface value for charge density was set at 0.0003 |e|. The cyan and yellow regions in the charge density represent electron depletion
and accumulation, respectively. The potential drop (ΔV) across the interface is also shown. Color code: Pt-grey; S-yellow; Se-light green; As-dark green; Zr-green; Hf-
golden yellow; Sn-granite grey. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

photocatalyst system.
To further demonstrate the Z-scheme mechanism, we calculate the
potential drop (ΔV) across the heterostructures interface, which ranges
from 0.22 eV to 3.22 eV (Fig. 5). The potential drop in heterostructures
containing H-phase monolayers (H-HfSe2, H–SnS2, and H–ZrSe2) is
calculated to be higher than that of the heterostructures containing T-
Phase monolayers (T-ZrS2, T-HfS2, and T-SnS2). The H-Phase and T-
phase differ by the relative positions of the surface atoms that leads to
different symmetry in the monolayer crystal structures. The potentials
drop in the heterostructures containing mixed of T-phase and H-phase
monolayer having different symmetry exhibit higher potential drop as
compared to the heterostructure containing both monolayers of the
same T-phase. Note that a significantly large drop in potential across the
interface of vdWH along with the decent bands edge position promotes
the interlayer carrier’s recombination and suppresses the intralayer
charge transfer in heterostructures, facilitating the direct Z-scheme
charge transfer pathways.
3.5. Gibb’s free energy profiles
Next, we calculate the HER and OER process mechanism for the in­
termediates and Gibbs’s free energy profiles using a 3 × 3 supercell. The
computation details are given in the supplementary information. In
addition, the H2O molecule adsorption feasibility on the heterostructure

