Research on Adjusting Electronic Transport with MoSi2N4/ZrS2(HfS2) II-Type Heterojunction for Photocatalytic Hydrogen Production

doi:10.6023/A25010029

Abstract

With the gradual depletion of traditional energy sources, hydrogen energy as a clean energy source has gradually attracted people's attention. Among various hydrogen-production methods, semiconductor photocatalytic water splitting stands out as a promising approach due to its numerous advantages, including low-cost operation and environmental friendliness. The efficiency of photocatalytic hydrogen production is intricately linked to the electronic properties of photocatalysts. One of the key factors is the recombination of electrons and holes, which can significantly reduce the utilization of photo-generated carriers. Therefore, precisely and rationally regulating the transfer of photoelectrons has emerged as a crucial strategy to enhance hydrogen production efficiency. In this paper, the electronic structure, optical properties, interfacial properties, and carrier transport after illumination of the MoSi₂N₄/ZrS₂(HfS₂) heterojunction were studied by using first-principles and nonadiabatic molecular dynamics. The results show that the MoSi₂N₄/ZrS₂(HfS₂) heterojunction exhibits stronger light absorption capability in the visible region, the carrier mobility in the heterojunction is significantly higher than that in the single phase, and the electron-hole separation efficiency is also effectively improved. Additionally, the interfacial properties, which play a vital role in carrier transfer between different materials, and the carrier transport behavior after illumination are studied in detail. The research findings reveal that within the visible-light region, the MoSi₂N₄/ZrS₂(HfS₂) heterojunctions demonstrate enhanced light-absorption capabilities. Moreover, the carrier mobility within these heterojunctions is remarkably higher compared to their single-phase counterparts. This higher mobility promotes the rapid movement of electrons and holes, effectively improving the efficiency of electron-hole separation. As a result, more electrons can participate in the hydrogen production reaction, simultaneously, the heterojunctions exhibit a higher hydrogen evolution efficiency. The ΔG_H* value in the hydrogen evolution reaction is lower than that of their single-component materials. A lower ΔG_H* indicates that the reaction requires less energy input, which can effectively enhance the performance of photocatalytic water splitting for hydrogen production. Based on these experimental results, the paper elaborates on the corresponding mechanisms in detail, aiming to provide in-depth insights into the underlying principles. This study offers a solid theoretical foundation for the further development of highly efficient two-dimensional heterojunction photocatalysts.

Key words: photocatalytic water splitting, MoSi₂N₄/ZrS₂(HfS₂), type-II heterojunction, first-principle, nonadiabatic molecular dynamics (NAMD)

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Ye Tian, Boyao Zhang, Junyu Chen, Mengxin Ji, Hao Ren, Yuhua Chi. Research on Adjusting Electronic Transport with MoSi₂N₄/ZrS₂(HfS₂) II-Type Heterojunction for Photocatalytic Hydrogen Production[J]. Acta Chimica Sinica, 2025, 83(5): 498-509.

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Fig. & Tab. 13

Figure 1. Electron transfer mechanism and catalytic performance of MoSi2N4/ZrS2(HfS2) heterojunction under illumination

Figure 2. Top and side views of the lattice structures of (a) MoSi2N4, (b) ZrS2, and (c) HfS2 monolayers

Figure 3. The AIMD simulation results of (a) MoSi2N4, (d) ZrS2, and (g) HfS2 at 300 K, electronic band structures of (b) MoSi2N4, (e) ZrS2 and (h) HfS2, and the single layer phonon spectra of (c) MoSi2N4, (f) ZrS2 and (i) HfS2

Figure 4. Top view (a) and side view (b) of the MoSi2N4/ZrS2(HfS2) heterojunctions, the AIMD simulation results of MoSi2N4/ZrS2 (c) and MoSi2N4/HfS2 (d) heterojunctions at 300 K

Figure 5. The band structure of MoSi2N4/ZrS2 (a) and MoSi2N4/HfS2 (d) heterojunctions. The Electrostatic potential diagrams of MoSi2N4/ZrS2 (b) and MoSi2N4/HfS2 (e) vdW heterojunctions along the z direction. The average plane charge density diagrams of MoSi2N4/ZrS2 (c) and MoSi2N4/HfS2 (f) heterojunctions (The blue and pink areas represent electron accumulation and consumption, respectively)

