Precise Engineering of Asymmetric Tri‐active Sites by Symbiotic Strategy for Photocontrolled Directional Reforming of Biomass

Sunlight‐driven production of high‐value chemicals from renewable resources represents a pivotal driver toward achieving sustainable energy supply. However, fundamental barriers include inadequate use of light energy and insufficient understanding of reactive oxygen species (ROS) regulating mechanisms in photocatalytic processes. To address this, a novel symbiotic strategy for design of Cux/TiO2 single‐atom catalysts (SACs) supported by density functional theory (DFT) calculations was proposed. The developed catalyst achieved nearly 100% conversion and selectivity for the directional photo‐oxidative transformation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) or 2,5‐furandicarboxylic acid (FDCA) under both vis‐light and UV‐vis light conditions. Importantly, compared to previous works, this catalyst exhibited highest photo‐oxidation activity while effectively suppressing over‐oxidation of HMF to CO2. Mechanistic investigations revealed that rational construction of Cu SAs could effectively create the asymmetric Cu‐Ov‐Ti structure, which significantly enhanced activation of O2 and HMF, facilitating generation of oxygen vacancy (Ov) and Ti3+. Furthermore, Cu SAs served as hole (h+) extractors in the photo‐oxidation process, promoting rapid charge carrier transfer and ROS formation. The applicability of this developed strategy was further demonstrated for photo‐oxidative conversion of various bio‐feedstocks including HMF and alcoholic substrates, indicating its great potential for harnessing light energy for sustainable valorization of biomass into high‐value chemicals.