Density-functional calculation of the adsorption and reaction of CO and H2O molecules over a 4Rh/CeO2(1 1 1) surface

Hui Lung Chen; Wei Tou Peng; Jia Jen Ho; Horng Ming Hsieh

doi:10.1016/j.chemphys.2008.02.064

Density-functional calculation of the adsorption and reaction of CO and H₂O molecules over a 4Rh/CeO₂(1 1 1) surface

Hui Lung Chen, Wei Tou Peng, Jia Jen Ho^*, Horng Ming Hsieh

^*此作品的通信作者

化學系

研究成果: 雜誌貢獻 › 期刊論文 › 同行評審

25 引文斯高帕斯（Scopus）

摘要

We apply periodic density-functional theory (DFT) to investigate the water-gas-shift reaction, CO + H₂O → CO₂ + H₂, on a 4Rh/CeO₂(1 1 1) surface. Our calculated result shows that the 4Rh atoms gather together to form a cluster shape on the CeO₂(1 1 1) surface (designated as 4Rh/CeO₂(Rh-cluster)) would possess the largest mean adsorption energy, while that locating separately on top of Ce's (designated as 4Rh/CeO₂(Rh-Ce)) the least. The CO molecule with its C-terminus facing toward the Rh atom at "a" position (Rh_a) of the 4Rh/CeO₂(Rh-cluster) surface (designated as OC-Rh_a(a)) is calculated to have the greatest adsorption energy, 67.44 kcal/mol. A similar adsorption conformation of greatest adsorption energy is found for the H₂O molecule, 24.2 kcal/mol. Among the possible reaction paths the one via carboxyl intermediate is more favorable. The calculated maximum barrier in this path is 25.87 kcal/mol, which involves the detachment of an H atom and the release of an CO_2(g) from the adsorbed carboxyl intermediate HOOC-Rh_a(a).

原文	英語
頁（從 - 到）	161-168
頁數	8
期刊	Chemical Physics
卷	348
發行號	1-3
DOIs	https://doi.org/10.1016/j.chemphys.2008.02.064
出版狀態	已發佈 - 2008 6月 2

ASJC Scopus subject areas

一般物理與天文學
物理與理論化學

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10.1016/j.chemphys.2008.02.064

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@article{5dd1a7e2f05e411cb6e7da1fb8f6e4c8,

title = "Density-functional calculation of the adsorption and reaction of CO and H2O molecules over a 4Rh/CeO2(1 1 1) surface",

abstract = "We apply periodic density-functional theory (DFT) to investigate the water-gas-shift reaction, CO + H2O → CO2 + H2, on a 4Rh/CeO2(1 1 1) surface. Our calculated result shows that the 4Rh atoms gather together to form a cluster shape on the CeO2(1 1 1) surface (designated as 4Rh/CeO2(Rh-cluster)) would possess the largest mean adsorption energy, while that locating separately on top of Ce's (designated as 4Rh/CeO2(Rh-Ce)) the least. The CO molecule with its C-terminus facing toward the Rh atom at {"}a{"} position (Rha) of the 4Rh/CeO2(Rh-cluster) surface (designated as OC-Rha(a)) is calculated to have the greatest adsorption energy, 67.44 kcal/mol. A similar adsorption conformation of greatest adsorption energy is found for the H2O molecule, 24.2 kcal/mol. Among the possible reaction paths the one via carboxyl intermediate is more favorable. The calculated maximum barrier in this path is 25.87 kcal/mol, which involves the detachment of an H atom and the release of an CO2(g) from the adsorbed carboxyl intermediate HOOC-Rha(a).",

keywords = "Adsorption, DFT, Rh/CeO(1 1 1), Surface, Water-gas-shift",

author = "Chen, {Hui Lung} and Peng, {Wei Tou} and Ho, {Jia Jen} and Hsieh, {Horng Ming}",

note = "Funding Information: Institute of Nuclear Energy Research, Atomic Energy Council, Taiwan, supported this research under contract NL940251, and National Center for High-Performance Computing provided computer time. Support from National Science Council of Republic of China (NSC 96–2113–M–003–007–MY3) is also grateful. We are deeply indebted to Professor M.C. Lin from NCTU in Taiwan for his persistent encouragement and instruction. We thank Professor J.C. Jiang, Professor M. Hayashi, Dr. Hsin-Tsung Chen and Dr. Shih-Hung Liu for their helpful discussion. ",

year = "2008",

month = jun,

day = "2",

doi = "10.1016/j.chemphys.2008.02.064",

language = "English",

volume = "348",

pages = "161--168",

journal = "Chemical Physics",

issn = "0301-0104",

publisher = "Elsevier",

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TY - JOUR

T1 - Density-functional calculation of the adsorption and reaction of CO and H2O molecules over a 4Rh/CeO2(1 1 1) surface

