Rational Design of Electron-Deficient COFs via Ketone and Sulfone Functionalization for Dramatically Enhanced Photocatalytic Hydrogen Peroxide Production

Abstract

Rational design of electron-deficient covalent organic frameworks (COFs) via strategic integration of ketone and sulfone moieties is demonstrated as an effective molecular engineering strategy for photocatalytic hydrogen peroxide production. This functionalization precisely tunes the electronic structure, creating an internal electric field that markedly optimizes charge separation and accelerates carrier mobility within the framework channels. Mechanistic studies reveal that the enhanced charge dynamics directly promote superoxide radical generation the crucial intermediate for H₂O₂ formation.Among the synthesized derivatives, the sulfone-functionalized Tp-DDS exhibits unprecedented photocatalytic activity, substantially outperforming its electron-rich counterpart. This work establishes a clear structure-activity relationship between electron-withdrawing functionalization and photocatalytic performance, providing a versatile pathway for designing next-generation COF-based photocatalysts for solar-to-chemical energy conversion.