Intramolecular noncovalent trans ring restricting free rotation of σ single bond enhances photosynthesis of hydrogen peroxide

• 成果类型: Article
• 署名作者: Guo, Yaru; Liu, Youxing; Li, Lu; Xu, Yachao; Lin, Zheng; Sun, Zongqiang; Luo, Mingchuan; Guo, Shaojun; Deng, Xuliang
• 署名单位: Peking University; Beijing University of Chemical Technology
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.2526675123
• 发表日期: 2026-02-10
• 页码: e2526675123
• 关键词: Solar energy; covalent organic framework; noncovalent trans ring; hydrogen peroxide; water; DISINFECTION; membrane

摘要

Solar energy-driven hydrogen peroxide (H2O2) synthesis from atmospheric oxygen and water represents a sustainable and highly promising avenue for the production of this essential chemical. Covalent organic frameworks (COFs) offer a molecular platform for the direct conversion of solar energy to H2O2, however, they are persistently plagued by the recombination of photogenerated charge carriers, a phenomenon induced by sigma-bond rotation under light irradiation, which typically leads to sluggish conversion kinetics and suboptimal efficiency. We herein present a molecular engineering strategy involving the construction of noncovalent trans rings (Nc-TRs) within COFs. This approach entails the precise introduction of noncovalent interactions between donor and acceptor moieties, thereby constraining the free rotation of sigma bonds and substantially suppressing the recombination of photogenerated charge carriers. Experimental and theoretical investigations demonstrate that the incorporation of Nc-TR within TAPT-DHBD COFs reduces the molecular dihedral angle from 37.33 degrees to 0 degrees, thereby optimizing molecular coplanarity and prolonging the photogenerated charge carrier lifetime by 820% compared to TAPT-TPD COFs devoid of Nc-TRs. Our findings further reveal that TAPT-DHBD COFs exhibit 5.0-fold and 3.6-fold enhancements in H2O2 photocatalytic conversion kinetics and solar-to-chemical conversion (SCC) efficiency, respectively, relative to TAPT-TPD COFs. We further demonstrate that H2O2 solutions generated in the flow-type photocatalytic system under solar irradiation exhibit a record-high antibacterial efficacy of 107 cfu s-1, and achieve a 100% wound healing rate within 7 d, markedly outperforming commercial physiological saline.