Adsorption and Dissociation of Methanol on Pd(111), Pd/Au(111) and Pd/Rh(111) Surfaces

作     者：PENG Xiao-Ying FENG Sheng-Lei 彭小英;冯胜雷

作者机构：Nanchang Key Laboratory of Material and Structure DetectionJiangxi University of TechnologyNanchang 33009SChina 

出 版 物：《Chinese Journal of Structural Chemistry》 (结构化学（英文）)

年 卷 期：2019年第38卷第12期

页      面：2057-2069页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(51668021) Natural Science Foundation of Jiangxi Province(20171BAB206052) Foundation of Jiangxi Educational Committee(GJJ171020,GJJ180968,GJJ180969) Natural Science Project of Jiangxi University of Technology(ZR1803) Opening Funds of State Key Laboratory of Building Safety and Built Environment and National Engineering Research Center of Building Technology(BSBE2018-10) 

主　　题：density functional theory methanol metal surface adsorption dissociation 

摘      要：The adsorption and dissociation behaviors of methanol on Pd(111), Pd/Au(111) and Pd/Rh(111) surfaces were studied using a periodical slab model and the PW91 generalized gradient approximation(GGA) within the framework of first-principles calculations based on density functional theory(DFT). The adsorption energy and geometric parameters for the three surfaces showed that methanol is preferentially adsorbed onto the top-Pd sites and that the adsorption energy of methanol on these surfaces decreases in the order Pd/Au(111) Pd/Rh(111) Pd(111). After adsorption, the C–O, C–H and O–H bonds in methanol adsorbed onto these surfaces are elongated and the vibrational stretching frequency of the O–H bond is obviously redshifted. Furthermore, the first step for the possible dissociation pathway for methanol on these surfaces was calculated. Our results indicate that the O–H bond in methanol decomposes producing methoxy and a hydrogen atom, with the Pd/Au(111) surface exhibiting the smallest dissociation barrier.