A key mechanism of ethanol electrooxidation reaction in a noble-metal-free metal-organic framework

Takayoshi Ishimoto; Teppei Ogura; Michihisa Koyama; Lifen Yang; Shozo Kinoshita; Teppei Yamada; Makoto Tokunaga; Hiroshi Kitagawa

doi:10.1021/jp4031046

A key mechanism of ethanol electrooxidation reaction in a noble-metal-free metal-organic framework

Takayoshi Ishimoto, Teppei Ogura, Michihisa Koyama, Lifen Yang, Shozo Kinoshita, Teppei Yamada, Makoto Tokunaga, Hiroshi Kitagawa

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Abstract

We elucidated theoretically an electrooxidation reaction mechanism of ethanol on a metal-organic framework (MOF) electrocatalyst, (HOC ₂H₄)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, C ₂H₅, 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 C ₂H₅). We are the first to demonstrate the oxidation reaction mechanism of the MOF electrocatalyst for ethanol with theoretical study.

Original language	English
Pages (from-to)	10607-10614
Number of pages	8
Journal	Journal of Physical Chemistry C
Volume	117
Issue number	20
DOIs	https://doi.org/10.1021/jp4031046
Publication status	Published - May 23 2013

All Science Journal Classification (ASJC) codes

Electronic, Optical and Magnetic Materials
Energy(all)
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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10.1021/jp4031046

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title = "A key mechanism of ethanol electrooxidation reaction in a noble-metal-free metal-organic framework",

abstract = "We elucidated theoretically an electrooxidation reaction mechanism of ethanol on a metal-organic framework (MOF) electrocatalyst, (HOC 2H4)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, C 2H5, 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 C 2H5). We are the first to demonstrate the oxidation reaction mechanism of the MOF electrocatalyst for ethanol with theoretical study.",

author = "Takayoshi Ishimoto and Teppei Ogura and Michihisa Koyama and Lifen Yang and Shozo Kinoshita and Teppei Yamada and Makoto Tokunaga and Hiroshi Kitagawa",

year = "2013",

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doi = "10.1021/jp4031046",

language = "English",

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T1 - A key mechanism of ethanol electrooxidation reaction in a noble-metal-free metal-organic framework

AU - Ishimoto, Takayoshi

AU - Ogura, Teppei

AU - Koyama, Michihisa

AU - Yang, Lifen

AU - Kinoshita, Shozo

AU - Yamada, Teppei

AU - Tokunaga, Makoto

AU - Kitagawa, Hiroshi

PY - 2013/5/23

Y1 - 2013/5/23

N2 - We elucidated theoretically an electrooxidation reaction mechanism of ethanol on a metal-organic framework (MOF) electrocatalyst, (HOC 2H4)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, C 2H5, 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 C 2H5). We are the first to demonstrate the oxidation reaction mechanism of the MOF electrocatalyst for ethanol with theoretical study.

AB - We elucidated theoretically an electrooxidation reaction mechanism of ethanol on a metal-organic framework (MOF) electrocatalyst, (HOC 2H4)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, C 2H5, 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 C 2H5). We are the first to demonstrate the oxidation reaction mechanism of the MOF electrocatalyst for ethanol with theoretical study.

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A key mechanism of ethanol electrooxidation reaction in a noble-metal-free metal-organic framework

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