International Journal of Hydrogen Energy 78 (2024) 761–772

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International Journal of Hydrogen Energy

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

Innovative 2D materials for efficient photocatalysis: A comparative study

for WSi2N4, WGe2N4, and their janus counterpart WSiGeN4 monolayers
F. Himmet a , G. Surucu b, * , S.B. Lisesivdin c , O. Surucu d , G. Altuntas e , B. Bostan e , A. Gencer f
a
Graduate School of Natural and Applied Sciences, Gazi University, 06500, Ankara, Turkiye
b
Department of Energy Systems Engineering, Faculty of Technology, Gazi University, 06500, Ankara, Turkiye
c
Department of Physics, Faculty of Science, Gazi University, 06500, Ankara, Turkiye
d
Department of Electrical and Electronics Engineering, Atilim University, 06836, Ankara, Turkiye
e
Department of Metallurgical and Materials Engineering, Faculty of Technology, Gazi University, 06500, Ankara, Turkiye
f
Department of Physics, Kamil Ozdag Faculty of Science, Karamanoglu Mehmetbey University, 70200, Karaman, Turkiye

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

Handling Editor: Suleyman I. Allakhverdiev In pursuit of environmentally friendly and effective photocatalytic materials for water splitting, this research
paper presents a thorough evaluation of WSi2N4, WGe2N4, and their Janus counterpart WSiGeN4 monolayers
Keywords: through the application of Density Functional Theory. The study elucidates the optical, electronic, and structural
MA2Z4 monolayers characteristics of these monolayers, thereby demonstrating their potential as highly favorable contenders for
Photocatalytic water splitting
applications involving photocatalytic water splitting. By means of comprehensive optimization and analysis, it is
Density functional theory
shown that these monolayers possess advantageous characteristics, such as favorable band gaps, stable work
Machine learning force fields (MLFF)
Electronic properties functions, and stability over a broad pH range. These attributes are of utmost importance in ensuring the
pH-dependent redox reaction levels effectiveness of hydrogen evolution reaction (HER). The inclusion of Janus WSiGeN4, which possesses an intrinsic
mirror asymmetry, significantly improves the photocatalytic efficacy of the material. This is achieved by meeting
the demands of optimal redox reaction levels in both the conduction and valence bands. In conjunction with
machine learning force fields, ab initio molecular dynamics (AIMD) simulations validate the thermal stability of
these monolayers at 300 K. In addition, our analysis of the optical properties reveals substantial absorption in the
visible spectrum - vital for photocatalytic applications powered by solar energy. In summary, the research
highlights the potential of Janus WSiGeN4, WGe2N4, and WSi2N4 monolayers as multifunctional and effective
substances for forthcoming photocatalytic water-splitting systems. This advancement indicates of a significant
stride in the direction of sustainable energy solution development.

1. Introduction tungsten diselenide and molybdenum disulfide, are two-dimensional

(2D) materials that have attracted interest due to their large surface
Hydrogen serves as a prominent source of sustainable and eco- areas and adjustable electronic structures. These properties make them
friendly energy, providing a crucial substitute for fossil fuels and tack­ potentially useful for improving the efficiency of HER [10–13]. More­
ling the environmental consequences of pollution, thereby leading us over, researchers are investigating the potential of MXenes, which
toward a more sustainable future [1–3]. Its production process relies possess exceptional electrical conductivity and surface reactivity, as well
heavily on electrocatalytic water reduction through Hydrogen Evolution as metal-free materials such as graphene and phosphorene, which are
Reaction (HER). This reaction occurs at the electrode surface and con­ plentiful and possess distinct chemical properties, for their compatibility
verts water into hydrogen gas, an essential component in numerous with HER [7,14–16]. The hunt for new 2D materials that can serve as
technologies and applications [4–6]. Platinum-based catalysts have efficient catalysts for HER and potentially replace platinum is a chal­
historically been the most effective in the HER process; however, their lenging scientific undertaking. This effort is backed by dedication on the
high cost and limited availability have prompted scientists to explore behalf of the worldwide scientific community to ongoing research and
alternative materials that can be used in sustainable energy systems innovation to establish a sustainable hydrogen economy.
[7–9]. In this respect, Transition Metal Dichalcogenides (TMDs), such as In the field of material science, the introduction of MoSi2N4 and