Figure 6. Band edges of MoSi2N4/ZrS2, MoSi2N4/HfS2 vs vacuum level

Figure 7. (a) Energy-time variation diagram near the Fermi level of MoSi2N4/ZrS2, (b) subcarrier position-time diagram of electrons, holes, and electron-hole recombination pathways, (c) averaged values of Nonadiabatic coupling (NAC) between different states. Time-dependent energy change for (d) electron transfer, (e) electron-hole recombination, and (f) hole transfer (The color bar on the right represents the distribution of electrons or holes in different energy states, and the dashed line represents the average electron or hole energy)

Figure 8. (a) Energy-time variation diagram near the Fermi level of MoSi2N4/HfS2, (b) Subcarrier position-time diagram of electrons, holes, and electron-hole recombination pathways. (c) Averaged values of NAC between different states. Time-dependent energy change for (d) electron transfer, (e) electron-hole recombination, and (f) hole transfer (The color bar on the right represents the distribution of electrons or holes in different energy states, and the dashed line represents the average electron or hole energy)

单层	方向	载波类型	C/(N•m^–1)	E_d/eV	m* (m₀)^a	μ/(cm²•V^–1•s^–1)
ZrS₂	x	e	5.191	–1.29	1.971	178.785
	x	h	5.191	–4.94	–1.719	16.119
	y	e	6.788	–1.95	0.657	927.459
	y	h	6.788	–4.83	–0.573	198.751
MoSi₂N₄	x	e	38.788	–16.57	2.236	6.342
	x	h	38.788	–6.59	–4.917	8.303
	y	e	38.964	–12.62	0.745	98.861
	y	h	38.964	–6.54	–1.639	75.998
HfS₂	x	e	7.072	–1.59	1.855	181.751
	x	h	7.072	–5.17	–1.767	19.022
	y	e	7.302	–1.58	0.618	1701.824
	y	h	7.302	–5.06	–0.589	184.695
MoSi₂N₄/ ZrS₂	x	e	50.568	–4.58	0.698	1112.332
	x	h	50.568	–8.43	–0.423	890.465
	y	e	50.807	–4.58	0.233	10029.576
	y	h	50.807	–8.85	–0.141	7299.525
MoSi₂N₄/ HfS₂	x	e	52.350	–4.54	0.689	1200.605
	x	h	52.350	–5.35	–1.340	228.467
	y	e	52.556	–4.52	0.229	11027.355
	y	h	52.556	–5.36	–0.447	2058.138

Table 1. Carrier mobility of MoSi2N4/ZrS2(HfS2) heterojunction and its single layer along the x and y directions

Figure 9. Light absorption coefficients of (a) MoSi2N4 and ZrS2 monolayers, MoSi2N4/ZrS2 heterojunction, (b) MoSi2N4 and HfS2 monolayers, MoSi2N4/ HfS2 heterojunction

Structure	χ(H₂)/eV	χ(O₂)/eV	E_g/eV (HSE)	η_abs/%	η_cu/%	η_STH/%
MoSi₂N₄	0.96	0.08	2.27	25.58	15.15	3.88
MoSi₂N₄/ZrS₂	0.81	1.01	1.39	67.73	60.44	40.94
MoSi₂N₄/HfS₂	0.85	1.08	1.66	53.08	54.85	29.12

Table 2. ηSTH of the MoSi2N4 and MoSi2N4/ZrS2(HfS2)

Figure 10. The STH efficiency of the GeS(SiH)/GeSe, Zr2CO2(WSSe)/ WSe2 and MoSi2N4/ZrS2(HfS2)

Figure 11. Free energy diagram of HER on the surface of MoSi2N4, ZrS2, HfS2 monolayers and MoSi2N4/ZrS2(HfS2) heterojunction

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MoSi₂N₄/ZrS₂(HfS₂) II型异质结调节电子传输用于光催化制氢的研究

Research on Adjusting Electronic Transport with MoSi₂N₄/ZrS₂(HfS₂) II-Type Heterojunction for Photocatalytic Hydrogen Production

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MoSi2N4/ZrS2(HfS2) II型异质结调节电子传输用于光催化制氢的研究