Density functional theory studies of ethanol decomposition on Rh(211)

Jia Zhang; X. M. Cao; P. Hu; Ziyi Zhong; Armando Borgna; Ping Wu

doi:10.1021/jp206837z

Density functional theory studies of ethanol decomposition on Rh(211)

Jia Zhang, X. M. Cao, P. Hu, Ziyi Zhong, Armando Borgna, Ping Wu^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

55 Scopus citations

Abstract

Density functional theory calculations were carried out to examine the mechanism of ethanol decomposition on the Rh(211) surface. We found that there are two possible decomposition pathways: (1) CH₃CH₂OH → CH₃CHOH → CH₃COH → CH₃CO → CH₃ + CO → CH₂ + CO → CH + CO → C + CO and (2) CH₃CH₂OH → CH₃CHOH → CH₃COH → CH₂COH → CHCOH → CHCO → CH + CO → C + CO. Both pathways have a common intermediate of CH₃COH, and the key step is the formation of CH₃CHOH species. According to our calculations, the mechanism of ethanol decomposition on Rh(211) is totally different from that on Rh(111): the reaction proceeds via CH₃COH rather than an oxametallacycle species (-CH₂CH₂O- for Rh(111)), which implies that the decomposition process is structure sensitive. Further analyses on electronic structures revealed that the preference of the initial C_α-H path is mainly due to the significant reduction of d-electron energy in the presence of the transition state (TS) complex, which may stabilize the TS-surface system. The present work first provides a clear picture for ethanol decomposition on stepped Rh(211), which is an important first step to completely understand the more complicated reactions, like ethanol steam reforming and electrooxidation.

Original language	English
Pages (from-to)	22429-22437
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	115
Issue number	45
DOIs	https://doi.org/10.1021/jp206837z
State	Published - 17 Nov 2011
Externally published	Yes

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title = "Density functional theory studies of ethanol decomposition on Rh(211)",

abstract = "Density functional theory calculations were carried out to examine the mechanism of ethanol decomposition on the Rh(211) surface. We found that there are two possible decomposition pathways: (1) CH3CH2OH → CH3CHOH → CH3COH → CH3CO → CH3 + CO → CH2 + CO → CH + CO → C + CO and (2) CH3CH2OH → CH3CHOH → CH3COH → CH2COH → CHCOH → CHCO → CH + CO → C + CO. Both pathways have a common intermediate of CH3COH, and the key step is the formation of CH3CHOH species. According to our calculations, the mechanism of ethanol decomposition on Rh(211) is totally different from that on Rh(111): the reaction proceeds via CH3COH rather than an oxametallacycle species (-CH2CH2O- for Rh(111)), which implies that the decomposition process is structure sensitive. Further analyses on electronic structures revealed that the preference of the initial Cα-H path is mainly due to the significant reduction of d-electron energy in the presence of the transition state (TS) complex, which may stabilize the TS-surface system. The present work first provides a clear picture for ethanol decomposition on stepped Rh(211), which is an important first step to completely understand the more complicated reactions, like ethanol steam reforming and electrooxidation.",

author = "Jia Zhang and Cao, {X. M.} and P. Hu and Ziyi Zhong and Armando Borgna and Ping Wu",

year = "2011",

month = nov,

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doi = "10.1021/jp206837z",

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T1 - Density functional theory studies of ethanol decomposition on Rh(211)

AU - Zhang, Jia

AU - Cao, X. M.

AU - Hu, P.

AU - Zhong, Ziyi

AU - Borgna, Armando

AU - Wu, Ping

PY - 2011/11/17

Y1 - 2011/11/17

N2 - Density functional theory calculations were carried out to examine the mechanism of ethanol decomposition on the Rh(211) surface. We found that there are two possible decomposition pathways: (1) CH3CH2OH → CH3CHOH → CH3COH → CH3CO → CH3 + CO → CH2 + CO → CH + CO → C + CO and (2) CH3CH2OH → CH3CHOH → CH3COH → CH2COH → CHCOH → CHCO → CH + CO → C + CO. Both pathways have a common intermediate of CH3COH, and the key step is the formation of CH3CHOH species. According to our calculations, the mechanism of ethanol decomposition on Rh(211) is totally different from that on Rh(111): the reaction proceeds via CH3COH rather than an oxametallacycle species (-CH2CH2O- for Rh(111)), which implies that the decomposition process is structure sensitive. Further analyses on electronic structures revealed that the preference of the initial Cα-H path is mainly due to the significant reduction of d-electron energy in the presence of the transition state (TS) complex, which may stabilize the TS-surface system. The present work first provides a clear picture for ethanol decomposition on stepped Rh(211), which is an important first step to completely understand the more complicated reactions, like ethanol steam reforming and electrooxidation.

AB - Density functional theory calculations were carried out to examine the mechanism of ethanol decomposition on the Rh(211) surface. We found that there are two possible decomposition pathways: (1) CH3CH2OH → CH3CHOH → CH3COH → CH3CO → CH3 + CO → CH2 + CO → CH + CO → C + CO and (2) CH3CH2OH → CH3CHOH → CH3COH → CH2COH → CHCOH → CHCO → CH + CO → C + CO. Both pathways have a common intermediate of CH3COH, and the key step is the formation of CH3CHOH species. According to our calculations, the mechanism of ethanol decomposition on Rh(211) is totally different from that on Rh(111): the reaction proceeds via CH3COH rather than an oxametallacycle species (-CH2CH2O- for Rh(111)), which implies that the decomposition process is structure sensitive. Further analyses on electronic structures revealed that the preference of the initial Cα-H path is mainly due to the significant reduction of d-electron energy in the presence of the transition state (TS) complex, which may stabilize the TS-surface system. The present work first provides a clear picture for ethanol decomposition on stepped Rh(211), which is an important first step to completely understand the more complicated reactions, like ethanol steam reforming and electrooxidation.

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Density functional theory studies of ethanol decomposition on Rh(211)

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