Intermetallic PdIn catalyst for CO2 hydrogenation to methanol: mechanistic studies with a combined DFT and microkinetic modeling method

doi:10.1039/c9cy01242g

	Intermetallic PdIn catalyst for CO2 hydrogenation to methanol: mechanistic studies with a combined DFT and microkinetic modeling method
	Wu, Panpan1,2,3 ; Yang, Bo1,4
	2019-11-07
发表期刊	CATALYSIS SCIENCE & TECHNOLOGY (IF:4.4[JCR-2023],4.7[5-Year])
ISSN	2044-4753
EISSN	2044-4761
卷号	9 期号:21 页码:6102-6113
发表状态	已发表
DOI	10.1039/c9cy01242g
摘要	Great efforts have been made to explore efficient catalysts for methanol synthesis from CO2 hydrogenation. Recently, it was found experimentally that the PdIn intermetallic catalyst showed high activity, selectivity and stability for this reaction. In order to understand the underlying reaction mechanisms over the PdIn intermetallic catalyst at the atomic level, we here investigate the reaction pathways of methanol and carbon monoxide formation over PdIn(110) and PdIn(211) with a combined density functional theory and microkinetic modeling approach. We find that CH3OH formation is mainly via HCOO -> HCOOH -> H2COOH -> CH2O + OH -> CH3O + OH -> CH3OH(g) + H2O(g) on both surfaces. The direct dissociation of CO2 to CO and O is favored on PdIn(110) for CO formation, whereas the preferred CO formation pathway on PdIn(211) is through the formation of COOH and its subsequent dissociation to give CO and OH on the surface. The microkinetic modeling results also show that, at steady state, the coverage of HCOO on both surfaces is rather high and may not be ignored. Degree of rate control (DRC) analysis results suggest that the transition state of O and CO2 hydrogenation over PdIn(110) and PdIn(211), respectively, can be considered rate controlling for CO formation. Regarding the formation of methanol, the DRC analysis results show that the transition state of HCOOH hydrogenation to H2COOH is the rate-controlling transition state on PdIn(110) over the whole temperature range studied. In contrast, the rate-controlling transition state varies from H2COOH dissociation to HCOOH hydrogenation with increase in temperature for PdIn(211). In addition, we propose an approach to estimate the formation rates of methanol at different formate coverages on the basis of the effective rate-controlling step identified from the DRC analysis. It was found that the activity of methanol formation on both surfaces studied is enhanced at high formate coverage under practical reaction conditions.
收录类别	SCI ; SCIE ; EI
语种	英语
资助项目	Foundation of Key Laboratory of Low-Carbon Conversion Science Engineering[KLLCCSE-201602]
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
WOS记录号	WOS:000493075200018
出版者	ROYAL SOC CHEMISTRY
EI主题词	Binary alloys ; Carbon dioxide ; Carbon monoxide ; Catalyst activity ; Catalyst selectivity ; Density functional theory ; Dissociation ; Formic acid ; Hydrogenation ; Intermetallics ; Methanol
WOS关键词	TOTAL-ENERGY CALCULATIONS ; CU BIMETALLIC CATALYSTS ; ACETYLENE HYDROGENATION ; SELECTIVE HYDROGENATION ; STEAM ; KINETICS ; SURFACES ; INSIGHT ; SITES ; WATER
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/80560
专题	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_博士生
通讯作者	Yang, Bo
作者单位	1.Shanghai Tech Univ, Sch Phys Sci & Technol, 393 Middle Huaxia Rd, Shanghai 201210, Peoples R China 2.Chinese Acad Sci, Shanghai Inst Ceram, Shanghai 200050, Peoples R China 3.Univ Chinese Acad Sci, Beijing 101407, Peoples R China 4.Chinese Acad Sci, CAS Key Lab Low Carbon Convers Sci & Engn, Shanghai Adv Res Inst, 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,Yang, Bo. Intermetallic PdIn catalyst for CO2 hydrogenation to methanol: mechanistic studies with a combined DFT and microkinetic modeling method[J]. CATALYSIS SCIENCE & TECHNOLOGY,2019,9(21):6102-6113.
APA	Wu, Panpan,&Yang, Bo.(2019).Intermetallic PdIn catalyst for CO2 hydrogenation to methanol: mechanistic studies with a combined DFT and microkinetic modeling method.CATALYSIS SCIENCE & TECHNOLOGY,9(21),6102-6113.
MLA	Wu, Panpan,et al."Intermetallic PdIn catalyst for CO2 hydrogenation to methanol: mechanistic studies with a combined DFT and microkinetic modeling method".CATALYSIS SCIENCE & TECHNOLOGY 9.21(2019):6102-6113.