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 CH₃O and H₂COOCH₃ which is formed from CH₃O and HCHO, whereas Cu⁺ sites cause rapid decomposition of formaldehyde generated on the Cu⁰ sites into CO and H₂.

中文翻译：

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一种高稳定度的铜基催化剂，用于阐明Cu0和Cu +物种在甲醇脱氢中的催化作用

由于Cu ⁰和Cu ⁺物种在反应过程中的迁移性和演化，因此鉴定活性铜物种以及进一步说明基于铜的催化剂的催化机理仍然是一个挑战。因此，通过将Cu纳米颗粒均匀地包埋在介孔二氧化硅壳中制备了前所未有的稳定的基于Cu的催化剂，从而通过结合同位素标记实验原位阐明了Cu ⁰和Cu ⁺在甲醇脱氢成甲酸甲酯中的催化作用。光谱和DFT计算。结果表明，Cu ⁰位促进了甲醇中OH键的裂解以及反应中间体CH _3中CH键的裂解。由CH ₃ O和HCHO形成的O和H ₂ COOCH ₃，而Cu ⁺位导致在Cu ⁰位上生成的甲醛迅速分解为CO和H ₂。