First principles studies on the selectivity of dimethoxymethane and methyl formate in methanol oxidation over V2O5/TiO2-based catalysts

doi:10.1039/c7cp02326j

	First principles studies on the selectivity of dimethoxymethane and methyl formate in methanol oxidation over V2O5/TiO2-based catalysts
	Li, Na 1,2; Wang, Shibin1,3 ; Sun, Yuhan1,3 ; Li, Shenggang1,3
	2017-08-07
发表期刊	PHYSICAL CHEMISTRY CHEMICAL PHYSICS (IF:2.9[JCR-2023],3.0[5-Year])
ISSN	1463-9076
卷号	19 期号:29 页码:19393-19406
发表状态	已发表
DOI	10.1039/c7cp02326j
摘要	First principles calculations using both molecular cluster and periodic slab models were performed to reveal the mechanism for the formation of dimethoxymethane (DMM) from methanol over V2O5/TiO2-based catalysts. Two different pathways were found, and the formation of DMM was predicted to be initiated by methanol chemisorption followed by a dehydration reaction with hemiacetal catalyzed by acidic sites. For unpromoted V2O5/TiO2 catalysts, we predicted the energy barrier for the rate determining step (RDS) to follow the order formaldehyde (FA)>4 methyl formate (MF) > DMM, consistent with the experimental observation for the preferential formation of DMM at a relatively low temperature and that of MF at a relatively high temperature. For sulfate-promoted catalysts, the energy barriers were calculated to follow the order FA > DMM > MF, so the sulfate promoter was predicted to mainly enhance the selectivity of MF, consistent with our previous experiment in which very high yield of MF was obtained with the sulfate-promoted catalyst. Calculated rate constants for the RDS were further used for semi-quantitative predictions of the product selectivities, which were found to be in quite good agreement with some of the recent experimental data in the literature, showing the validity of our approach. We also investigated the effects of the titania support and the polymerization of the vanadia species on the reactivity of the V2O5/TiO2 catalyst. Finally, we benchmarked several popular exchange-correlation functionals for calculating the reaction energies for the formation of FA, MF, and DMM from methanol oxidation, and the M06 hybrid functional was found to be superior to other semi-local and hybrid functionals studied.
收录类别	SCI
语种	英语
资助项目	Science and Technology Commission of Shanghai Municipality[14DZ1203700] ; Science and Technology Commission of Shanghai Municipality[14DZ1207602]
WOS研究方向	Chemistry ; Physics
WOS类目	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS记录号	WOS:000406334300060
出版者	ROYAL SOC CHEMISTRY
WOS关键词	GENERALIZED GRADIENT APPROXIMATION ; TOTAL-ENERGY CALCULATIONS ; NANOTUBES SUPPORTED V2O5 ; ELASTIC BAND METHOD ; ONE-STEP OXIDATION ; WAVE BASIS-SET ; OXIDE CATALYSTS ; SADDLE-POINTS ; EFFICIENT ; PERFORMANCE
原始文献类型	Article
通讯作者	Li, Shenggang
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/2871
专题	物质科学与技术学院物质科学与技术学院_特聘教授组_孙予罕组物质科学与技术学院_特聘教授组_李圣刚组物质科学与技术学院_博士生
通讯作者	Li, Shenggang
作者单位	1.Chinese Acad Sci, Shanghai Adv Res Inst, CAS Key Lab Low Carbon Convers Sci & Engn, 100 Haike Rd, Shanghai 201210, Peoples R China 2.Shanghai Univ, Dept Chem, 99 Shangda Rd, Shanghai 200444, Peoples R China 3.ShanghaiTech Univ, Sch Phys Sci & Technol, 100 Haike Rd, Shanghai 201210, Peoples R China
通讯作者单位	物质科学与技术学院
推荐引用方式 GB/T 7714	Li, Na,Wang, Shibin,Sun, Yuhan,et al. First principles studies on the selectivity of dimethoxymethane and methyl formate in methanol oxidation over V2O5/TiO2-based catalysts[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2017,19(29):19393-19406.
APA	Li, Na,Wang, Shibin,Sun, Yuhan,&Li, Shenggang.(2017).First principles studies on the selectivity of dimethoxymethane and methyl formate in methanol oxidation over V2O5/TiO2-based catalysts.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,19(29),19393-19406.
MLA	Li, Na,et al."First principles studies on the selectivity of dimethoxymethane and methyl formate in methanol oxidation over V2O5/TiO2-based catalysts".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 19.29(2017):19393-19406.