Ethanol Steam Reforming on Rh Catalysts: Theoretical and Experimental Understanding

被引:38
作者
Zhang, Jia [1 ]
Zhong, Ziyi [2 ]
Cao, X. -M. [3 ,4 ]
Hu, P. [3 ,4 ,5 ]
Sullivan, Michael B.
Chen, Luwei [2 ]
机构
[1] Agcy Sci Technol & Res, Inst High Performance Comp, Singapore 138632, Singapore
[2] Agcy Sci Res & Technol, Inst Chem Engn & Sci, Singapore 627833, Singapore
[3] E China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Chem Engn, Shanghai 200237, Peoples R China
[4] E China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China
[5] Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland
关键词
ethanol steam reforming; Rh catalyst; reaction mechanism; DFT calculations; real-time GC/MS analysis; GAS SHIFT REACTION; INITIO MOLECULAR-DYNAMICS; LOW-TEMPERATURE; HYDROGEN-PRODUCTION; H-2; PRODUCTION; REACTION-MECHANISM; FUEL-CELL; WATER; DEACTIVATION; TRANSITION;
D O I
10.1021/cs400725k
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Through combined theoretical and experimental efforts, the reaction mechanism of ethanol steam reforming on Rh catalysts was studied. The results suggest that acetaldehyde (CH3CHO) is an important reaction intermediate in the reaction on nanosized Rh catalyst. Our theoretical work suggests that the H-bond effect significantly modifies the ethanol decomposition pathway. The possible reaction pathway on Rh (211) surface is suggested as CH3CH2OH -> CH3CH2O -> CH3CHO -> CH3CO -> CH3 + CO -> CH2 + CO -> CH + CO -> C + CO, followed by the water gas shift reaction to yield H-2 and CO2. In addition, we found that the water-gas shift reaction, not the ethanol decomposition, is the bottleneck for the overall ethanol steam reforming process. The CO + OH association is considered the key step, with a sizable energy barrier of 1.31 eV. The present work first discusses the mechanisms and the water effect in ethanol steam reforming reactions on Rh catalyst from both theoretical and experimental standpoints, which may shed light on designing improved catalysts.
引用
收藏
页码:448 / 456
页数:9
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