Mechanism regulation over dual-atom catalyst enables high-performance oxidative alcohol esterification  

双原子催化剂的机理调节实现高性能醇氧化酯化反应

作　　者：Ce Liu Teng Li Xingchao Dai Jian Zhao Liping Zhang Xinjiang Cui 刘策;李腾;代兴超;赵坚;张丽萍;崔新江

机构地区：[1]State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization,State Key Laboratory for Oxo Synthesis and Selective Oxidation,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China [2]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Science Bulletin》2025年第1期78-89,共12页科学通报(英文版)

基　　金：supported by the National Natural Science Foundation of China(22372180 and 22202216);the Natural Science Foundation of Gansu Province and the Major Project of Gansu Province(21JR7RA096 and 21ZD4WA021);the Youth Innovation Promotion Association(2023441);Lanzhou Institute of Chemical Physics(LICP)Cooperation Foundation for Young Scholars(HZJJ21-06);Key Program of the Lanzhou Institute of Chemical Physics(KJZLZD-2)。

摘　　要：The development of heterogeneous catalysts with well-defined uniform isolated or multiple active sites is of great importance for understanding catalytic performances and studying reaction mechanisms.Herein,we present a CoCu dual-atom catalyst(CoCu-DAC)where bonded Co-Cu dual-atom sites are embedded in N-doped carbon matrix with a well-defined Co(OH)CuN_(6)structure.The CoCu-DAC exhibits higher catalytic activity and selectivity than the Co single-atom catalyst(Co-SAC)and Cu single-atom catalyst(CuSAC)counterparts in the catalytic oxidative esterification of alcohols and a variety of methyl and alkyl esters have been successfully synthesized.Kinetic studies reveal that the activation energy(29.7 kJ mol^(-1))over CoCu-DAC is much lower than that over Co-SAC(38.4 kJ mol^(-1))and density functional theory(DFT)studies disclose that two different mechanisms are regulated over CoCu-DAC and Co-SAC/Cu-SAC in three-step esterification of alcohols.The bonded Co-Cu and adjacent N species efficiently catalyze the elementary reactions of alcohol dehydrogenation,O2activation and ester formation,respectively.The stepwise alkoxy pathway(O-H and C-H scissions)is preferred for both alcohol dehydrogenation and ester formation over CoCu-DAC,while the progressive hydroxylalkyl pathway(C-H and O-H scissions)for alcohol dehydrogenation and simultaneous hemiacetal dehydrogenation are favored over Co-SAC and Cu-SAC.Characteristic peaks in the Fourier transform infrared spectroscopy analysis may confirm the formation of the metal-C intermediate and the hydroxylalkyl pathway over Co-SAC.

关 键 词：Dual-atom catalysts Oxidative esterification Mechanism regulation ALCOHOL 

分 类 号：O643.36[理学—物理化学] O621.256.4[理学—化学]