Construction of Frustrated Lewis Pairs on Covalent Organic Framework for Water‐Assisted Catalytic Hydrogenation of Furfural Compounds

Furfural (FAL), a key biomass‐derived platform compound, upgrading to furfuryl alcohol (FOL) relies heavily on transition metal catalysts, which suffer from high cost, toxicity, and harsh reaction conditions. Herein, we developed a metal‐free heterogeneous catalyst (PCOFs‐BCF) by synthesizing quinoline‐linked phosphorus‐containing covalent organic frameworks (PCOFs), then postmodifying tris(pentafluorophenyl)borane (BCF) to construct frustrated Lewis pairs (FLPs). Phenylsilane as reducing agent and water as coreagent, PCOFs‐BCF achieved excellent conversion and yield, outperforming homogeneous FLPs and phosphine‐free analogs. Mechanistic studies confirmed that FLPs activate phenylsilane to generate hydrides for FAL carbonyl reduction, while water provides protons for silyl ether hydrolysis to FOL. This work offers a recyclable FLP catalyst strategy for sustainable biomass FAL valorization.