Catalytic Mechanisms of Methanol Oxidation to Methyl Formate on Vanadia-Titania and Vanadia-Titania-Sulfate Catalysts

doi:10.1021/acs.jpcc.6b10289

	Catalytic Mechanisms of Methanol Oxidation to Methyl Formate on Vanadia-Titania and Vanadia-Titania-Sulfate Catalysts
	Li, Na 1,2; Wang, Shibin2,3 ; Ren, Qinghua 1; Li, Shenggang2,3 ; Sun, Yuhan2,3
	2016-12-29
发表期刊	JOURNAL OF PHYSICAL CHEMISTRY C (IF:3.3[JCR-2023],3.5[5-Year])
ISSN	1932-7447
卷号	120 期号:51 页码:29290-29301
发表状态	已发表
DOI	10.1021/acs.jpcc.6b10289
摘要	Density functional theory calculations were carried out using both cluster and slab models to investigate the catalytic reaction network and the effect of sulfate promoter on methanol selective oxidation using the V2O5/TiO2 catalyst. The hemiacetal mechanism was reaffirmed to be the most favorable reaction pathway for the formation of methyl formate (MF) by the prediction of another reaction pathway involving formic acid. Molecular oxygen was found to assist the desorption of the reaction products from the reduced catalyst active site, both formaldehyde and methyl formate (MF). The mechanism of catalyst regeneration was elucidated based solely on first principles calculations, which involve the conversion of another methanol molecule to formaldehyde over a peroxo species. This leads to our formulation of a complete catalytic reaction network for methanol selective oxidation to formaldehyde and MF on the V(2)O5(/)TiO(2) catalyst. In addition, the detailed mechanism for the formation of formaldehyde and MF was also predicted on the sulfate-promoted V2O5/TiO2 catalyst. Based on the calculated reaction networks, the preferred formation of MF on the V2O5/TiO2-based catalysts was attributed to the lower energy barrier of the oxidative dehydrogenation (ODH) of the CH3OCH2O* intermediate than that of CH3O. Furthermore, our calculated energy barriers also suggest that the sulfate promoted V2O5/TiO2 catalyst has not only higher catalytic activity for methanol conversion but also higher selectivity of MF over CH2O, consistent with previous experimental observations. The sulfate promoter was found to increase the positive charge at the V site, leading to a lower energy barrier for the ODH of CH3O than the unpromoted catalyst.
收录类别	SCI ; EI
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 ; Science & Technology - Other Topics ; Materials Science
WOS类目	Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
WOS记录号	WOS:000391160400042
出版者	AMER CHEMICAL SOC
EI入藏号	20173404070785
EI主题词	Calculations ; Catalysis ; Catalyst regeneration ; Catalyst selectivity ; Catalysts ; Catalytic oxidation ; Chemical reactions ; Dehydrogenation ; Density functional theory ; Energy barriers ; Formaldehyde ; Methanol ; Molecular oxygen ; Oxidation ; Reaction intermediates ; Sulfur compounds ; Titanium dioxide
EI分类号	Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Mathematics:921 ; Probability Theory:922.1
WOS关键词	PHOTOCATALYTIC SELECTIVE OXIDATION ; RUTHENIUM OXIDE CATALYSTS ; TOTAL-ENERGY CALCULATIONS ; NANOTUBES SUPPORTED V2O5 ; ELASTIC BAND METHOD ; ONE-STEP OXIDATION ; MN/CA-ZR CATALYST ; CARBON-DIOXIDE ; DIMETHYL ETHER ; LIQUID-PHASE
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/1592
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.Shanghai Univ, Dept Chem, 99 Shangda Rd, Shanghai 200444, Peoples R China 2.Chinese Acad Sci, Shanghai Adv Res Inst, CAS Key Lab Low Carbon Convers Sci & Engn, 100 Haike Rd, Shanghai 201210, 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,Ren, Qinghua,et al. Catalytic Mechanisms of Methanol Oxidation to Methyl Formate on Vanadia-Titania and Vanadia-Titania-Sulfate Catalysts[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2016,120(51):29290-29301.
APA	Li, Na,Wang, Shibin,Ren, Qinghua,Li, Shenggang,&Sun, Yuhan.(2016).Catalytic Mechanisms of Methanol Oxidation to Methyl Formate on Vanadia-Titania and Vanadia-Titania-Sulfate Catalysts.JOURNAL OF PHYSICAL CHEMISTRY C,120(51),29290-29301.
MLA	Li, Na,et al."Catalytic Mechanisms of Methanol Oxidation to Methyl Formate on Vanadia-Titania and Vanadia-Titania-Sulfate Catalysts".JOURNAL OF PHYSICAL CHEMISTRY C 120.51(2016):29290-29301.