* Corresponding author.
E-mail address: [email protected] (G. Surucu).

https://doi.org/10.1016/j.ijhydene.2024.06.304
Received 21 April 2024; Received in revised form 4 June 2024; Accepted 21 June 2024
0360-3199/© 2024 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and
similar technologies.
F. Himmet et al. International Journal of Hydrogen Energy 78 (2024) 761–772

Fig. 1. The side and top views of the crystal structures of the (a) WSi2N4, (b) WGe2N4, and (c) Janus WSiGeN4 monolayers.

WSi2N4 has been a significant advancement, specifically in the exami­ This study casts a spotlight on the WSi2N4 and WGe2N4 monolayers
nation of 2D-layered materials. The production of these materials by alongside their Janus counterpart, WSiGeN4, through the meticulous
chemical vapor deposition is a unique process since they do not possess lens of Density Functional Theory. The concept of Janus materials—so
the usual three-dimensional parent structures commonly seen in such named for their intrinsic mirror asymmetry—opens the door to a realm
materials [17]. This milestone has sparked a surge of research into the of properties poised to revolutionize photocatalytic water splitting. The
2D MA2Z4 system, exploring its complex structure and diverse features. present investigation involves a careful optimization of the structures of
The MA2Z4 family is renowned for its wide-ranging features throughout WSi2N4 and WGe2N4 monolayers, as well as the Janus WSiGeN4 mono­
the electrical, optical, and mechanical domains [18–20]. Therefore, the layer. By doing so, we establish a strong basis for our stability assess­
primary objective of future studies in this field appears to be enhancing ments and engage in comprehensive discussions regarding the
the electronic structure within this group to utilize distinct physical revolutionary modifications observed in the Janus structure. By
properties; among them, modifiable Rashba spin splitting, which has employing a systematic approach to electronic property analysis that
significant promises for spintronic applications. Furthermore, the MA2Z4 combines the PBE and HSE methodologies, we are able to not only
system has demonstrated a modifiable non-linear optical reaction, analyze electronic properties, but also to ensure that the obtained
which creates opportunities for cutting-edge technological uses and es­ electronic band gaps correspond to the ideal spectrum required for
tablishes these materials as crucial components in future technological photocatalytic water splitting. In addition to conducting structural and
advancements [19]. electronic assessments, our research delves into the critical comparison
Expanding upon this basis, it becomes more and more compelling to between the minimum levels of the conduction and valence bands and
investigate the unexplored capabilities of MA2Z4 materials beyond their the potentials for water oxidation and reduction. To ensure the precise
current known uses. Although the electrical, optical, and mechanical measurement of photocatalytic efficiency, we take into account the pH
properties of these materials have been thoroughly examined, the dependencies. The inquiry is further broadened to include the optical
septuple-atomic-layer structure, which is exclusive to these materials, characteristics, thereby providing valuable insights into the optical ap­
suggests the existence of a large, unknown area of photocatalytic ac­ peal exhibited by these monolayers.
tivity. Considering the pressing need to discover sustainable energy This investigation delves into the intricate domains of WSi2N4,
solutions, it is not only timely, but imperative to investigate these ma­ WGe2N4, and their Janus variant, WSiGeN4. Ab Initio Molecular Dy­
terials for their potential use in water-splitting photocatalysis and namics (AIMD) is employed to conduct an unprecedented in-depth
hydrogen evolution electrocatalysis. The inherent structural benefits of investigation into these materials, which were previously examined
MA2Z4 materials, particularly considering the potential of producing not only with respect to their photocatalytic capabilities, but also to
Janus 2D materials by replacing the A element, point to a future filled their elastic and dynamic properties. This concentrated inquiry unveils
with invention and exploration [3,19,21,22]. the novel aspects of these substances, with the potential of Janus

