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

作者：Qiong Yan, Yang Chen, Bing Tang, Xu Wu, Heng Zhou, Hao Wang, Hui Li, Lanlu Lu, Heng Zhang, Song Yang, Chunbao Xu, Tianyi Ma · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202505718 · 被引用次数：98 · 研究领域：Electrocatalysts for Energy Conversion、Advanced Photocatalysis Techniques、Catalysis for Biomass Conversion

Abstract 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 the design of Cu x /TiO 2 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 photooxidative 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 the highest photooxidation activity reported to date while effectively suppressing the over‐oxidation of HMF to CO 2 . Mechanistic investigations revealed that rational construction of Cu single‐atoms (SAs) could effectively create the asymmetric Cu–Ov–Ti structure, which significantly enhanced the activation of O 2 and HMF, facilitating generation of oxygen vacancy (Ov) and Ti 3+ . Furthermore, Cu SAs served as hole (h + ) extractors in the photooxidation process, promoting rapid charge carrier transfer and ROS formation. The applicability of this developed strategy was further demonstrated for photooxidative conversion of various bio‐feedsto...