文献类型：期刊文献

英文题名：Role of CO₂ in ethylbenzene dehydrogenation over Fe₂O₃(0001) from first principles

作者：He, Xiao-Xiang[1];Fan, Chen[1];Gu, Xiong-Yi[1];Zhou, Xing-Gui[1];Chen, De[2];Zhu, Yi-An[1]

机构：[1]E China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol NTNU, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2011

卷号：344

期号：1-2

起止页码：53

外文期刊名：JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000292799200007)】；

基金：This research is supported by Science and Technology Innovation Foundation of China National Petroleum Corporation (No. 2008D-5006-05-05), Natural Science Foundation of China (Nos. 21003046, 20736011), Doctoral Fund of Ministry of Education of China (No. 200802511007), and Fundamental Research Funds for Central Universities (No. WA1014027). The computational time provided by Notur project is highly acknowledged (nn4685k).

语种：英文

外文关键词：DFT; Ethylbenzene dehydrogenation; CO2; Fe2O3(0001)

摘要：First-principles calculations based on density functional theory have been performed to elucidate the reaction mechanism for ethylbenzene dehydrogenation and the role of CO2 in H removal. On the basis of the experimental information and theoretical prediction, three model surfaces with Fe-, ferryl- and O-termination are constructed to represent the active Fe2O3(0 0 0 1) surface. The calculated results indicate that on all of the three surfaces the C-H activation in the methylene group followed by the dehydrogenation of the methyl group is kinetically more favorable. The energy barriers for ethylbenzene dehydrogenation are lowest on the O-terminated surface, but the generated styrene is adsorbed too strongly to be released. As CO2 decomposition and the formation of HCOO are hindered by the relatively high activation energies, CO2 cannot serve as the oxidant to recover the O- and ferryl-terminated surfaces to keep the redox cycle. At the steady state of the reaction the coupling mechanism dominates on the Fe-terminated surface, with the synergistic effect between ethylbenzene dehydrogenation and the reverse water-gas shift reaction. Since the energy barrier for the formation of COOH is comparable to that for H-2 formation, both the one-step and two-step pathways are predicted to contribute to the coupling mechanism, although the former is more probable. (C) 2011 Elsevier B.V. All rights reserved.