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Mechanism regulation over dual-atom catalyst enables high-performance oxidative alcohol esterification.
Liu, Ce; Li, Teng; Dai, Xingchao; Zhao, Jian; Zhang, Liping; Cui, Xinjiang.
Afiliación
  • Liu C; 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.
  • Li T; 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.
  • Dai X; 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.
  • Zhao J; 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.
  • Zhang L; 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; University of Chinese Academy of Sciences, Beijing 100049, China.
  • Cui X; 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. Electronic address: xinjiangcui@licp.cas.cn.
Sci Bull (Beijing) ; 2024 Sep 01.
Article en En | MEDLINE | ID: mdl-39277521
ABSTRACT
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)CuN6 structure. The CoCu-DAC exhibits higher catalytic activity and selectivity than the Co single-atom catalyst (Co-SAC) and Cu single-atom catalyst (Cu-SAC) 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, O2 activation 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.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Sci Bull (Beijing) Año: 2024 Tipo del documento: Article País de afiliación: China Pais de publicación: Países Bajos
Texto completo
Añadir a Mi BVS
Imprimir
XML
PubMed Links
Buscar en Google

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Sci Bull (Beijing) Año: 2024 Tipo del documento: Article País de afiliación: China Pais de publicación: Países Bajos