Essential Role of Water in the Autocatalysis Behavior of Methanol Synthesis from CO2 Hydrogenation on Cu: A Combined DFT and Microkinetic Modeling Study

doi:10.1021/acs.jpcc.8b12460

	Essential Role of Water in the Autocatalysis Behavior of Methanol Synthesis from CO2 Hydrogenation on Cu: A Combined DFT and Microkinetic Modeling Study
	Xu, Dongyang1 ; Wu, Panpan1,2,3 ; Yang, Bo1,4
	2019-04-11
发表期刊	JOURNAL OF PHYSICAL CHEMISTRY C
ISSN	1932-7447
卷号	123 期号:14 页码:8959-8966
发表状态	已发表
DOI	10.1021/acs.jpcc.8b12460
摘要	Water is able to promote many chemical reactions in an autocatalysis manner, and the essential role that water plays in the system is still worth discussing. In the process of methanol synthesis from CO2 hydrogenation on Cu, whether the promoting species is molecular water or water derived O/OH is controversial. To systematically understand the influence of the presence of O/OH on the reaction kinetics of CO2 hydrogenation to methanol, we here carry out density functional theory calculations to obtain the energetics over O/OH preadsorbed Cu(211) and further use them for microkinetic modeling in order to calculate the formation rate of methanol. The calculation results show that the free energy barriers of CO2 activation by molecular water through both HCOO and COOH routes are higher than those by the hydrogen atom on clean and OH or O preadsorbed Cu(211). The subsequent microkinetic modeling indicates that the formation rate of methanol over Cu(211) is improved in the presence of O/OH. Detailed analyses on the coverage and degree of rate control of surface species reveal that the presence of O/OH on the catalyst surface will destabilize the spectating formate and lower the energies of rate-controlling transition states. The formate coverage effect is further included in the microkinetic modeling, and we find that the reaction rate is further increased at lower temperatures. Our current work provides evidence that the surface adsorbed O and OH are able to promote the formation of methanol from CO2 hydrogenation and, more importantly, highlights the fact that the activity of methanol formation is sensitive to the surface adsorbates.
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, Shanghai Advanced Research Institute, Chinese Academy of Sciences[KLLCCSE-201602]
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:000464768600055
出版者	AMER CHEMICAL SOC
EI入藏号	20191306708093
EI主题词	Atoms ; Carbon dioxide ; Density functional theory ; Free energy ; Hydrogenation ; Methanol ; Reaction kinetics ; Synthesis gas manufacture
WOS关键词	FISCHER-TROPSCH SYNTHESIS ; TOTAL-ENERGY CALCULATIONS ; ACETYLENE HYDROGENATION ; METAL-SURFACES ; CATALYSTS ; MECHANISM ; CU(111) ; SELECTIVITY ; KINETICS ; FORMATE
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/34324
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	1.ShanghaiTech 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, Shanghai Adv Res Inst, CAS Key Lab Low Carbon Convers Sci & Engn, 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	Xu, Dongyang,Wu, Panpan,Yang, Bo. Essential Role of Water in the Autocatalysis Behavior of Methanol Synthesis from CO2 Hydrogenation on Cu: A Combined DFT and Microkinetic Modeling Study[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2019,123(14):8959-8966.
APA	Xu, Dongyang,Wu, Panpan,&Yang, Bo.(2019).Essential Role of Water in the Autocatalysis Behavior of Methanol Synthesis from CO2 Hydrogenation on Cu: A Combined DFT and Microkinetic Modeling Study.JOURNAL OF PHYSICAL CHEMISTRY C,123(14),8959-8966.
MLA	Xu, Dongyang,et al."Essential Role of Water in the Autocatalysis Behavior of Methanol Synthesis from CO2 Hydrogenation on Cu: A Combined DFT and Microkinetic Modeling Study".JOURNAL OF PHYSICAL CHEMISTRY C 123.14(2019):8959-8966.