Tandem Photocatalytic H ₂ O ₂ Production and In Situ Upgrading Enabled by Docking and Locking Engineered Covalent Organic Frameworks

Abstract

ABSTRACT Photocatalytic H 2 O 2 generation is hindered by low concentrations and energy‐intensive purification, posing major barriers to practical application. Herein, a tandem catalytic strategy that integrates H 2 O 2 generation with its in situ utilization in organic synthesis is reported to overcome these constraints. Covalent organic frameworks (COFs) engineered through a “docking and locking” strategy provide an ideal platform for enabling such tandem transformations. The optimized TTPh–OH COF delivers benchmark H 2 O 2 production rates of 11.42 mmol g −1 h −1 in pure water and 61.96 mmol g −1 h −1 in isopropanol/water (9:1 v/v). Leveraging the high efficiency, a single‐photocatalyst tandem platform generates 22.1 mM H 2 O 2 , which is subsequently consumed to drive the hydrobromination of 4‐methylstyrene with 99% conversion and 87% selectivity, demonstrating the practical utility of in situ photocatalytic H 2 O 2 . This integrated approach outlines a blueprint for circular, solar‐driven photoredox catalysis that upgrades O 2 and H 2 O into value‐added organic products.