The reaction network of oxidative carbonylation of methanol (CH₃OH) over CuY catalyst prepared by solid-state ion exchange of HY zeolite with CuCl was enriched by combination of in-situ diffuse reflectance infrared fourier transform spectroscopy and mass spectrometric. Based on the proposed mechanism of dimethyl carbonate formation on CuY in literature, this study mainly focused on the origin of the O atom in methoxyl and the reaction pathway for by-products formation. The interaction of the catalyst with different reactants and reactant mixtures (CH₃OH, CH₃¹⁸OH, HCHO, O₂, CH₃OH/HCHO and CH₃¹⁸OH/CO/O₂) was studied in detail. It was found that in the presence of CuO_x or oxygen, methoxide species are generated by breaking of the O–H bond. Reaction of methoxide species with oxygen leads to the formation of formaldehyde (HCHO), followed by the generation of formate species through consecutive oxidation of HCHO.

Graphic Abstract

中文翻译：

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CuY催化剂上甲醇氧羰基化的补充机理：甲氧基中氧原子的起源和副产物的形成

结合原位漫反射红外傅里叶变换光谱和质谱分析技术，丰富了HY沸石与CuCl的固态离子交换制备的CuY催化剂上甲醇（CH ₃ OH）的氧化羰基化反应网络。基于文献中提出的在CuY上形成碳酸二甲酯的机理，该研究主要集中在甲氧基中O原子的起源以及副产物形成的反应途径上。催化剂与不同反应物和反应物混合物（CH ₃ OH，CH ₃ ¹⁸ OH，HCHO，O ₂，CH ₃ OH / HCHO和CH ₃ ¹⁸ OH / CO / O ₂的相互作用））进行了详细的研究。发现在CuO _x或氧的存在下，OH键断裂会生成甲醇盐。甲醇与氧气的反应会导致甲醛（HCHO）的形成，然后通过HCHO的连续氧化生成甲酸盐类。

图形摘要