物理化学学报 >> 2026, Vol. 42 >> Issue (3): 100172.doi: 10.1016/j.actphy.2025.100172

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通过间接两电子还原的HOF/BiVO4 (010) S型光催化剂增强H2O2生产性能

周玲1,†, 李龙1,†, 黄礼文2,*(), 吴艳1,*()   

  1. 1 中国地质大学(武汉), 材料与化学学院, 湖北 武汉 430078
    2 湖北工程学院, 化学与材料科学学院, 湖北 孝感 432000
  • 收稿日期:2025-07-15 修回日期:2025-08-20 录用日期:2025-08-24 发布日期:2026-01-05
  • 通讯作者: Email: wuyan@cug.edu.cn (吴艳)hlw@hbeu.edu.cn (黄礼文)
  • 作者简介:

    † Equally contributed to this work.

Enhanced H2O2 production performance via indirect two-electron reduction of HOF/BiVO4 (010) S-scheme photocatalyst

Ling Zhou1, Long Li1, Liwen Huang2,*(), Yan Wu1,*()   

  1. 1 Faculty of Materials Science and Chemistry, China University of Geosciences (Wuhan), Wuhan 430078, Hubei Province, China
    2 College of Chemistry and Materials Science, Hubei Engineering University, Xiaogan 432000, Hubei Province, China
  • Received:2025-07-15 Revised:2025-08-20 Accepted:2025-08-24 Published:2026-01-05
  • Contact: Email: wuyan@cug.edu.cn (Yan Wu)hlw@hbeu.edu.cn (Liwen Huang)

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摘要：

太阳能驱动的氧还原制取H2O2为传统工业蒽醌法和直接H2/O2合成法提供了一种绿色、高效且环境友好的替代方案。本研究通过定向晶面工程，将氢键有机框架(HOF)选择性锚定在BiVO4的(010)晶面上，构建了以HOF为还原端、通过氧还原反应生成H2O2的S型异质结。该结构使H2O2产率显著提升至555 μmol g−1 h−1，较随机锚定的HOF/BiVO4体系提高约37%。原位开尔文探针力显微镜(KPFM)揭示了原始BiVO4的(110)与(010)晶面间存在内建电场，且(010)晶面在光照下富集电子。对HOF定向锚定于BiVO4 (010)晶面的材料研究表明，两组分间还建立了额外的内建电场。由此，我们提出了一种在异质结中具有双内建电场的新型HOF/BiVO4 (010)光催化材料，这种结构显著促进了单晶BiVO4不同晶面与S型异质结界面的双向定向电荷转移。原位X射线光电子(XPS)进一步证实了S型异质结的电子转移机制。通过引入电子清除剂与空穴捕获剂，我们证实该异质结介导的光催化过程遵循两电子氧还原反应(ORR)路径。电子顺磁共振(EPR)光谱检测到超氧自由基(∙O2−)的存在，表明ORR通过间接两电子转移机制进行。双内建电场、S型异质结结构与两电子ORR路径的协同效应共同促成了该体系优异的光催化性能。

关键词: S型异质结, 双内建电场, 氢键有机框架, BiVO4, 两电子ORR

Abstract:

Solar-driven oxygen reduction for H2O2 production offers a green, efficient, and environmentally friendly alternative to the conventional industrial anthraquinone process and direct H2/O2 synthesis. In this study, through targeted crystal facet engineering, a hydrogen-bonded organic framework (HOF) was selectively anchored onto the (010) facet of BiVO4, forming an S-scheme heterojunction where the HOF is the reducing side and oxygen reduction occurs to produce H2O2. This configuration significantly enhanced the H2O2 yield to 555 μmol g−1 h−1, representing a ~37% improvement compared to randomly contacted HOF/BiVO4 systems. In situ Kelvin probe force microscopy (KPFM) revealed the formation of an intrinsic electric field between the (110) and (010) facets of pristine BiVO4, with the (010) facet becoming electron-rich under illumination. Further investigation of the HOF/BiVO4 (010) material, where HOF is directionally anchored to the (010) facet of BiVO4, demonstrated the establishment of an additional built-in electric field between the two components. Thus, we propose a novel HOF/BiVO4 (010) photocatalytic material featuring dual built-in electric fields in the heterojunctions, which significantly promote the dual directed charge transfer in the different facets of single crystal BiVO4 and the interface of the S-scheme heterojunction. In situ X-ray Photoelectron Spectroscopy (XPS) further confirmed the S-scheme heterojunction electron transfer mechanism. By introducing electron scavengers and hole trappers, we conclusively verified that the heterojunction-mediated photocatalytic process follows a two-electron Oxygen Reduction Reaction (ORR) pathway. Electron Paramagnetic Resonance (EPR) spectroscopy detected the presence of superoxide radicals (∙O2−), indicating that the ORR proceeds via an indirect two-electron transfer mechanism. The synergistic effects of the dual built-in electric fields, S-scheme heterojunction structure, and two-electron ORR pathway collectively contribute to the superior photocatalytic performance of this system.

Key words: S-scheme heterojunction, Dual built-in electric fields, Hydrogen-bonded organic framework, BiVO4, Two-electron ORR