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Table 1
The lattice parameter (a in Å), bond lengths (dW-X, dX-N in Å and X is Si and Ge for Wsi2N4 and Wge2N4, respectively), cohesive energy (Ecoh in eV/atom), elastic
constants (C11 and C12 in N/m), Young’s modulus (Y2D in N/m), shear modulus (G2D in N/m), and Poisson’s ratio (ν) for the WSi2N4, WGe2N4, and Janus WSiGeN4
monolayers.
Monolayer a dW-N dX-N Ecoh C11 C12 Y2D G2D ν
WSi2N4 2.94 2.12 1.77 − 1.43 549.84 141.05 513.65 204.39 0.26
2.91 [44] 2.10 [44] 1.75 [44]
2.91 [45]
WGe2N4 3.07 2.16 1.88 − 0.61 432.97 128.61 394.77 152.18 0.30
3.02 [44] 2.12 [44] 1.85 [44]
WSiGeN4 3.00 2.14 1.80 (Si–N) − 1.00 487.76 133.92 450.99 176.92 0.27
2.97 [46] 1.85 (Ge–N)

Fig. 2. The phonon dispersion curves of the (a) WSi2N4, (b) WGe2N4, and (c) Janus WSiGeN4 monolayers.

structures for advanced photocatalytic applications being particularly obtained using the gamma-centered scheme [28]. The valence electron
emphasized. Our investigation into these complex particulars aims to configuration of the elements in these monolayers are considered as
establish a foundation for groundbreaking sustainable energy technol­ 5d46s2, 3s23p2, 4s24p2, and 2s22p3 for the W, Si, Ge, and N atoms,
ogies, signifying a substantial progression in the comprehension and respectively. The calculations are performed until an energy conver­
implementation of these unprecedented 2D materials. gence criterion of 10− 5 eV per unit cell and a force convergence criterion
of 10− 4 eV/Å are reached. In addition, the vacuum space of 15 Å is
2. Computational methods included to prevent any interactions among the layers. The mechanical
stabilities of these monolayers are examined with the determination of
In this study, the WSi2N4, WGe2N4 and Janus WSiGeN4 monolayers the elastic constants using the energy-strain method implemented in the
are examined using the Vienna Ab-initio Simulation Package (VASP) ELASTOOL program [29,30]. The dynamical stabilities of these mono­
[23,24], which is based on Density Functional theory (DFT). The cal­ layers are determined with phonon dispersion curves obtained using the
culations are performed using Generalized Gradient Approximation Phonopy program [31,32], which employs the linear response method.
(GGA) with Perdew-Burke-Ernzerhof (PBE) functional [25] for the ex­ The electronic band gaps are obtained using the PBE method, whose
change and correlation terms of the electron-electron interactions, and underestimation of the band gaps is well-known in the literature.
the Projector Augmented Wave (PAW) method [26,27] for the Therefore, the Heyd–Scuseria–Ernzerhof (HSE) hybrid functional [33] is
electron-ion interactions. The monolayers are optimized using an energy employed to obtain more accurate band gaps. For the HSE method, the
cut-off for the plane waves as 610 eV, and the k-points as 18 × 18 × 1, screened HSE06 hybrid functional is considered with a 0.2 Å− 1 screening

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Fig. 3. The total energy for the (a) WSi2N4, (b) WGe2N4, and (c) Janus WSiGeN4 monolayers as a function of time during AIMD calculations.

parameter, and the exchange part is mixed with 25% of the exact the machine-learned force field (MLFF) implemented in VASP [38,39].
non-local Hartree-Fock exchange [34]. The band structure visualizations The descriptors based on the Gaussian representation of atomic distri­
are performed using the Sumo tools [35]. In addition, the ab-initio butions [38,40] are used for the description of the machine-learned
molecular dynamics calculations are performed using a 4 × 4 × 1 potential energy surface. Furthermore, the target properties including
supercell at zero pressure and 300 K temperature using the dynamical energy, forces, and stress tensor components are obtained with Bayesian
variables as the atomic positions and lattice parameters. The Langevin linear regression [39,41], which yields reliable estimates. The crystal
thermostat [36,37] is employed with 20 ps− 1, 15 ps− 1, 15 ps− 1, 8 ps− 1, visualizations are obtained using the VESTA program [42].
and 12 ps− 1 atomic frictions for W, Si, Ge, N atoms and lattice frictions,
respectively. The Verlet algorithm is applied to integrate the equations 3. Structural and stability analysis
of motion related to the ions with a 2 fs time step. For the AIMD cal­
culations, the k-points are taken as 3 × 3 × 1. The AIMD calculations are The WSi2N4 and WGe2N4 monolayers belong to the MA2Z4 family,
computationally expensive and time-consuming, encouraging to use of and the WSiGeN4 is the Janus structure of this family. Fig. 1 shows the

