Modulating Local Proton Coverage and *OOH Generation via Coupled Multiple Sites for Enhanced Photocatalytic H2O2 Production

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-03-29 DOI:10.1021/acscatal.5c01205

Wengao Zeng, Yuchen Dong, Xiaoyuan Ye, Yi Zhao, Ziying Zhang, Tuo Zhang, Lei Zhang, Jie Chen, Xiangjiu Guan

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Abstract

Rationally modulating the adsorption of reaction intermediates on the surface sites of carbon nitride-based catalysts could facilitate the photocatalytic reduction of O₂ to H₂O₂. Herein, theoretical calculations reveal that multiple sites of heteroatoms and defects can synergistically increase local proton coverage and lower the kinetic barrier for O₂ protonation, thereby promoting the production of *OOH and the subsequent generation of H₂O₂. As a proof of concept, carbon nitride (BPMC-Vs) with multiheteroatoms (B and P) and multidefects (N defects, ─C≡N) was successfully synthesized, achieving optimized solar-to-chemical conversion efficiency and selectivity of 0.33% and 95.2%, respectively. In situ spectroscopic characterization combined with theoretical calculations confirms that P atoms and ─C≡N groups increase proton coverage, while B atoms and N defects effectively promote the protonation of O₂ to *OOH, thereby significantly enhancing the generation of H₂O₂. This work provides insightful guidance for carbon nitride catalysis at the atomic scale for boosting photocatalytic H₂O₂ production.

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合理调节反应中间产物在氮化碳催化剂表面位点上的吸附，可促进光催化将 O2 还原成 H2O2。在此，理论计算揭示了杂原子和缺陷的多个位点可以协同增加局部质子覆盖率，降低 O2 质子化的动力学障碍，从而促进 *OOH 的产生和随后 H2O2 的生成。作为概念验证，我们成功合成了具有多外原子（B 和 P）和多缺陷（N 缺陷，-C≡N）的氮化碳（BPMC-Vs），其太阳能-化学转换效率和选择性分别达到 0.33% 和 95.2%。原位光谱表征结合理论计算证实，P 原子和 -C≡N 基团增加了质子覆盖率，而 B 原子和 N 缺陷则有效促进了 O2 向 *OOH 的质子化，从而显著提高了 H2O2 的生成。这项工作为氮化碳在原子尺度上催化促进光催化产生 H2O2 提供了深刻的指导。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.