A Highly Stable Copper‐Based Catalyst for Clarifying the Catalytic Roles of Cu⁰ and Cu⁺ Species in Methanol Dehydrogenation

Abstract

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 Cu⁰ 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 Cu⁰ 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 Cu⁰ sites promote the cleavage of the O-H bond in methanol and of the C-H bond in the reaction intermediates CH₃ O and H₂ COOCH₃ which is formed from CH₃ O and HCHO, whereas Cu⁺ sites cause rapid decomposition of formaldehyde generated on the Cu⁰ sites into CO and H₂ .