Ketyl radical-mediated exfoliation and electron storage for solar hydrogen peroxide production

作者：Bing Han, Huarui He, Jiali Liu, Yihui Jia, Siyue Wang, Jingyi Xu, Min Qiao, Wenting Li, Wenyu Yuan, Yaxin Zhai, Liping Ding, Yongfa Zhu, Xiaolin Zhu · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-66852-z · 被引用次数：11 · 研究领域：Metal-Catalyzed Oxygenation Mechanisms、Covalent Organic Framework Applications、Nanoplatforms for cancer theranostics

Efficient photocatalytic production of hydrogen peroxide is a sustainable strategy for green chemical synthesis and environmental remediation. Herein, we report TPM-DADK, a segmented π-conjugation polymer containing redox-active anthrazolines and tetraphenylmethane nodes, enabling visible-light-driven hydrogen peroxide generation through a direct two-electron oxygen reduction reaction pathway. Conjugation breaks promote electron localization and the formation of long-lived ketyl radical anions, which act as both electron reservoirs and triggers light-induced exfoliation into nanosheets with abundant active sites. This structural evolution, together with localized negative charges, enhances oxygen adsorption and activation through proton-coupled electron transfer. Spectroscopic and kinetic analyses reveal more efficient charge separation, longer excited-state lifetimes, and reduced recombination after exfoliation. In this work, we show that TPM-DADK achieves a hydrogen peroxide production rate of 17.22 mmol g-1 h-1 under simulated sunlight with a solar-to-chemical conversion efficiency of 3.07%, demonstrating that precise π-topology control and radical stabilization synergistically enhance solar-to-chemical conversion for sustainable photosynthesis. This study reports a conjugated polymer photocatalyst, TPM-DADK, that enables light-driven hydrogen peroxide production via stable ketyl radicals, achieving efficient electron storage and dynamic exfoliation for enhanced solar-to-c...