Methane Reacts with Heteropolyacids Chemisorbed on Silica to Produce Acetic Acid under Soft Conditions

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• 作者：Miao Sun ; Edy Abou-Hamad ; Aaron J. Rossini ; Jizhe Zhang ; Anne Lesage ; Haibo Zhu ; Jeremie Pelletier ; Lyndon Emsley ; Valerie Caps ; Jean-Marie Basset
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：January 16, 2013
• 年：2013
• 卷：135
• 期：2
• 页码：804-810
• 全文大小：427K
• 年卷期：v.135,no.2(January 16, 2013)
• ISSN：1520-5126

文摘

Selective functionalization of methane at moderate temperature is of crucial economic, environmental, and scientific importance. Here, we report that methane reacts with heteropolyacids (HPAs) chemisorbed on silica to produce acetic acid under soft conditions. Specially, when chemisorbed on silica, H₄SiW₁₂O₄₀, H₃PW₁₂O₄₀, H₄SiMo₁₂O₄₀, and H₃PMo₁₂O₄₀ activate the primary C鈥揌 bond of methane at room temperature and atmospheric pressure. With these systems, acetic acid is produced directly from methane, in a single step, in the absence of Pd and without adding CO. Extensive surface characterization by solid-state NMR spectroscopy, IR spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy suggests that C鈥揌 activation of methane is triggered by the protons in the HPA鈥搒ilica interface with concerted reduction of the Keggin cage, leading to water formation and hydration of the interface. This is the simplest and mildest way reported to date to functionalize methane.