Monolayer MoSi2N4-x as promising electrocatalyst for hydrogen evolution reaction: A DFT prediction

doi:10.1016/j.jmst.2021.06.004

Abstract

Abstract:

The density functional theory (DFT) calculations have been performed to investigate the catalytic properties of monolayer MoSi₂N₄ for hydrogen evolution reaction (HER). The DFT results show that similar to the majority of other two-dimensional (2D) materials, the pristine MoSi₂N₄ is inert for HER due to its weak affinity toward hydrogen, while monolayer MoSi₂N_4-_x (x = 0‒0.25) exhibits the highly desirable HER catalytic activities by introducing surface nitrogen vacancy (NV). The predicted HER overpotential (0‒60 mV) of monolayer MoSi₂N_4-_x is lower than that (90 mV) of noble metal Pt, when the concentration of surface NV is lower than 5.6%. Electronic structure calculations show that the spin-polarized states appear around the Fermi level after introducing surface NV, thus making the surface NV on 2D MoSi₂N₄ a quite suitable site for HER. Moreover, the HER activity of MoSi₂N_4-_x is highly dependent on the surface NV concentration, which can be further related to the center of Si-3p band. Our results demonstrate that the newly discovered 2D MoSi₂N₄ can be served as a promising electrocatalyst for HER via appropriate defect engineering.

Key words: Hydrogen evolution reaction, Electrocatalyst, 2D material, MoSi₂N₄, Surface nitrogen vacancy

Wangwang Qian, Zhe Chen, Jinfeng Zhang, Lichang Yin. Monolayer MoSi₂N_4-_x as promising electrocatalyst for hydrogen evolution reaction: A DFT prediction[J]. J. Mater. Sci. Technol., 2022, 99: 215-222.

Figures/Tables 8

Fig. 1. (a) Top and side views of the 4 × 4 supercell of pristine MoSi2N4 with a hydrogen atom adsorption. Three possible sites for atomic hydrogen adsorption on monolayer MoSi2N4, including the top site of surface Si atom, the top site of surface N atom and the center of surface N-Si six-member ring, are labelled by numbers 1, 2 and 3, respectively. (b) Top and side views of the 4 × 4 supercell of defective MoSi2N4 with a surface NV. The surface NV is highlighted by red dotted circle and three Si atoms around the surface NV is marked by three green dashed circles. (c) Top and side views of one hydrogen atom adsorption on the 4 × 4 supercell of defective MoSi2N4 with one surface NV. The Mo, Si, N and H atoms are represented by purple, blue, grey and red balls, respectively.

Fig. 2. (a) The formation energy of surface NV in defective MoSi2N4 with different NV concentrations under the N-rich condition. (b) The formation energies for surface NV (red line) and inner NV (blue line) as a function of the chemical potential of N.

Table 1 The adsorption energies (ΔEH*), the ΔZPE-TΔS term, the Gibbs free energies (ΔGH*) of atomic hydrogen adsorption on monolayer MoSi2N4 with different surface NV concentrations (CNV), and the band gap (Eg) of corresponding defective MoSi2N4. The defective MoSi2N4 with CNV of 12.5% and 8.3% are metallic.

Supercell	C_NV	ΔE_H*(eV)	ΔZPE-TΔS(eV)	ΔG_H*(eV)	E_g(eV)
2 × 2	12.5%	0.37	0.23	0.60	‒
2 × 3	8.3%	-0.07	0.24	0.17	‒
3 × 3	5.6%	-0.18	0.24	0.06	0.38
3 × 4	4.2%	-0.23	0.24	0.01	0.66
4 × 4	3.1%	-0.24	0.24	0.00	0.74
5 × 5	2.0%	-0.27	0.24	-0.03	0.82

Fig. 3. The free energy diagram of (a) the HER on defective MoSi2N4 with different NV concentrations and (b) the HER on defective MoSi2N4 with 3.1% NV concentration (4 × 4 supercells) at different hydrogen coverages.

Fig. 4. The spin-polarized band structures of (a) the pristine MoSi2N4, (b?e) the defective MoSi2N4 with CNV of 12.5%, 5.6%, 3.1% and 2.0%, and (f) the defective MoSi2N4 with CNV of 3.1% after one hydrogen adsorption. The corresponding band gap values of semiconducting systems are presented. The Fermi levels are set to be 0 eV and denoted by black dashed lines for all cases.

Fig. 5. The spin-polarized DOS plots for (a) the pristine MoSi2N4, (b?e) the defective MoSi2N4 with CNV of 12.5%, 5.6%, 3.1% and 2.0%, and (f) the defective MoSi2N4 with CNV of 3.1% after one hydrogen adsorption. The Fermi levels are set to be 0 eV and denoted by black dotted lines for all cases.

Fig. 6. LDOS plots of three Si atoms around the surface NV in defective MoSi2N4 with CNV of (a) 12.5%, (b) 5.6%, (c) 3.1% and (d) 2.0%. The Fermi levels denoted by black dotted lines are set to be 0 eV. The Si-3p band centers are indicated by red dotted lines and the corresponding energies are also given.

Fig. 7. The relationship between the Si-3p band center (εSi-3p) and the Gibbs free energy of atomic hydrogen adsorption (ΔGH*) on defective MoSi2N4 with different CNV. After fitting, a linear function between εSi-3p and ΔGH* can be obtained and is also presented.

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Monolayer MoSi₂N_4-_x as promising electrocatalyst for hydrogen evolution reaction: A DFT prediction

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