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Fig. 4. The temperature for the (a) WSi2N4, (b) WGe2N4, and (c) Janus WSiGeN4 monolayers as a function of time during AIMD calculations.

side and top views of the crystal structures of these monolayers. The consistent with the bond lengths of the WSi2N4 and WGe2N4 monolayers.
MA2Z4 family is a seven-layer system, and Fig. 1 shows the distances The cohesive energy calculations are performed for these monolayers
between layers as well. These monolayers are optimized, and the lattice using the equation given in Ref. [43]. The obtained cohesive energy
constants and the bond lengths are listed in Table 1. Accordingly, the values are listed in Table 1, and the results show that these monolayers
obtained results are consistent with the available literature. The lattice are energetically stable.
parameter increases when the Si atom is replaced with a Ge atom. After determining the energetic stability of the WSi2N4, WGe2N4 and
Additionally, the lattice parameter of the Janus WSiGeN4 monolayer is Janus WSiGeN4 monolayers, the elastic constants are calculated using
in between the lattice parameters of the WSi2N4 and the WGe2N4 the energy-strain method implemented in the ELASTOOL program and
monolayers. The bond length between the W and N atoms is similar for listed in Table 1. Fig. S1 in the Supplementary File shows the change in
these monolayers, while the bond length between the X and N atoms strain energy density as a function of strain. As can be seen from the
increases when the X atom changes from the Si atom to the Ge atom. figure, higher strain energy densities are obtained for the − 0.06 strains.
Furthermore, for the Janus WSiGeN4 monolayer, there are both bond These monolayers have a hexagonal structure, and the required elastic
lengths between the Si and N atoms and the Ge and N atoms which are constants are C11 and C12 for any 2D hexagonal structure [47]. In

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Fig. 5. The electronic band structures for the (a) WSi2N4, (b) WGe2N4, and (c) Janus WSiGeN4 monolayers obtained using the HSE method.

addition, to be a mechanically stable 2D structure, the Born stability of these monolayers are determined using the phonon dispersion curves
criteria [47,48] must be satisfied which are C11 > 0 and C11>|C12| for as shown in Fig. 2. These curves are obtained using the linear response
hexagonal structures. According to Table 1, the elastic constants of these method with a 2 × 2 × 1 super cell. The phonon dispersion curves have
monolayers satisfy the Born stability criteria to represent mechanical no imaginary frequencies, known as soft modes, indicating the dynam­
stability. Table 1 also lists the Young’s modulus (Y2D), shear modulus ical stability of these monolayers as shown in Fig. 2. The phonon density
(G2D), and Poisson’s ratio (ν) for these monolayers. The Y2D is the of states (DOS) are shown in Fig. 2. Accordingly, the N atoms in these
in-plane stiffness of these monolayers and, according to the table, the monolayers contribute more to the higher frequencies, while the W, Si,
Y2D decreases as the Si atom changes to the Ge atom. What is more, the and Ge atoms contribute more to the lower frequencies.
Y2D of the Janus WSiGeN4 monolayer is in between the Y2D of the WSi2N4 After the considerations pertaining to the thermodynamic, me­
and WGe2N4 monolayers. When the calculated Y2D values are compared chanic, and dynamic stabilities of these monolayers, the ab-initio mo­
with the other 2D materials in the literature [49–51], it is found that lecular dynamics (AIMD) calculations with machine learning force fields
these monolayers have high in-plane stiffness. The behavior of the G2D is (MLFF) are performed. Figs. 3 and 4 show the total energy and tem­
similar to that of the Y2D of these monolayers. The ν is defined by the perature change as a function of time for these monolayers. As can be
ratio of the transverse strain to the longitudinal strain, reflecting the seen from the figures, the total energy and temperature oscillate within a
response to the uniaxial strain. As listed in Table 1, the ν values increase small range, implying that these monolayers are stable at 300 K. The
as the Si atom changes to the Ge atom. The ν of the Janus WSiGeN4 initial and final crystal configurations are shown in Figs. 3 and 4, which
monolayer is in between the ν of the WSi2N4 and WGe2N4 monolayers. represent no significant deformations in these monolayers. The AIMD
Furthermore, the polar plots for ν and Y2D are presented in Fig. S2 in the calculations with MLFF point to the thermal stability of these mono­
Supplementary File for the WSi2N4, WGe2N4 and Janus WSiGeN4 layers, which also possess mechanical and dynamic stabilities.
monolayers along the different lattice planes. As can be seen from this
figure, these monolayers have an anisotropic character in ν and Y2D
along the different lattice planes. Additionally, the dynamical stabilities

