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

Han, Bing; He, Huarui; Liu, Jiali; Jia, Yihui; Wang, Siyue; Xu, Jingyi; Qiao, Min; Li, Wenting et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

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<sup>-1</sup> h<sup>-1</sup> 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.