Density Functional Theoretical Studies on the Methanol Adsorption and Decomposition on Ru(0001) Surfaces

doi:10.1007/s40242-016-5416-z

Chemical Research in Chinese Universities ›› 2016, Vol. 32 ›› Issue (2): 234-241.doi: 10.1007/s40242-016-5416-z

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Density Functional Theoretical Studies on the Methanol Adsorption and Decomposition on Ru(0001) Surfaces

LIU Jianhong¹, LÜ Cunqin^1,2, JIN Chun¹, GUO Yong¹, WANG Guichang³

1. College of Chemistry and Enviromental Engineering, Shanxi Datong University, Datong 037009, P. R. China;
2. Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education,
3. Department of Chemistry, Center of Theoretical Chemistry Study, Nankai University, Tianjin 300071, P. R. China

Received:2015-10-27 Revised:2015-12-28 Online:2016-04-01 Published:2016-01-14
Contact: LÜ Cunqin, WANG Guichang E-mail:wangguichang@nankai.edu.cn;lcq173@126.com
Supported by:
Supported by the Key Program of Natural Science of Tianjin, China(No.13JCZDJC26800), the National Natural Science Foundation of China(Nos.21503122, 21346002), the Shanxi Province Science Foundation for Youths, China(No.2014021016-2), the Scientific and Technological Programs in Shanxi Province, China(No.2015031017) and the Foundation of Key Laboratory of Advanced Energy Materials Chemistry of Ministry of Education of China.

Abstract

Abstract:

Periodic density functional theory(DFT) calculations are presented to describe the adsorption and decomposition of CH₃OH on Ru(0001) surfaces with different coverages, including p(3×2), p(2×2), and p(2×1) unit cells, corresponding to monolayer(ML) coverages of 1/6, 1/4, and 1/2, respectively. The geometries and energies of all species involved in methanol dissociation were analyzed, and the initial decomposition reactions of methanol and the subsequent dehydrogenations reactions of CH₃O and CH₂OH were all computed at 1/2, 1/4, and 1/6 ML coverage on the Ru(0001) surface. The results show that coverage exerts some effects on the stable adsorption of CH₃O, CH₂OH, and CH₃, that is, the lower the coverage, the stronger the adsorption. Coverage also exerts effects on the initial decomposition of methanol. C-H bond breakage is favored at 1/2 ML, whereas C-H and O-H bond cleavages are preferred at 1/4 and 1/6 ML on the Ru(0001) surface, respectively. At 1/4 ML coverage on the Ru(0001) surface, the overall reaction mechanism can be written as 9CH₃OH→3CH₃O+6CH₂OH+9H→6CH₂O+3CHOH+18H→7CHO+COH+CH+OH+26H→8CO+C+O+36H.

Key words: Methanol decomposition, Ru(0001), Coverage effect, Density functional theory calculation, Slab model

LIU Jianhong, LÜ Cunqin, JIN Chun, GUO Yong, WANG Guichang. Density Functional Theoretical Studies on the Methanol Adsorption and Decomposition on Ru(0001) Surfaces[J]. Chemical Research in Chinese Universities, 2016, 32(2): 234-241.

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Density Functional Theoretical Studies on the Methanol Adsorption and Decomposition on Ru(0001) Surfaces

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