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Fig. 6. The electrostatic potential profiles along the thickness of the (a) WSi2N4, (b) WGe2N4, and (c) Janus WSiGeN4 monolayers obtained using the HSE method.

Fig. 7. The schematic representation of the conduction band minimum (CBM) and the valence band maximum (VBM) for the (a) WSi2N4, (b) WGe2N4, and (c) Janus
WSiGeN4 monolayers obtained using the HSE method.

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Fig. 8. The schematic representation of the conduction band minimum (CBM) and the valence band maximum (VBM) for the (a) WSi2N4, (b) WGe2N4, and (c) Janus
WSiGeN4 monolayers obtained using the HSE method with the reduction and oxidation potentials of photocatalytic water splitting as a function of pH. The pho­
tocatalytic active region is highlighted with a yellow rectangle. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web
version of this article.)

4. Electronic and optical properties Ref. [46], showing that the results in this study are consistent with the
literature. Consequently, the band gap requirement for photocatalytic
The electronic band structures of the WSi2N4, WGe2N4 and Janus water splitting is satisfied for these monolayers.
WSiGeN4 monolayers are obtained using both the PBE and HSE methods. The work function is a critical parameter for semiconductors, and it
The PBE method underestimates the band gap of the semiconductors as is defined as the required minimum energy for the release of an electron
it is well-known in the literature; as such, the HSE method is employed [52]. The work functions for these monolayers are calculated using
to obtain the band gaps consistent with the experimental ones. Fig. S3 Equation (1) [53].
shows the band structures obtained using the PBE method where the
W = Evac − EF (1)
WSi2N4, WGe2N4 and Janus WSiGeN4 monolayers have 2.07 eV, 1.16 eV,
and 1.59 eV indirect band gaps, respectively. In addition, Fig. S4 shows In Equation (1), W, Evac, and EF correspond to the work function, the
the corresponding density of states (DOS) for these monolayers. Ac­ vacuum level electrostatic potential, and the Fermi level, respectively.
cording to the figure, the most contribution above the Fermi level comes Fig. 6 shows the obtained electrostatic potential profiles along the
from the d orbitals of the W atoms, while the p orbitals of N atoms thickness of these monolayers. The obtained work functions are 4.70 eV,
contribute more between − 6 eV and − 2 eV, while the d orbitals of the W 4.79 eV, and 4.94 eV for the WSi2N4, WGe2N4 and Janus WSiGeN4
atoms contribute more between − 2 eV and 0 eV below the Fermi level. monolayers, respectively. In addition, the Janus WSiGeN4 monolayer
Fig. 5 shows the electronic band structures for these monolayers ob­ has a mirror asymmetry, which results in a work function difference
tained using the HSE method. The WSi2N4, WGe2N4 and Janus WSiGeN4 between the top and bottom surfaces of the monolayer. This difference
monolayers have 2.68 eV, 1.65 eV, and 2.12 eV indirect band gaps, suggests an electrostatic field across the monolayers and, possibly, a
respectively. In addition, the valence band maximum is at the Γ point, considerable impact on their carrier dynamics [54].
and the conduction band minimum is at the K point, as seen in Fig. 5. A good photocatalyst should meet both the band gap requirement
The band gap values decline when the Si atom changes to a Ge atom, and and the energy levels for the reduction and oxidation potentials. The
the Janus WSiGeN4 monolayer has a band gap value between the band conduction band minimum (CBM) should be more positive than the
gaps of the WSi2N4 and WSiGeN4 monolayers. In the literature, the band reduction potential of the H+/H2 reaction which is − 4.44 eV, while the
gaps of the WSi2N4 and WGe2N4 monolayers are found as 2.68 eV and valence band maximum (VBM) should be more negative than the
1.53 eV in Ref. [44], and 2.57 eV and 1.51 eV in Ref. [22], respectively; oxidation potential of the O2/H2O reaction which is − 5.67 eV with
whereas, the band gap for the Janus WSiGeN4 monolayer is 2.02 eV in respect to the vacuum level [55]. Fig. 7 shows the schematic

