Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (05): 1075-1080.doi: 10.3866/PKU.WHXB20110444


Adsorption and Dissociation of Methanol on Perfect FeS2(100) Surface

DU Yu-Dong1, ZHAO Wei-Na1, GUO Xin2, ZHANG Yong-Fan1, CHEN Wen-Kai1   

  1. 1. Department of Chemistry, Fuzhou University, Fuzhou 350108, P. R. China;
    2. State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 410074, P. R. China
  • Received:2010-12-15 Revised:2011-03-06 Published:2011-04-28
  • Contact: CHEN Wen-Kai
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (90922022), State Key Laboratory of Coal Combustion Foundation of Huazhong University of Science and Technology, China (FSKLCC0814), and New Century Excellent Talents Program in University of Fujian Province, China (HX2006-103).


First-principles calculations based on density functional theory (DFT) and the periodical slab model were used to study the adsorption and dissociation of methanol on the perfect FeS2(100) surface. The adsorption energy and the geometric parameters on the different adsorption sites showed that the Fe site was the most favorable adsorption site and O atoms were found to bind to Fe atoms. After adsorption, the C―O and O―H bonds of methanol were elongated and the vibrational stretch frequency was red shifted. The calculation results proved that methanol was prone to decomposition resulting in methoxy groups and hydrogen. We calculated the adsorption behavior of these methoxy groups and hydrogen on the FeS2(100) surface and found that the Fe sites were also the most favorable adsorption sites. A possible decomposition pathway was investigated using transition state searching methods: first the O―H bond of methanol was decomposed producing the intermediate methoxy group and subsequently the C―H bond of the methoxy group was broken resulting in final products of formaldehyde and hydrogen.

Key words: Density functional theory, Methanol, FeS2(100) surface, Adsorption, Transition state