文献类型：期刊文献

英文题名：Density Functional Theory Studies of Ethanol Decomposition on Rh(211)

作者：Zhang, Jia[1];Cao, X. -M.[2,3];Hu, P.[2,3,4];Zhong, Ziyi[5];Borgna, Armando[5];Wu, Ping[1]

机构：[1]Inst High Performance Comp, Singapore 138632, Singapore;[2]E China Univ Sci & Technol, State Key Lab Chem Engn, Ctr Computat Chem, Shanghai 200237, Peoples R China;[3]E China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[4]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland;[5]Inst Chem Engn & Sci, Singapore 627833, Singapore

年份：2011

卷号：115

期号：45

起止页码：22429

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20114614519800);WOS:【SCI-EXPANDED(收录号:WOS:000296685800042)】；

语种：英文

外文关键词：Rhodium compounds - Density functional theory - Steam reforming - Electron energy levels - Electrooxidation - Ethanol

摘要：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) CH(3)CH(2)OH -> CH(3)CHOH -> CH(3)COH -> CH(3)CO -> CH(3) + CO -> CH(2) + CO -> CH + CO -> C + CO and (2) CH(3)CH(2)OH -> CH(3)CHOH -> CH(3)COH -> CH(2)COH -> CHCOH -> CHCO -> CH + CO -> C + CO. Both pathways have a common intermediate of CH(3)COH, and the key step is the formation of CH(3)CHOH 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 CH(3)COH rather than an oxametallacycle species (-CH(2)CH(2)O- 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(alpha)-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.