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Fig. 9. (a) Real and imaginary parts of the dielectric function, (b) absorption, (c) reflection, and (d) transmission spectra of the WSi2N4 monolayer from 0 to 6 eV (the
visible light region is marked with a rainbow bar).

representation of the CBM and VBM levels for the WSi2N4, WGe2N4 and purpose, the frequency-dependent dielectric function is determined, as
Janus WSiGeN4 monolayers obtained using the HSE method. According given in Equation (4) [57].
to Fig. 7(a) and (b), the WSi2N4 and WGe2N4 monolayers satisfy the CBM
ε(ω) = ε1 (ω) + iε2 (ω) (4)
requirement, while the VBM is more positive than the required oxidation
potential for pH = 0 conditions. However, the Janus WSiGeN4 mono­ In Equation (4), ε1 (ω) is the real and ε2 (ω) is the complex part of the
layer satisfies the requirements for both CBM and VBM for pH = 0 con­ dielectric function. Using this function, the absorption (A), the reflection
ditions, as shown in Fig. 7(c). In addition, a potential catalyst must also (R), and the transmission (T) can be obtained. Since the monolayers are
operate over a wide pH range. The redox potential of water splitting is 2D materials, the parameters are given in normalized values because of
directly proportional to pH, and the pH-dependent reduction and the slab thickness, and it should be noted that the summation of the A +
oxidation potentials are given in Equation (2) and Equation (3), R + T must be equal to 1. Fig. 9(a), Fig. 10(a), and Fig. 11(a) show the
respectively [56]. Using these equations, the pH dependent reduction ε1 (ω) and ε2 (ω) along the xx and yy directions for the WSi2N4, WGe2N4
and oxidation potentials are determined and the obtained CBM and VBM and Janus WSiGeN4 monolayers, respectively. The real part of the
are compared, as shown in Fig. 8. According to this analysis, the WSi2N4 dielectric function has 4.70, 5.88, and 5.14 values at 0 eV for the
monolayer also satisfies the requirements for both CBM and VBM for pH WSi2N4, WGe2N4, and Janus WSiGeN4 monolayers, respectively. In
= 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14. For the WGe2N4 monolayer, addition, the maximum peaks of the real part of the dielectric function is
CBM and VBM are levels with appropriate potentials at pH = 1, 2, 3, 4, 5, in the visible region for the WSi2N4 and Janus WSiGeN4 monolayers.
6, and 7. The Janus WSiGeN4 monolayer has already satisfied the CBM When the spectrum of the real part of the dielectric function is analyzed,
and VBM requirements at pH = 0, and it also has CBM and VBM levels there are no negative values indicating the semiconducting character of
with appropriate potentials at pH = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and these monolayers between 0 and 6 eV [58]. The imaginary part of the
13. These detailed analyses show that these monolayers are promising dielectric function is also shown in the figures related to the optical band
candidates for photocatalytic water splitting. gaps. As can be seen from the figures, the obtained optical band gaps are
2.04 eV, 1.11 eV, and 1.55 eV for the WSi2N4, WGe2N4, and Janus
E H+ = (− 4.44 + pH × 0.059)eV (2)
/H2 WSiGeN4 monolayers, respectively. These results are consistent with the
electronic band gaps obtained using the GGA-PBE method.
E O2 = (− 5.67 + pH × 0.059)eV (3) Figs. 9(b)–. 10(b) and 11(b) show the absorption along the xx and yy
/H2 O
directions for the WSi2N4, WGe2N4, and Janus WSiGeN4 monolayers,
In addition to the detailed electronic characteristics of these mono­ respectively. The absorption coefficient refers to the absorption energy
layers presented, the optical properties are studied to reveal the per­ when light passes through a material. These monolayers have high ab­
formance of these monolayers for photocatalytic water splitting. For this sorption coefficients, which is crucial for photocatalytic water splitting,

