Theoretical understanding on the selectivity of acrolein hydrogenation over silver surfaces: the non-Horiuti-Polanyi mechanism is the key
2017-09-21
发表期刊CATALYSIS SCIENCE & TECHNOLOGY (IF:4.4[JCR-2023],4.7[5-Year])
ISSN2044-4753
卷号7期号:18页码:4024-4033
发表状态已发表
DOI10.1039/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
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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
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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.
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