硫诱导电荷位点重构与原位生成ZnO2保护层实现稳定高效的太阳能制备H2O2

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

催化学报 ›› 2026, Vol. 88: 207-217.DOI: 10.1016/S1872-2067(26)65124-8

硫诱导电荷位点重构与原位生成ZnO₂保护层实现稳定高效的太阳能制备H₂O₂

孙宇航^a^,¹, 李旭^a^,¹, 曾众天^a, 魏华^b, 赵宇龙^a, 蔡晓燕^a^,^*(), 毛梁^a^,^c^,^*(), 谭昌龙^d, 沈博^d, 徐艺军^d^,^*()

^a 中国矿业大学材料与物理学院, 江苏徐州 221116
^b 中国矿业大学先进分析与计算中心, 江苏徐州 221116
^c 德爱威杭州有限公司, 浙江杭州 311200
^d 电子科技大学基础与前沿研究院, 四川成都 611731

收稿日期:2026-01-26 接受日期:2026-03-19 出版日期:2026-09-18 发布日期:2026-09-05
通讯作者: *电子信箱: xycai@cumt.edu.cn (蔡晓燕),
maoliang@cumt.edu.cn (毛梁),
yjxu@uestc.edu.cn (徐艺军).
基金资助:
国家自然科学基金(22309204);国家自然科学基金(22209203);中国博士后科学基金(2023M733742);中国博士后科学基金(2024M763540);中国矿业大学材料科学与工程学科指导基金(CUMTMS202202);中国矿业大学材料科学与工程学科指导基金(CUMTMS202207)

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

Yuhang Sun^a^,¹, Xu Li^a^,¹, Zhongtian Zeng^a, Hua Wei^b, Yulong Zhao^a, Xiaoyan Cai^a^,^*(), Liang Mao^a^,^c^,^*(), Chang-Long Tan^d, Bo Shen^d, Yi-Jun Xu^d^,^*()

^a School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
^b Advanced Analysis and Computation Center, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
^c Caparol Hangzhou Ltd., Hangzhou 311200, Zhejiang, China
^d Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China

Received:2026-01-26 Accepted:2026-03-19 Online:2026-09-18 Published:2026-09-05
About author:First author contact:1 共同第一作者.
1 Contributed equally to this work.
Supported by:
The National Natural Science Foundation of China(22309204);The National Natural Science Foundation of China(22209203);The China Postdoctoral Science Foundation(2023M733742);The China Postdoctoral Science Foundation(2024M763540);The Material Science and Engineering Discipline Guidance Fund of China University of Mining and Technology(CUMTMS202202);The Material Science and Engineering Discipline Guidance Fund of China University of Mining and Technology(CUMTMS202207)

摘要/Abstract

摘要：

过氧化氢(H₂O₂)是一种用途广泛的绿色氧化剂, 但主要依赖高能耗的蒽醌法生产, 这促使人们寻求可持续替代方案. 人工光合作用合成H₂O₂, 为实现原位、按需且环境友好的制备方式提供了理想路径. 石墨相氮化碳作为一种经典的非金属光催化剂, 虽具有高稳定性、可调的电子结构和低成本等优势, 但其快速的电荷载流子复合极大制约了活性提升. 为此, 研究者开发了异质结工程、形貌调控和杂原子掺杂等多种策略, 然而一个常被忽视的关键挑战是累积H₂O₂的快速分解, 其高反应活性易在光照下通过自由基途径降解, 不仅降低了净产率, 也阻碍了达到实际应用所需的高浓度. 因此, 构建兼具H₂O₂高效生成、分解抑制与长期运行稳定性的光催化体系, 是推进太阳能驱动H₂O₂合成走向实际应用的核心挑战.
本文提出一种“三通道调控”新策略, 通过同步强化H₂O₂生成路径与抑制其分解途径, 实现了高效、稳定的光催化H₂O₂合成. 该策略有机整合了硫(S)介导的电荷位点重构、增强的Z型内建电场, 以及光催化过程中原位形成的无定形ZnO₂保护层, 三者协同构筑了兼具高活性与高稳定性的光催化体系. 基于该策略构建的Z型异质结光催化剂S-ZnO/ZnO₂@CN, 在保留催化剂强氧化与还原能力的同时, 显著提升了光生载流子的分离与传输效率. 具体而言, Z型异质结通过能带匹配与界面电场驱动电子从S-ZnO向S-CN的有效迁移, 既抑制了电荷复合, 又确保了参与表面反应的光生电子与空穴具备充足的热力学驱动力; S掺杂一方面诱导g-C₃N₄中碳原子的sp²→sp³杂化重构, 在分子水平上调控氧还原中间体的吸附与脱附行为, 优化了氧还原反应动力学, 另一方面显著放大了Z型异质结的内建电场强度, 使光生电荷的分离与转移效率得到进一步提升; 此外, 在光催化反应过程中动态形成的无定形ZnO₂层, 通过Zn-O₆终端配位结构增强了O₂吸附能力, 并有效钝化了S-ZnO表面易引发H₂O₂分解的活性位点, 抑制了类芬顿循环的进行, 从而显著降低了H₂O₂的分解速率. 上述三方面机制并非简单叠加, 而是在电荷输运、界面反应与表面保护等多个维度形成深度协同: Z型异质结提供高效电荷分离骨架, S掺杂同时强化了电荷分离驱动力与表面反应选择性, 而ZnO₂层则为生成的H₂O₂提供了稳定的微环境. 得益于此, 该催化剂实现了优异的光催化性能, H₂O₂生成速率高达13.8 mmol/(g·h), 2.5 h内累积浓度达到9 mmol/L, 且连续运行20 h仍保持优异的催化稳定性.
综上, 本工作揭示了电荷位点工程与表面保护策略的协同作用机制, 为突破传统光催化H₂O₂合成体系的瓶颈、实现太阳能驱动H₂O₂的稳定高效生产提供了全新研究思路.

关键词: 异质结光催化剂, H₂O₂生产, 可持续化学, 表面钝化, 杂化工程

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

孙宇航, 李旭, 曾众天, 魏华, 赵宇龙, 蔡晓燕, 毛梁, 谭昌龙, 沈博, 徐艺军. 硫诱导电荷位点重构与原位生成ZnO₂保护层实现稳定高效的太阳能制备H₂O₂[J]. 催化学报, 2026, 88: 207-217.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65124-8

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

图/表 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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硫诱导电荷位点重构与原位生成ZnO₂保护层实现稳定高效的太阳能制备H₂O₂

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

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