First-Principles-Based Microkinetic Simulations of CO2 Hydrogenation to Methanol over Intermetallic GaPd2: Method Development to Include Complex Interactions between Surface Adsorbates

doi:10.1021/acs.jpcc.0c03975

	First-Principles-Based Microkinetic Simulations of CO2 Hydrogenation to Methanol over Intermetallic GaPd2: Method Development to Include Complex Interactions between Surface Adsorbates
	Wu, Panpan; Zaffran, Jeremie; Xu, Dongyang; Yang, Bo
	2020-07-23
发表期刊	JOURNAL OF PHYSICAL CHEMISTRY C
ISSN	1932-7447
EISSN	1932-7455
卷号	124 期号:29 页码:15977-15987
发表状态	已发表
DOI	10.1021/acs.jpcc.0c03975
摘要	To computationally design efficient solid catalysts, density functional theory (DFT) calculations are widely used in combination with microkinetic modeling (MKM). However, MKM results are often biased due to the overestimation of adsorption strength in DFT calculations that are usually performed at an arbitrary low coverage of surface intermediates. We hereby developed a new iterative approach focusing on the main species present on the catalyst at the steady state, hence allowing adsorption energy calculation only in the presence of relevant intermediates. In this way, the complex parametrization process to determine scaling relations between adsorption energies and coverages is avoided, which will increase the efficiency and accuracy of the iteration process. When applying this approach to CO2 hydrogenation over GaPd2, we found within few iterations that only when running DFT calculations using the surface with both CO and HCOO precovered, the coverage of surface species obtained from MICVI analysis can be consistent with that used in DFT calculations. It stems from our theoretical study that all the species coverages must be self-consistent in order to predict methanol selectivity in fair agreement with experiment.
关键词	Adsorption Calculations Catalysts Design for testability Intermetallics Iterative methods MethanolAdsorption energies Adsorption strength Iterative approach Methanol selectivity Method development Microkinetic modeling Surface adsorbates Surface intermediates
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收录类别	SCI ; SCIE ; EI
语种	英语
资助项目	National Natural Science Foundation of China[21950410522][91745102] ; Shanghai Pujiang Program[16PJ1406800] ; Shanghai Young Eastern Scholar Program[QD2016049]
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science
WOS类目	Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
WOS记录号	WOS:000555507000033
出版者	AMER CHEMICAL SOC
EI主题词	Density functional theory
WOS关键词	EVANS-POLANYI RELATION ; DENSITY-FUNCTIONAL THEORY ; TOTAL-ENERGY CALCULATIONS ; PT-CATALYZED NO ; VOLCANO CURVE ; COMBINED DFT ; STRUCTURE SENSITIVITY ; UNDERSTANDING TRENDS ; ACTIVATION-ENERGIES ; REACTION-MECHANISM
原始文献类型	Article
引用统计
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/122930
专题	物质科学与技术学院_博士生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	ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, 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	Wu, Panpan,Zaffran, Jeremie,Xu, Dongyang,et al. First-Principles-Based Microkinetic Simulations of CO2 Hydrogenation to Methanol over Intermetallic GaPd2: Method Development to Include Complex Interactions between Surface Adsorbates[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2020,124(29):15977-15987.
APA	Wu, Panpan,Zaffran, Jeremie,Xu, Dongyang,&Yang, Bo.(2020).First-Principles-Based Microkinetic Simulations of CO2 Hydrogenation to Methanol over Intermetallic GaPd2: Method Development to Include Complex Interactions between Surface Adsorbates.JOURNAL OF PHYSICAL CHEMISTRY C,124(29),15977-15987.
MLA	Wu, Panpan,et al."First-Principles-Based Microkinetic Simulations of CO2 Hydrogenation to Methanol over Intermetallic GaPd2: Method Development to Include Complex Interactions between Surface Adsorbates".JOURNAL OF PHYSICAL CHEMISTRY C 124.29(2020):15977-15987.