文献类型：期刊文献

英文题名：Density functional theory study of decalin dehydrogenation for hydrogen release on Pt(111) and Pt(211)

作者：Tuo, Yongxiao[1];Yang, Liu[1];Cheng, Hongye[1];Yang, Minglei[1];Zhu, Yi-An[1];Li, Ping[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2018

卷号：43

期号：42

起止页码：19575

外文期刊名：INTERNATIONAL JOURNAL OF HYDROGEN ENERGY

收录：;EI(收录号：20183905874885);WOS:【SCI-EXPANDED(收录号:WOS:000449237200028)】；

基金：The authors are grateful for the financial support of the National Natural Science Foundation of China (No. 21276077).

语种：英文

外文关键词：Density functional theory; Dehydrogenation; Decalin isomer van der Waals force; Pt catalyst; Stepped surface

摘要：The catalytic dehydrogenation of organic hydrides on transition metal surfaces is of fundamental importance to hydrogen storage technologies based on organic hydrides. Density functional theory (DFT) calculations were performed to study the dehydrogenation of both trans- and cis-decalin on flat Pt(111) and stepped Pt(211) surfaces. Considering that long-range van der Waals (vdW) forces play an important role in the adsorption and reaction of large organic molecules on metal surfaces, a recently developed vdW-inclusive method (optB88-vdW) was adopted in the computational procedure for accurate adsorption results. It revealed that the adsorption energies of decalin on Pt(111) and Pt(211) have little difference due to the dominant role of vdW forces during adsorption instead of chemical interaction. The possible dehydrogenation pathways of decalin on Pt(211) and Pt(111) are found to be clearly dependent on the isomeric molecular structures of decalin and the metal crystal facets. The dehydrogenation is more favourable for cis-decalin than for trans-decalin when on Pt(211) compared to on Pt(111). Taking the Gibbs free energy calculated for the experimental conditions (500 K, 1 atm) as the descriptor, it was observed that the energy barrier for the desorption of reaction product (naphthalene) is much higher than that of every elementary dehydrogenation step. Therefore, desorption of naphthalene is critical in determining the dehydrogenation reaction rate, especially on stepped Pt surfaces. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.