Sulfur-induced charge-site reconstruction and in-situ formed ZnO2 protection enable robust solar H2O2 production

doi:10.1016/S1872-2067(26)65124-8

Abstract

Abstract:

Solar-driven synthesis of hydrogen peroxide (H₂O₂) using semiconductor-based catalysts for practical applications is hindered by intrinsically inefficient separation and transfer of charge carriers, and rapid H₂O₂ decomposition. Herein, we designed a sulfur (S)-doped g-C₃N₄/ZnO Z-scheme heterojunction, wherein an amorphous ZnO₂ layer is in-situ formed during photocatalysis reaction (denoted as S-ZnO/ZnO₂@CN), to achieve robust H₂O₂ production. Mechanism analysis reveals that S doping enhances the built-in electric field to promote efficient charge carrier separation and induces sp²→sp³ hybridization reconstruction in g-C₃N₄ to create electron-rich active sites that accelerate O₂ reduction kinetics and stabilize the critical *OOH intermediates. Concurrently, the in-situ formed ZnO₂ layer on the S-doped ZnO surface dynamically passivates decomposition-prone sites through Zn-O₆ terminal coordination, spatially isolating reactive intermediates and suppressing H₂O₂ decomposition via Fenton-like cycle inhibition. The triple synergy between S-tailored charge dynamics, ZnO₂-enabled interfacial protection and strengthened Z-scheme built-in electric field maximizes charge separation and transfer while stabilizing the generation of H₂O₂, thereby resulting in a robust H₂O₂ production (13.8 mmol/(g·h), reaching 9 mmol/L within 2.5 h, apparent quantum yield: 32.4% at 365 nm). This work establishes a “triple-channel regulation” paradigm toward high activity with operational stability in solar-driven chemical synthesis.

Key words: Heterojunction photocatalyst, H₂O₂ production, Sustainable chemistry, Surface passivation, Hybridization engineering

Yuhang Sun, Xu Li, Zhongtian Zeng, Hua Wei, Yulong Zhao, Xiaoyan Cai, Liang Mao, Chang-Long Tan, Bo Shen, Yi-Jun Xu. Sulfur-induced charge-site reconstruction and in-situ formed ZnO₂ protection enable robust solar H₂O₂production[J]. Chinese Journal of Catalysis, 2026, 88: 207-217.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65124-8

https://www.cjcatal.com/EN/Y2026/V88/I9/207

Figures/Tables 5

Fig. 1. (a) Schematic illustration of the preparation route of S-ZnO/ZnO2@CN. (b) Schematic illustration of the in-situ formation of the ZnO2 protective layer. HRTEM images of S-ZnO@CN (c) and S-ZnO/ZnO2@CN (d). (e) High-resolution XPS spectra of Zn 2p and O 1s for S-ZnO@CN (before reaction) and S-ZnO/ZnO2@CN (after reaction). (f) XANES spectra of Zn foil, ZnO, ZnS, S-ZnO@CN and S-ZnO/ZnO2@CN.

Fig. 2. Photocatalytic H2O2 production over different samples: yield-time curves (a), comparison of yield in the first hour (b), optimization of sample parameter including S-doping, ZnO loading amount and sulfidation temperature (c), and cyclic stability test (d). (e) Wavelength dependence of AQY. (f) Decomposition of H2O2 over different samples. (g) Kf and Kd for different samples. (h) One-hour H2O2 yield for S-ZnO/ZnO2@CN compared with the reported photocatalysts. Reaction conditions: catalyst, 10 mg; solution, 25 mL of ethanol aqueous solution (16 vol%) with O2 bubbling; light source, Xe lamp equipped with an optical cutoff filter (λ ≥ 350 nm); reaction temperature, 298.15 K. Error bars represent the standard deviation of the mean (n = 3).

Fig. 3. (a) UV-vis DRS of different samples. Spatial charge density distribution of CBM and VBM of CN (b), S-CN (c), ZnO (d), and S-ZnO (e). KPFM images and the corresponding surface potentials of ZnO@CN (f) and S-ZnO@CN (g) under dark and illumination conditions. In-situ XPS spectra of N 1s (h) and Zn 2p (i).

Fig. 4. (a) I-t curves of different samples under O2 and Ar atmospheres. EPR signals of DMPO-•O2- (b) and DMPO-•OH (c) for different samples under illumination for 2 min. (d) The Z-scheme charge transfer route in S-ZnO@CN and S-ZnO/ZnO2@CN. Gibbs free energy profiles for O2→H2O2 (e), H2O→H2O2 (f), and H2O2→*OOH (g) pathways on different photocatalyst surfaces.

Fig. 5. DOS of C sites in CN (a), S-CN (b) and S-CN/S-ZnO (c) before and after *OOH adsorption. Reaction mechanisms and structural schematics for H2O2 production: O2 reduction pathways and C-site hybridization states (O2 or *OOH adsorption) on the surface of CN (planar sp2 hybridization) (d), S-CN (distorted sp3 hybridization, sp2→sp3 transition induced by S doping) (e), and S-CN/S-ZnO (split spx + pypz hybridization upon *OOH adsorption) (f), with inset schematics illustrating the orbital configuration of each hybridization state. H2O oxidation pathways on the surface of ZnO or S-ZnO (g), and S-ZnO/ZnO2 (h).

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Sulfur-induced charge-site reconstruction and in-situ formed ZnO₂ protection enable robust solar H₂O₂production

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