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Fig. 10. (a) Real and imaginary parts of the dielectric function, (b) absorption, (c) reflection, and (d) transmission spectra of the WGe2N4 monolayer from 0 to 6 eV
(the visible light region is marked with a rainbow bar).

and they also have a significant absorption in the visible range. In of the WGe2N4 and WSi2N4 monolayers are advantageous. These band
addition, the maximum peaks of the absorption is in the ultraviolet re­ gaps are even more precisely optimized in the Janus WSiGeN4 mono­
gion, as can be seen from the figures. layer to meet the criteria necessary for efficient photocatalytic water
Figs. 9(c)–. 10(c) and 11(c) show the reflection along the xx and yy splitting. The superior photocatalytic activity of the Janus WSiGeN4
directions for the WSi2N4, WGe2N4, and Janus WSiGeN4 monolayers, monolayer is demonstrated by electronic analyses, which highlight its
respectively. The reflectivity is defined as the reflected light from a exceptional band alignment. This alignment fulfills the conduction and
material that is irradiated with light. These monolayers have zero valence band criteria, necessary for efficient redox reaction levels across
reflectivity when the photon energy is zero, and reflectivity increases as a wide pH range. The results of the stability evaluations, which include
the photon energy increases. The maximum reflectivity is obtained at the thermodynamic, mechanical, and dynamic stabilities, demonstrate
higher photon energies. the structural integrity of these monolayers. Furthermore, their thermal
Figs. 9(d)–. 10(d) and 11(d) show the transmission along the xx and stability at 300 K is confirmed through AIMD simulations. This char­
yy directions for the WSi2N4, WGe2N4, and Janus WSiGeN4 monolayers, acteristic is essential for real-world implementations as it guarantees the
respectively. The transmission is related to how much light passes structural soundness of the materials while in use. The notable absorp­
through a material without reflection or absorption. As can be seen from tion capabilities of the monolayers in the visible spectrum are revealed
the figures, the transmission is high for lower photon energies, while the through optical property analysis, underscoring their appropriateness
transmission declines at high photon energies. This result is consistent for utilizing solar energy in photocatalytic processes.
with the absorption spectra. The research findings suggest a potentially fruitful avenue for uti­
lizing these innovative 2D materials in environmentally friendly energy
5. Conclusion applications, specifically in the realm of water splitting for the hydrogen
fuel production. In summary, the Janus WSiGeN4, WGe2N4, and WSi2N4
This study embarks on an exploratory journey into the photocatalytic monolayers emerge as highly promising contenders for photocatalytic
efficiencies of the WSi2N4, WGe2N4, and Janus WSiGeN4 monolayers, water splitting due to their exhibited stability and favorable electronic
employing a rigorous framework of Density Functional Theory com­ and optical characteristics. The implications of the results obtained in
bined with Ab-initio Molecular Dynamics (AIMD) simulations. The the present paper lay the groundwork for additional investigation and
structural, electronic, and optical properties of these 2D materials are progress in this domain, potentially yielding substantial progressions in
profoundly elucidated by the exhaustive investigations carried out here. the pursuit of environmentally favorable and sustainable energy
The obtained information supports their potential to propel forward the sources.
field of photocatalytic water splitting for hydrogen production. The
primary discoveries of our study indicate that the electronic band gaps

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Fig. 11. (a) Real and imaginary parts of the dielectric function, (b) absorption, (c) reflection, and (d) transmission spectra of the Janus WSiGeN4 monolayer from 0 to
6 eV (the visible light region is marked with a rainbow bar).

CRediT authorship contribution statement Appendix A. Supplementary data

F. Himmet: Writing – original draft, Investigation, Data curation. G. Supplementary data to this article can be found online at https://doi.
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