Significance of Surface Formate Coverage on the Reaction Kinetics of Methanol Synthesis from CO2 Hydrogenation over Cu

doi:10.1021/acscatal.7b01910

	Significance of Surface Formate Coverage on the Reaction Kinetics of Methanol Synthesis from CO2 Hydrogenation over Cu
	Wu, Panpan1,2,3 ; Yang, Bo1,4
	2017-10
发表期刊	ACS CATALYSIS (IF:11.3[JCR-2023],12.6[5-Year])
ISSN	2155-5435
卷号	7 期号:10 页码:7187-7195
发表状态	已发表
DOI	10.1021/acscatal.7b01910
摘要	The hydrogenation of CO, to methanol over copper-based catalysts has attracted considerable attention recently. Among all the proposed reaction mechanisms, a large number of experimental and theoretical studies have focused on the one that includes a HCOO intermediate due to the fact that high coverages of formate over catalyst surfaces were observed experimentally. To systematically understand the influence of formate species coverage on the reaction kinetics of methanol synthesis, the energetics of the CO, hydrogenation pathway over clean and one- or two-formate preadsorbed Cu(211) are obtained using density functional theory calculations, and these energetics are further employed for microkinetic modeling. We find that the adsorption energies of the intermediates and transition states involved in the reaction pathway are changed in the presence of spectating formate species, and consequently, the potential energy diagrams are varied. analysis shows that the turnover frequencies (TOFs) over different formate preadsorbed surfaces vary under the same reaction condition. In particular, the reaction rates obtained over clean Cu(211) are generally the lowest, while those over one- or two formate preadsorbed surfaces depend on the reaction temperatures and pressures. Meanwhile, we find that only when the formate coverage effect is considered, some of the TOFs obtained from microkinetic modeling are in fair agreement with previous experimental results under similar conditions. After the degree of rate control analysis, it is found that the combination of HCOO and HCOOH hydrogenation steps can be treated as the "effective rate-determining step", which can be written as HCOO* + 2H* -> H2COOH* + 2*. Therefore, the formation of methanol is mainly controlled by the surface coverage of formate and hydrogen at the steady state, as well as the free energy barriers of the effective rate-determining step, i.e., effective free energy barriers.
关键词	density functional theory formate coverage effect CO2 hydrogenation methanol synthesis degree of rate control BEEF-vdW
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:000412795700090
出版者	AMER CHEMICAL SOC
EI入藏号	20174504368826
EI主题词	Association reactions ; Carbon dioxide ; Catalysts ; Copper compounds ; Density functional theory ; Energy barriers ; Free energy ; Hydrogenation ; Methanol ; Potential energy ; Reaction intermediates ; Reaction rates ; Surface reactions ; Synthesis gas manufacture ; Van der Waals forces
EI分类号	Thermodynamics:641.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Probability Theory:922.1
WOS关键词	DENSITY-FUNCTIONAL THEORY ; WATER-GAS SHIFT ; ADSORBATE-ADSORBATE INTERACTIONS ; HORIUTI-POLANYI MECHANISM ; TOTAL-ENERGY CALCULATIONS ; CU(110) MODEL CATALYSTS ; AUGMENTED-WAVE METHOD ; HETEROGENEOUS CATALYSIS ; ACETYLENE HYDROGENATION ; SELECTIVE HYDROGENATION
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/9895
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_博士生
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, 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	Wu, Panpan,Yang, Bo. Significance of Surface Formate Coverage on the Reaction Kinetics of Methanol Synthesis from CO2 Hydrogenation over Cu[J]. ACS CATALYSIS,2017,7(10):7187-7195.
APA	Wu, Panpan,&Yang, Bo.(2017).Significance of Surface Formate Coverage on the Reaction Kinetics of Methanol Synthesis from CO2 Hydrogenation over Cu.ACS CATALYSIS,7(10),7187-7195.
MLA	Wu, Panpan,et al."Significance of Surface Formate Coverage on the Reaction Kinetics of Methanol Synthesis from CO2 Hydrogenation over Cu".ACS CATALYSIS 7.10(2017):7187-7195.