C−H Activation of Methane to Formaldehyde on Ce_1−xZr_xO₂ Thin Films: A Step to Bridge the Material Gap

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• 作者：Anjani Dubey ; Dr. Sadhu K. Kolekar and Prof. Chinnakonda S. Gopinath
• 刊名：ChemCatChem
• 出版年：2016
• 出版时间：December 7, 2016
• 年：2016
• 卷：8
• 期：23
• 页码：3650-3656
• 全文大小：1547K
• ISSN：1867-3899

文摘

Ce_1−xZr_xO₂ (CZ) thin films were prepared by a combination of sol–gel and spin-coating methods and were evaluated for the C−H activation of methane by using a molecular beam set-up with the aim to bridge the material gap. The C−H activation of methane begins at 950 K, and a Ce-rich CZ composition displays a high selectivity (4–12 %) to the partially oxidised product, formaldehyde. A 10–12 % selectivity towards HCHO with 1.6 % methane conversion was observed with methane-rich CH₄/O₂ reactant compositions at 1050 K. Short contact times, prevalent under molecular beam conditions, could be a possible reason for HCHO formation. Although combustion products were observed instantly upon shining the mixture of reactants on CZ surfaces, up to 20 s delay was observed before formaldehyde generation, which indicates that the oxygen vacancy migration contributes to the rate-determining step and the diffusion-controlled nature of the reaction. A burst in HCHO generation at the point of molecular beam opening, after beam-closed conditions, suggests that the diffusion of oxygen vacancies to the surface is the reason for HCHO formation. Kinetics results also indicate the necessity of reduction sites for HCHO generation.