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A Highly Stable Copper‐Based Catalyst for Clarifying the Catalytic Roles of Cu 0 and Cu + Species in Methanol Dehydrogenation
Author(s) -
Yang Huanhuan,
Chen Yanyan,
Cui Xiaojing,
Wang Guofu,
Cen Youliang,
Deng Tiansheng,
Yan Wenjun,
Gao Jie,
Zhu Shanhui,
Olsbye Unni,
Wang Jianguo,
Fan Weibin
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201710605
Subject(s) - dehydrogenation , catalysis , methanol , chemistry , methyl formate , copper , bond cleavage , formate , formaldehyde , inorganic chemistry , photochemistry , nanoparticle , organic chemistry , materials science , nanotechnology
Identification of the active copper species, and further illustration of the catalytic mechanism of Cu‐based catalysts is still a challenge because of the mobility and evolution of Cu 0 and Cu + species in the reaction process. Thus, an unprecedentedly stable Cu‐based catalyst was prepared by uniformly embedding Cu nanoparticles in a mesoporous silica shell allowing clarification of the catalytic roles of Cu 0 and Cu + in the dehydrogenation of methanol to methyl formate by combining isotope‐labeling experiment, in situ spectroscopy, and DFT calculations. It is shown that Cu 0 sites promote the cleavage of the O−H bond in methanol and of the C−H bond in the reaction intermediates CH 3 O and H 2 COOCH 3 which is formed from CH 3 O and HCHO, whereas Cu + sites cause rapid decomposition of formaldehyde generated on the Cu 0 sites into CO and H 2 .