A Key Mechanism of Ethanol Electrooxidation Reaction in a Noble-Metal-Free Metal鈥揙rganic Framework

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• 作者：Takayoshi Ishimoto ; Teppei Ogura ; Michihisa Koyama ; Lifen Yang ; Shozo Kinoshita ; Teppei Yamada ; Makoto Tokunaga ; Hiroshi Kitagawa
• 刊名：The Journal of Physical Chemistry C
• 出版年：2013
• 出版时间：May 23, 2013
• 年：2013
• 卷：117
• 期：20
• 页码：10607-10614
• 全文大小：465K
• 年卷期：v.117,no.20(May 23, 2013)
• ISSN：1932-7455

文摘

We elucidated theoretically an electrooxidation reaction mechanism of ethanol on a metal鈥搊rganic framework (MOF) electrocatalyst, (HOC₂H₄)₂dtoaCu (H₂dtoa = dithiooxamide), by using the density functional theory method. The indirect proton transfer from ethanol to the MOF via the HOC₂H₄ group is revealed to be a key mechanism controlling the reactivity of ethanol oxidation on MOF. We have also studied the ethanol oxidation reaction pathways on a series of R₂dtoaCu (R = HOC₃H₆, C₂H₅, C₃H₇, CH₃, and H). Three dominant factors in the electrooxidation activity of R₂dtoaCu were identified: (1) adsorptive interaction with the MOF; (2) strain in the backbone structure that enhances its activity as a proton acceptor; and (3) a proton-transfer pathway from ethanol to R₂dtoaCu. These theoretical identifications are confirmed with the experimental results for ethanol sorption isotherms and the activity of the ethanol electrooxidation reaction measured for R₂dtoaCu (R = HOC₃H₆ and C₂H₅). We are the first to demonstrate the oxidation reaction mechanism of the MOF electrocatalyst for ethanol with theoretical study.