Mechanisms of selective hydrogenation of crotonaldehyde on In/Au(111) and Ir/Au(111) surfaces

XIA Shengjie1 LUO Wei1 XUE Jilong1 MENG Yue1,2 JIANG Junhui1 NI Zheming1

(1.College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang, China 310014)
(2.School of Life Sciences, Huzhou University, Huzhou, Zhejiang, China 313000)

【Abstract】From stable structures of vertical crotonaldehyde (CAL) adsorption on alloy surfaces of M/Au(111) (M = In, Ir), reaction mechanisms of incomplete hydrogenation (C=O addition, C=C addition, and 1,4-conjugate addition) of CAL on the M/Au(111) surface were studied by density functional theory (DFT) in combination with periodic slab model. The calculation of activation energy and heat of elementary step reactions and analysis of conformation change at various hydrogenation mechanisms showed that CAL on the In/Au(111) and Ir/Au(111) planes first hydrogenated near-surface C=O by A2 mechanism in which an H atom was first added to active C on generation of MS1 and then another H atom was added to intermediate MS1. Both elementary reactions were exothermic but the first one was the rate-determining step due to higher activation energy. The maximum energy barrier of elementary reactions of CAL hydrogenation by the optimal hydrogenation mechanism on In/Au(111) surface was 0.969 eV, which was much lower than that of 1.332 eV on the Ir/Au(111) surface. Hence, In/Au(111) had better catalytic activity than Ir/Au(111) surface for incomplete hydrogenation of CAL. The adsorption of reactant and products on M/Au(111) surface indicated that the formation of strong chemical adsorption between crotonaldehyde O atom and alloy doping element M improved the selectivity of M/Au(111) to C=O hydrogenation.

【Keywords】 DFT; crotonaldehyde; computational chemistry; hydrogenation; adsorption; In/Au(111); Ir/Au(111);

【DOI】

【Funds】 National Natural Science Foundation of China (21503188) Natural Science Foundation of Zhejiang Province (LQ15B030002)

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This Article

ISSN:0438-1157

CN: 11-1946/TQ

Vol 69, No. 04, Pages 1476-1483

April 2018

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Article Outline

Abstract

  • Introduction
  • 1 Calculation method and model
  • 2 Results and discussion
  • 3 Conclusions
  • Symbol description
  • References