Theoretical Construction of Hittorf’s Violet Phosphorene/SnS2 van der Waals Heterojunction as Direct Photocatalyst for Overall Water Splitting

doi:10.6023/A24120382

Abstract

Seeking efficient direct Z-scheme heterojunction photocatalysts for water splitting and hydrogen production is an effective way to solve energy crises and environmental problems. Here, we used first-principles calculations based on density functional theory (DFT) to systematically study the electronic structure, optical properties, and photocatalytic performance of the constructed two-dimensional Hittorf’s violet phosphorene (HP)/SnS₂ heterojunction. To achieve more accurate results, the Heyd-Scuseria-Ernzerhof (HSE06) calculations are performed to verify the results, especially for the calculations of the electronic structure and the optical properties. The hybrid functional computational results showed that the HP/SnS₂ heterojunction is a direct bandgap semiconductor with a bandgap value of 1.30 eV. The staggered band structure and the built-in electric field induced by interlayer charge transfer result in a direct Z-scheme carrier migration mechanism, giving it a stronger oxidation-reduction ability to trigger water-splitting reactions. Under illumination conditions, the external voltage provided by the photogenerated electrons on the HP side and the photogenerated holes on the SnS₂ side can significantly reduce the Gibbs free energy of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which is substantially lower than Gibbs free energy required for single-layer HP and two-dimensional SnS₂ to catalyze the same reaction, resulting in excellent hydrogen evolution activity and oxygen evolution activity. In addition, theoretical calculations showed that biaxial strain can effectively regulate the photocatalytic ability and light absorption characteristics of HP/SnS₂ heterojunction. We found that at a strain of –10%, the HP/SnS₂ heterojunction exhibits the strongest light absorption ability under visible light, with a light absorption coefficient of up to 1.71×10⁶ cm^-1. By comparing the oxidation-reduction potentials of water, it was found that HP/SnS₂ heterojunction can meet the conditions for photocatalytic overall water splitting when the strain ranges from –10% to 8%. Its solar to hydrogen (STH) conversion efficiency can reach up to 54.90%, far exceeding the commercial requirement of 10%. In summary, HP/SnS₂ heterojunction is an excellent candidate material for overall photocatalytic water splitting under visible light.

Key words: Z-scheme heterojunction, photocatalytic overall water splitting, biaxial strain, density functional theory

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Yi-Lin Lu, Shengjie Dong, Fangchao Cui, Tingting Bo, Zhuo Mao. Theoretical Construction of Hittorf’s Violet Phosphorene/SnS₂ van der Waals Heterojunction as Direct Photocatalyst for Overall Water Splitting[J]. Acta Chimica Sinica, 2025, 83(4): 377-389.

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Fig. & Tab. 13

Figure 1. The top view of (a) HP monolayer and (b) SnS2 monolayer crystal structure. The electronic band structure calculated by HSE06 functional of (c) HP monolayer and (d) SnS2 monolayer

Figure 2. Top view (upper panel) and side view (down panel) of the HP/SnS2 heterojunction in four possible stacking configurations: (a) H1 pattern, (b) H2 pattern, (c) H3 pattern, and (d) H4 pattern

Figure 3. The ab initio molecular dynamics (AIMD) results of variations of total energy and temperature against the time for simulations at 300 K. The inset represents side views of the snapshots of the geometric structures before and after 3000 fs simulations for the H3 pattern

Figure 4. HSE06 level calculated (a) electronic band structure, (b) total and projected density of states, and (c) side view (left panel) and top view (right panel) of the charge densities of the VBM and the CBM of the HP/SnS2 heterojunction

Figure 5. (a) The electrostatic potentials of the HP monolayer, SnS2 monolayer, and the HP/SnS2 heterojunction, (b) planar-averaged electron density difference with z direction, and (c) the electron density difference of the HP/SnS2 heterojunction

Figure 6. Schematic diagram of direct Z-scheme carrier transfer mode and band edge position of the HP/SnS2 heterojunction

Figure 7. (a) The Gibbs free energy illustration of hydrogen evolution reaction (HER) on the HP monolayer and the HP surface of the HP/SnS2 heterojunction. The side views of the structures of H atom on (b) the HP monolayer and (c) the HP surface of the HP/SnS2 heterojunction

Figure 8. The Gibbs free energy illustration of oxygen evolution reaction (OER) on (a) the SnS2 monolayer and (b) the SnS2 surface of the HP/SnS2 heterojunction. The side views of the optimized geometries of OER intermediates on (c) the SnS2 monolayer and (d) the SnS2 surface of the HP/SnS2 heterojunction

Figure 9. Projected density of states and p-band center of (a) the P atoms of the HP monolayer and HP/SnS2 heterojunction, and (b) the S atoms of the SnS2 monolayer and the HP/SnS2 heterojunction

Figure 10. At HSE06 level, variations of the band gap and strain energy as a function of the biaxial strain in the HP/SnS2 heterojunction

Figure 11. At HSE06 level, the relation between the band edge positions of HP/SnS2 heterojunction and the redox potential of water splitting when biaxial strains are applied

Figure 12. At HSE06 level, (a) optical absorbance spectra of HP and SnS2 monolayers and the HP/SnS2 heterojunction; (b) optical absorbance spectra of HP/SnS2 heterojunction under diverse biaxial strains (left axis). The incident AM 1.5 G solar flux spectrum (right axis)[43]

Figure 13. At HSE06 level, the STH efficiency of the HP/SnS2 heterojunction under diverse biaxial strain

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希托夫紫磷烯/SnS₂范德华异质结作为直接全解水光催化剂的理论构建

Theoretical Construction of Hittorf’s Violet Phosphorene/SnS₂ van der Waals Heterojunction as Direct Photocatalyst for Overall Water Splitting

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希托夫紫磷烯/SnS2范德华异质结作为直接全解水光催化剂的理论构建