Au^(δ-)-O_(v)-Ti^(3+):Active site of MO_(x)-Au/TiO_(2) catalysts for the aerobic oxidation of 5-hydroxymethylfurfural  

作　　者：Weiyao Yang Mengchen Fu Chenyu Yang Yiwen Zhang Chun Shen 

机构地区：[1]Beijing Key Laboratory of Bioprocess,College of Life Science and Technology,Beijing University of Chemical Technology,No.15 of North Three-Ring East Road,Chaoyang District,Beijing,100029,China [2]The State Key Laboratory of Chemical Engineering,Department of Chemical Engineering,Tsinghua University,Beijing,100084,China

出　　处：《Green Energy & Environment》2023年第3期785-797,共13页绿色能源与环境（英文版）

基　　金：support of State Key Laboratory of Chemical Engineering (No.SKL-ChE-20A02);the support of International Clean Energy Talent Program by China Scholarship Council.

摘　　要：Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of metal oxide modified MO_(x)-Au/TiO_(2)(M=Fe,Co,Ni)catalysts with low Au loading amount of 0.5 wt%were synthesized.Addition of transition metal oxides promotes electron transfer and generation of the Au^(δ-)-O_(v)-Ti^(3+)interface.A combination study reveals that the dual-active site(Au^(δ-)-O_(v)-Ti^(3+))governs the catalytic performance of the ratedetermining step,namely hydroxyl group oxidation.Au^(δ-) site facilitates chemisorption and activation of O_(2) molecules.At the same time,O_(v)-Ti^(3+) site acts as the role of“killing two birds with one stone”:enhancing adsorption of both reactants,accelerating the activation and dissociation of H_(2)O,and facilitating activation of the adsorbed O_(2).Besides,superoxide radicals instead of base is the active oxygen species during the rate-determining step.On this basis,a FDCA yield of 71.2% was achieved under base-free conditions,complying with the“green chemistry”principle.This work provides a new strategy for the transition metal oxides modification of Au-based catalysts,which would be constructive for the rational design of other heterogeneous catalysts.

关 键 词：5-HYDROXYMETHYLFURFURAL Base-free oxidation Interfacial catalysis Active oxygen species 

分 类 号：TQ426[化学工程]