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surfaces is determined by calculating the H2O molecule adsorbed on
each heterostructure surface in a 2 × 2 supercell. The adsorption energy
is calculated as Ead = (E∗H2 O − E∗ − EH2 O )/A, where E∗H2 O , E∗ and EH2 O
are the total energy of a heterostructure with adsorbed H2O molecules, a
pristine heterostructure and a water molecule, respectively, ’A’ is the
supercell surface area of heterostructure. The relaxed H2O adsorbed
heterostructures are shown in Fig. S7. The calculated Ead of water
molecules on the heterostructure surface ranges from − 0.79 eV/Å2 to
− 1.27 eV/Å2. The negative value indicates the feasibility of H2O
adsorption on the vdWHs considered in the study.
Following the well-known two-electron (2e) reaction pathway
mechanism for HER on the heterostructure surfaces, the proton-electron
combination in the first step is energetically unfavourable and exhibits
an HER barrier ranging from 1.26 eV to 1.48 eV without light irradiation
(U = 0). Note that the rate-limiting potential in the Gibbs free energy
profile is the external potential without light irradiation required to
derive the HER or OER. In the second step, the H2 molecule is released
by a favourable exothermic process. The photogenerated electron po­
tential for various heterostructures ranges from 0.5 eV to 1.75 eV,
reducing the HER barrier (Fig. 6). Particularly, the HER process on the
surface of PtSSe/As and PtSeS/As can occur spontaneously with light
irradiation. However, to trigger the HER process on the other vdWHs
surface, an additional external potential in the range of 0.56–0.93 eV is
required. These values are lower than or comparable to the values re­
ported for other 2D HER materials such as β-PtSSe (0.69 eV) [75], SiP2
(0.83 eV) [82], PE-AgBiP2Se6 (1.06 eV) and FE-AgBiP2Se6 (1.62 eV)
[83].
On the other hand, the OER mechanism on the heterostructure sur­
faces is given by the four-electron (4e) reaction pathway. Without light
irradiation, the OER barrier for all the heterostructures except PtSSe/H-
HfSe2 is given by the OOH* intermediate formation step, with the values
ranging from 1.66 eV to 3.43 eV (Fig. 7).
The photogenerated hole potential for various heterostructures
(0.25 eV–1.80 eV) reduces the OER barrier. However, an additional
external potential (0.26–2.13 eV) is required for the spontaneous OER
process on the heterostructure surfaces considered in the study. These
values are lower than or comparable to the other reported 2D materials
for OER, such as g-C6N6/WTe2 (1.16 eV) [84], β-PtSSe (1.27 eV) [75],
Fig. 6. The reaction coordinates for the 2e pathways in hydrogen evolution reaction (HER) on the surface of various Janus vdWHs at pH = 0. Vertical red arrows also
show the rate-limiting potential during the HER process. The external potential (ηHER) required for the HER to happen on the heterostructure surface is also given.
(For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
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International Journal of Hydrogen Energy 66 (2024) 268–277
GaAs (1.39 eV) [85], g-C3N4 (1.45 eV) [86], CuCl (1.61 eV) [87], Janus
Pd4S3Se3 (1.76 eV) [88], β-Te2S (2.01 eV) [16], β-PdS2 (1.97 eV) [7], C3S
(2.03 eV) [89] and PtS2/As (2.10 eV) [54].
3.6. Absorption spectrum and STH conversion efficiency
Next, we calculate the absorption spectrum to check the light-
harvesting ability of the vdWHs considered in the study. The light ab­
sorption coefficients are determined from the real (ε1) and imaginary
(ε2) parts of the dielectric function as:
√2ω [( 2 )1 ]
α(ω) = ϵ1 (ω) + ϵ22 (ω) 2 − ϵ1 (ω) (1)
c
Fig. S8 shows the in-plane and out-of-plane light absorption co­
efficients (α) of the vdWHs obtained using HSE06 hybrid functional
calculations. The highest value of visible region in-plane absorption
coefficients of these vdWHs is calculated in the range of 5.3–5.7 × 104
cm− 1. Also, the out-of-plane absorption coefficients of these vdWHs in
the visible region reach as high as 1.1–5.0 × 104 cm− 1 (Fig. S8), indi­
cating their good visible light harvesting capability.
In addition, we calculate the excitons binding energy (Eexb) of
vdWHs using the Mott-Wannier hydrogenic model [54]: Eexb = 13.6μex
,
m0 ϵ2s
m∗e m∗h
where μex = m∗e +m∗h is effective excitons mass and ε is static dielectric
constant. The values of static dielectric constant along in-plane and
out-of-plane directions are listed in Table 1. For excitons binding energy
calculations, static dielectric constants are taken as an average of
in-plane and out-of-plane values. Table 1 shows the calculated values of
excitons binding energy. The low excitons binding energy (0.06–0.37
eV) of these vdWHs indicates the better separation of charge carriers for
the water splitting process.
Also, besides constructing the direct Z-scheme vdWH photocatalysts
with good optical absorption ability, the STH conversion efficiency is an
important criterion to determine the economic value of a commercial
photocatalyst, which is regarded as over 10% [90]. STH conversion ef­
ficiency under the assumption of 100% quantum efficiency is given as
[91]:
P. Jamdagni et al. International Journal of Hydrogen Energy 66 (2024) 268–277

Fig. 7. The reaction coordinates for the 4e pathways in oxygen evolution reaction (OER) on the surface of various Janus vdWHs at pH = 0. Vertical red arrows also
show the rate-limiting potential during the OER process. The external potential (ηOER) required for OER to happen on the heterostructure surface is also given. (For
interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

vdWHs and these values are given in Table S8. The STH conversion ef­
Table 1
ficiency of Janus PtSSe monolayer is calculated to be 9.8%. On con­
The static dielectric constants (εs) along in-plane (εxx) and out-of-plane(εzz) di­
structing vdWHs of Janus PtSSe monolayer, the STH conversion
rections and excitons binding energy (Eexb) of various Janus vdWHs.
efficiency is estimated to be ~7–18%, as shown in Fig. 9.
ε_xx ε_zz Eexb (eV)
The calculated STH conversion efficiency of these heterostructures is
PtSSe/As 9.29 4.97 0.06 comparable with the recently reported 2D vdWHs such as As/ZrS2 (6%)
PtSeS/As 6.25 3.72 0.20 [55], WSe2/SnSe2 (9.53%) [96], MoSe2/SnSe2(10.5%) [96], CdO/As
PtSSe/H-HfSe2 5.07 3.51 0.37
PtSSe/H–SnS2 6.45 5.18 0.10
(11.67%) [97], MoSe2/Ti2CO2(12%) [98], SnS2/β-As(17.18%) [56],
PtSSe/H–ZrSe2 5.35 3.70 0.35 In2Se3/SnP3 (19.26%) [10] and GaN/BS (19.95%) [62].
PtSSe/T-ZrS2 4.92 2.78 0.32
PtSSe/T-HfS2 4.76 2.72 0.30 4. Conclusions
PtSSe/T-SnS2 5.03 3.15 0.21

