Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (7): 1140-1152.DOI: 10.6023/A26040135 Previous Articles     Next Articles

Article

S/B/K共掺杂调控氮化碳电子结构用于高效光催化合成H2O2

冯丹宁a, 封波a, 万坤a, 谢颂海a, 裴燕a, 乔明华a,*(), 宗保宁b,*()   

  1. a 复旦大学化学系多孔材料与分离转化全国重点实验室 上海市分子催化和功能材料重点实验室 上海 200438
    b 中国石化石油化工科学研究院催化材料与反应工程国家重点实验室 催化材料与反应工程国家重点实验室 北京 100083
  • 投稿日期:2026-04-24 发布日期:2026-06-24
  • 基金资助:
    国家重点研发专项项目(2021YFA1501404); 国家自然科学基金(22272030); 上海市重点实验室专项经费(2024DZSYS02)

Electronic Structure Engineering of g-C3N4 via S/B/K Co-Doping for Efficient Photocatalytic H2O2 Synthesis

Danning Fenga, Bo Fenga, Kun Wana, Songhai Xiea, Yan Peia, Minghua Qiaoa,*(), Baoning Zongb,*()   

  1. a State Key Laboratory of Porous Materials for Separation and Conversion and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200438, China
    b State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing,SINOPEC, Beijing 100083, China
  • Received:2026-04-24 Published:2026-06-24
  • Contact: * E-mail: mhqiao@fudan.edu.cn; zongbn.ripp@sinopec.com; Tel.: 021-31244679
  • Supported by:
    National Key Research and Development Project of China(2021YFA1501404); National Natural Science Foundation of China(22272030); Science and Technology Commission of Shanghai Municipality(2024DZSYS02)

Efficient photocatalytic reduction of O2 to H2O2 over graphitic carbon nitride (g-C3N4) is of significant practical value. To overcome the intrinsic drawbacks of g-C3N4 including high electronic structure symmetry, severe photogenerated carrier recombination, weak O2 activation ability, and low photocatalytic H2O2 synthesis efficiency, herein a regulation strategy of electronic structure via multi-element co-doping coupled with defect engineering was proposed. A S/B/K ternary co-doped g-C3N4 catalyst (denoted as KBSCN) was fabricated by a facile two-step calcination followed by ionothermal treatment. This strategy enabled the simultaneous homogeneous incorporation of electron-rich S and electron-deficient B into the g-C3N4 framework, intercalation of K, as well as the introduction of cyano groups (−C≡N) and nitrogen vacancies (Nv). The structural and photoelectrochemical properties of KBSCN were systematically characterized, and its photocatalytic performance in photocatalytic reduction of O2 to H2O2 was evaluated. Combined with density functional theory (DFT) calculations, the synergistic regulation mechanism of multi-element doping on the electronic structure and reaction kinetics of KBSCN was elucidated. S/B/K ternary co-doping can effectively break the inherent symmetric structure and broaden the visible light response range of g-C3N4. In photocatalytic reduction of O2, under visible light irradiation, KBSCN exhibited a H2O2 production rate of 8132 μmol•g−1•h−1, which was 185 times that of pristine g-C3N4. Mechanistic studies indicate that S/B/K co-doping greatly promotes the separation and migration of photogenerated carriers by inducing the spatial separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Moreover, by combining radical scavenging experiments, in situ electron paramagnetic resonance (EPR), in situ diffuse reflectance infrared Fourier transform (in situ DRIFT) spectroscopy characterizations and Bader charge analysis for electron transfer, it is revealed that S/B/K co-doping drives the photocatalytic O2 reduction reaction (ORR) to proceed via an indirect two-electron reduction pathway with superoxide radicals (•O2) as the intermediate, thus significantly boosting the reaction kinetics of the 2e-ORR process. This work provides a new avenue for the design of g-C3N4-based catalysts for efficient visible light-driven H2O2 synthesis via synergistic regulation of electronic structure and surface reaction kinetics.

Key words: photocatalysis, H2O2, g-C3N4, multi-element co-doping, synergistic effect