AU - Chen, Hui Lung

AU - Peng, Wei Tou

AU - Ho, Jia Jen

AU - Hsieh, Horng Ming

N1 - Funding Information: Institute of Nuclear Energy Research, Atomic Energy Council, Taiwan, supported this research under contract NL940251, and National Center for High-Performance Computing provided computer time. Support from National Science Council of Republic of China (NSC 96–2113–M–003–007–MY3) is also grateful. We are deeply indebted to Professor M.C. Lin from NCTU in Taiwan for his persistent encouragement and instruction. We thank Professor J.C. Jiang, Professor M. Hayashi, Dr. Hsin-Tsung Chen and Dr. Shih-Hung Liu for their helpful discussion.

PY - 2008/6/2

Y1 - 2008/6/2

N2 - We apply periodic density-functional theory (DFT) to investigate the water-gas-shift reaction, CO + H2O → CO2 + H2, on a 4Rh/CeO2(1 1 1) surface. Our calculated result shows that the 4Rh atoms gather together to form a cluster shape on the CeO2(1 1 1) surface (designated as 4Rh/CeO2(Rh-cluster)) would possess the largest mean adsorption energy, while that locating separately on top of Ce's (designated as 4Rh/CeO2(Rh-Ce)) the least. The CO molecule with its C-terminus facing toward the Rh atom at "a" position (Rha) of the 4Rh/CeO2(Rh-cluster) surface (designated as OC-Rha(a)) is calculated to have the greatest adsorption energy, 67.44 kcal/mol. A similar adsorption conformation of greatest adsorption energy is found for the H2O molecule, 24.2 kcal/mol. Among the possible reaction paths the one via carboxyl intermediate is more favorable. The calculated maximum barrier in this path is 25.87 kcal/mol, which involves the detachment of an H atom and the release of an CO2(g) from the adsorbed carboxyl intermediate HOOC-Rha(a).

AB - We apply periodic density-functional theory (DFT) to investigate the water-gas-shift reaction, CO + H2O → CO2 + H2, on a 4Rh/CeO2(1 1 1) surface. Our calculated result shows that the 4Rh atoms gather together to form a cluster shape on the CeO2(1 1 1) surface (designated as 4Rh/CeO2(Rh-cluster)) would possess the largest mean adsorption energy, while that locating separately on top of Ce's (designated as 4Rh/CeO2(Rh-Ce)) the least. The CO molecule with its C-terminus facing toward the Rh atom at "a" position (Rha) of the 4Rh/CeO2(Rh-cluster) surface (designated as OC-Rha(a)) is calculated to have the greatest adsorption energy, 67.44 kcal/mol. A similar adsorption conformation of greatest adsorption energy is found for the H2O molecule, 24.2 kcal/mol. Among the possible reaction paths the one via carboxyl intermediate is more favorable. The calculated maximum barrier in this path is 25.87 kcal/mol, which involves the detachment of an H atom and the release of an CO2(g) from the adsorbed carboxyl intermediate HOOC-Rha(a).

KW - Adsorption

KW - DFT

KW - Rh/CeO(1 1 1)

KW - Surface

KW - Water-gas-shift

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U2 - 10.1016/j.chemphys.2008.02.064

DO - 10.1016/j.chemphys.2008.02.064

M3 - Article

AN - SCOPUS:43849094838

SN - 0301-0104

VL - 348

SP - 161

EP - 168

JO - Chemical Physics

JF - Chemical Physics

IS - 1-3

ER -

Density-functional calculation of the adsorption and reaction of CO and H2O molecules over a 4Rh/CeO2(1 1 1) surface

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Density-functional calculation of the adsorption and reaction of CO and H₂O molecules over a 4Rh/CeO₂(1 1 1) surface