TY - JOUR
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
N1 - Copyright:
Copyright 2013 Elsevier B.V., All rights reserved.
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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U2 - 10.1021/jp4031046
DO - 10.1021/jp4031046
M3 - Article
AN - SCOPUS:84878119125
VL - 117
SP - 10607
EP - 10614
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 20
ER -