Synergy in magnetic Ni_(x)Co_(1)O_(y) oxides enables base-free selective oxidation of 5-hydroxymethylfurfural on loaded Au nanoparticles  

作　　者：Hao Zhang Yinghao Wang Qizhao Zhang Bang Gu Qinghu Tang Qiue Cao Kun Wei Wenhao Fang 

机构地区：[1]School of Chemical Science and Technology,National Demonstration Center for Experimental Chemistry and Chemical Engineering Education,Yunnan University,Kunming 650091,Yunnan,China [2]School of Chemistry and Chemical Engineering,Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals,Key Laboratory of Green Chemical Media and Reactions,Ministry of Education,Henan Normal University,Xinxiang 453007,Henan,China

出　　处：《Journal of Energy Chemistry》2023年第3期526-536,I0014,共12页能源化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22272149,22062025,21763031);the Yunnan Fundamental Research Projects(202001AW070012,202101AT070171);the Yunnan University’s Research Innovation Fund for Graduate Students(KC-22221892);the Open Research Fund of School of Chemistry and Chemical Engineering of Henan Normal University;the Workstation of Academician Chen Jing of Yunnan Province(202105AF150012);the Free Exploration Fund for Academician(202205AA160007)。

摘　　要：The base-free aerobic oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-furandicarboxylic acid(FDCA)in water is recognized as an important and sustainable upgrading process for cellulosic carbohydrates.However,selectivity control still remains a challenge.Here,we disclose that the unique synergy in magnetic Ni_(x)Co_(1)O_(y)(x=1,3 and 5) bimetallic oxides can induce reactive oxygen defects and simultaneously stabilize small-sized metallic Au nanoparticles in the Au/Ni_(x)Co_(1)O_(y)catalysts.Such catalytic features render effective adsorption and activation of O_(2),OH and C=O groups,realizing selective oxidation of HMF to FDCA.On a series of magnetic Au/Ni_(x)Co_(1)O_(y)catalysts with almost identical Au loadings(ca.0.5 wt%) and particle sizes(ca.2.7 nm),the variable Ni/Co molar ratios give rise to the tunable electron density of Au sites and synergistic effect between NiO and CoO_(y).The initial conversion rates of HMF and its derived intermediates(i.e., DFF,HMFCA and FFCA) show a volcano-like dependence on the number of oxygen defects(i.e.,O_(2)^(-)and O^(-)) and electron-rich Au0sites.The optimum Au/Ni3Co1Oycatalyst exhibits a highest productivity of FDCA(12.5 mmol_(FDCA)mol_(Au)^(-1)h^(-1)) among all the Au catalysts in the literature and achieves> 99% yield of FDCA at 120℃ and 10 bar of O_(2).In addition,this catalyst can be easily recovered by a magnet and show superior stability and reusability during six consecutive cycling tests.This work may shed a light on Au catalysis for the base-free oxidation of biomass compounds by smartly using the synergy in bimetallic oxide carriers.

关 键 词：Aerobic oxidation 2 5-Furandicarboxylic acid C=O group conversion Magnetic catalyst Oxygen defects Synergistic effect 

分 类 号：TQ251.1[化学工程—有机化工] TQ426