Using first-principles density functional calculations, various Janus

∫∞
P(ℏω)d(ℏω)
∫ ∞ P(ℏω) PtSSe-based vdWHs are characterized for efficient photocatalytic water
ΔG d(ℏω)
(2) splitting. After analyzing their electronic properties, determining the
E E ℏω
ηSTH = ηabs × ηcu = ∫ ∞g × ∫∞
P(ℏω)d(ℏω) P(ℏω)d(ℏω)
0 Eg most stable stacking configurations among various possible stacking
ηabs and ηcu represent the light absorption efficiency and carrier patterns with type-II bands alignments and analyzing the thermody­
utilization efficiency, respectively. P(ħω) is AM1.5G solar energy flux at namical stability of energetically most stable heterostructures configu­
photon energy ħω. The value of Eg is taken to be of the monolayer ration, we constructed the typical direct Z-scheme vdWHs
separated from the corresponding heterostructure and having a larger photocatalysts for water splitting. The small inter-layer band gap
band gap than another monolayer of heterostructure. A similar method (~0.6–1.6 eV) with the appropriate close position of band edges pro­
to obtain STH conversion efficiency has been adopted by various authors motes the inter-layer carrier’s recombination between the CBM of one
in recent studies [92–95]. The calculated value of the band gap of in­ layer and the VBM of other layers in vdWHs. Hence, both the robust
dividual monolayers separated from corresponding heterostructures has redox ability and the good spatial carrier separation exist simulta­
been given in Table S7. Also, the absorption spectrum of separated neously in a photocatalyst, which effectively improves the photo­
monolayers from corresponding heterostructures is shown in Fig. 8. The catalytic water splitting performance of direct Z-scheme vdWHs. The
monolayers in heterostructures show absorption in visible regions, HER process can occur spontaneously on the surface of PtSSe/As and
indicating that heterostructures respond well to solar light. The details PtSeS/As with light irradiation. In contrast, an external potential is
of calculations are given in supplementary information. The bandgap, required to trigger the HER and OER processes on the surface of other
overpotentials (χ(H2 ) and χ(O2 )), ηabs , ηcu , and ηSTH are listed in Table S8. vdWHs considered in the study. The excellent visible light absorption
The intrinsic electric field-induced corrections in the STH conversion ability and outstanding STH conversion efficiency of these vdWHs make
efficiency in the Janus vdWHs is given as [14,16]: them potential candidates for efficient photocatalytic water splitting.
∫∞
η′STH = ηSTH × ∫ ∞ E
P(ℏω)d(ℏω)
∫ ∞ ω) (3) CRediT authorship contribution statement
E0
P(ℏω )d(ℏ ω ) + ΔΦ Eg P(ℏ ℏω
d(ℏω)
Pooja Jamdagni: Data curation, Formal analysis, Methodology,
where ΔΦ represents the electrostatic potential difference of Janus Software, Writing – original draft. Ashok Kumar: Conceptualization,
Methodology, Writing – review & editing. Sunita Srivastava: Formal

274
P. Jamdagni et al.
Fig. 8. The optical absorption spectrum calculated at the HSE06 level of theory for various Janus vdWHs and constituent monolayers isolated from corresponding
vdWHs. The standard solar spectral irradiance is also projected for reference.
Fig. 9. The solar-to-hydrogen (STH) conversion efficiency (η′STH) of various
Janus vdWHs.
analysis, Writing – review & editing. Ravindra Pandey: Conceptuali­
zation, Supervision, Writing – review & editing. K. Tankeshwar: Su­
pervision, Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
275
International Journal of Hydrogen Energy 66 (2024) 268–277
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
PJ gratefully acknowledges the UGC for the D. S. Kothari Post-
Doctoral Fellowship. Superior, a high-performance computing cluster
at Michigan Technological University, MI, Houghton, was used to obtain
the results presented in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijhydene.2024.04.118.
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