Band Structure Engineering of Polyimide Photocatalyst for Efficient and Selective Oxidation of Biomass‐Derived 5‐Hydroxymethylfurfural

Abstract Solar‐driven high‐value utilization of biomass and its derivatives has attracted tremendous attention in replacing fossil sources to generate chemicals. Developing high‐performance photocatalysts to selectively catalyze bio‐platform molecules remains a challenge. Herein, biomass‐based 5‐hydroxymethylfurfural (HMF) was efficiently and selectively photooxidized to 2, 5‐diformylfuran (DFF) using a metal‐free polyimide (PI). PI with moderate photooxidation capacity delivered high DFF selectivity of 91 % and high apparent quantum efficiency of 1.13 %, nearly 7 times higher than that of graphitic carbon nitride. Experimental measurements and theoretical calculations revealed that the band structure and photooxidation capability of PI can be continuously modulated by varying the molar ratio of amine and anhydride. Mechanism analysis depicted that holes and superoxide radicals play crucial roles in the efficient photooxidation of HMF to DFF. This work provides guidance on designing efficient polymeric photocatalysts for oxidating biomass and its derivatives to value‐added chemicals.