Theoretical understanding on the selectivity of acrolein hydrogenation over silver surfaces: the non-Horiuti-Polanyi mechanism is the key

doi:10.1039/c7cy01500c

	Theoretical understanding on the selectivity of acrolein hydrogenation over silver surfaces: the non-Horiuti-Polanyi mechanism is the key
	Wang, Kaili1,2,3 ; Yang, Bo1
	2017-09-21
发表期刊	CATALYSIS SCIENCE & TECHNOLOGY (IF:4.4[JCR-2023],4.7[5-Year])
ISSN	2044-4753
卷号	7 期号:18 页码:4024-4033
发表状态	已发表
DOI	10.1039/c7cy01500c
摘要	Chemoselective hydrogenation of alpha,beta-unsaturated aldehydes to unsaturated alcohols is not only an important reaction in the chemical industry but also a good model system to understand the catalytic selectivity in heterogeneous catalysis. In the current work, the selectivity of partial hydrogenation of acrolein (C3H4O), the simplest alpha,beta-unsaturated aldehyde, is investigated employing density functional theory (DFT) calculations. Two hydrogenation mechanisms, namely the Horiuti-Polanyi mechanism and the non-Horiuti-Polanyi mechanism, are employed to study the partial hydrogenation of acrolein over Ag(111), Ag(100), Ag(211) and Ag.111)-mono surfaces. It is found that the hydrogenation of C3H4O to C3H5O at the terminal carbon and oxygen atoms follows the non-Horiuti-Polanyi mechanism in which C3H4O reacts with hydrogen molecules directly over all the silver surfaces studied, whilst atomic hydrogen is the active hydrogen species for the hydrogenation of C3H5O to C3H6O. Subsequently, the selectivities between partial hydrogenation products, i.e. propenol, propanal and enol, over silver surfaces with different morphologies are compared by calculating the energy difference between the rate-determining transition states. We find that the selectivity of propenol formation increases with the coordination number of surface silver atoms, which is in good agreement with the trend of selectivities obtained experimentally. It is also interesting to find that the selectivity trend obtained based solely upon the Horiuti-Polanyi mechanism for the hydrogenation of C3H4O to C3H5O and C3H5O to C3H6O cannot explain the experimental results. In other words, the non-Horiuti-Polanyi mechanism is able to give a more reasonable explanation for the selectivity trend observed experimentally than the normally used Horiuti-Polanyi mechanism in heterogeneous catalysis. Our work highlights the significance of the non-Horiuti-Polanyi mechanism in understanding heterogeneous catalytic hydrogenation reactions.
收录类别	SCI ; EI
语种	英语
资助项目	Shanghai Young Eastern Scholar Program[QD2016049]
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
WOS记录号	WOS:000411012900008
出版者	ROYAL SOC CHEMISTRY
EI入藏号	20173904204773
EI主题词	Alcohols ; Aldehydes ; Atoms ; Carbon ; Catalysis ; Chemical industry ; Density functional theory ; Herbicides ; Silver
EI分类号	Precious Metals:547.1 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Chemical Engineering, General:805 ; Atomic and Molecular Physics:931.3
WOS关键词	DENSITY-FUNCTIONAL THEORY ; INITIO MOLECULAR-DYNAMICS ; TOTAL-ENERGY CALCULATIONS ; UNSATURATED ALDEHYDES ; ALPHA,BETA-UNSATURATED ALDEHYDES ; ACETYLENE HYDROGENATION ; HETEROGENEOUS CATALYSIS ; CHEMO-REGIOSELECTIVITY ; STRUCTURE SENSITIVITY ; SUPPORTED SILVER
原始文献类型	Article
引用统计	正在获取...
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/4633
专题	物质科学与技术学院物质科学与技术学院_PI研究组_杨波组物质科学与技术学院_硕士生
通讯作者	Yang, Bo
作者单位	1.ShanghaiTech Univ, Sch Phys Sci & Technol, 393 Middle Huaxia Rd, Shanghai 201210, Peoples R China 2.Chinese Acad Sci, Shanghai Inst Organ Chem, Shanghai 200032, Peoples R China 3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
第一作者单位	物质科学与技术学院
通讯作者单位	物质科学与技术学院
第一作者的第一单位	物质科学与技术学院
推荐引用方式 GB/T 7714	Wang, Kaili,Yang, Bo. Theoretical understanding on the selectivity of acrolein hydrogenation over silver surfaces: the non-Horiuti-Polanyi mechanism is the key[J]. CATALYSIS SCIENCE & TECHNOLOGY,2017,7(18):4024-4033.
APA	Wang, Kaili,&Yang, Bo.(2017).Theoretical understanding on the selectivity of acrolein hydrogenation over silver surfaces: the non-Horiuti-Polanyi mechanism is the key.CATALYSIS SCIENCE & TECHNOLOGY,7(18),4024-4033.
MLA	Wang, Kaili,et al."Theoretical understanding on the selectivity of acrolein hydrogenation over silver surfaces: the non-Horiuti-Polanyi mechanism is the key".CATALYSIS SCIENCE & TECHNOLOGY 7.18(2017):4024-4033.