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Acta Phys. Chim. Sin.  2013, Vol. 29 Issue (09): 1916-1922    DOI: 10.3866/PKU.WHXB201307101
THEORETICAL AND COMPUTATIONAL CHEMISTRY     
Adsorption and Decarbonylation Reaction of Furfural on Pt(111) Surface
NI Zhe-Ming, XIA Ming-Yu, SHI Wei, QIAN Ping-Ping
Laboratory of Advanced Catalytic Materials, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China
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Abstract  

The reaction mechanismof furan formation during decarbonylation of furfural on the Pt(111) plane was investigated by density functional theory generalized gradient approximation calculations with the slab model. The adsorption energy of furfural was calculated to determine preferred adsorption sites on the Pt(111) plane. The revealed possible mechanisms for the decarbonylation of furfural on the Pt(111) plane were studied. The results showed that a furfural molecule loses 0.765 electrons after adsorption on the Pt(111) surface. The d orbitals of the metal surface interact strongly with the π bonds of the furfural ring. This reduced the aromaticity of the furfural ring and the Catoms showed characteristics consistent with sp3 hybridization. The molecular plane of the adsorbate was distorted, and corresponding changes of bond lengths were found. The C―H(O) bonds and―CHO of furfural tilted away from the Pt surface. The calculations showthat furan was a possible product of the decarbonylation reaction. We then searched the transition states (TSs) and reaction potential energy surfaces with the linear and quadratic synchronous transit (LST/QST) complete search. By comparing energy barriers, we obtained the optimal path, which involved furfural forming an acyl intermediate by loss of the Hatom from the branched chain rather than direct decarburization. Furan was then formed by decarburization and hydrogenation of the acyl intermediate. The calculated barrier for the rate-determining step(C4H3O)CO*+*→C4H3O*+ CO* (* is adsorption site) is 127.65 kJ·mol-1.



Key wordsPt(111) surface      Density functional theory      Adsorption      Furfural      Decarbonylation reaction     
Received: 26 March 2013      Published: 10 July 2013
MSC2000:  O641  
Corresponding Authors: NI Zhe-Ming     E-mail: jchx@zjut.edu.cn
Cite this article:

NI Zhe-Ming, XIA Ming-Yu, SHI Wei, QIAN Ping-Ping. Adsorption and Decarbonylation Reaction of Furfural on Pt(111) Surface. Acta Phys. Chim. Sin., 2013, 29(09): 1916-1922.

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http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/10.3866/PKU.WHXB201307101     OR     http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/Y2013/V29/I09/1916

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