How significant the charge density of olefins to their epoxidation reactions over M4+-substituted zeolitic catalysts: A DFT investigation
文献类型：期刊论文
| 作者 | Wu, Xiaomin1; Yang, Gang1,3; Zhou, Lijun1; Han, Xiuwen2,3 |
| 刊名 | computational and theoretical chemistry
 |
| 出版日期 | 2013-08-01 |
| 卷号 | 1017页码:109-116 |
| 关键词 | Active site Activation free energy Charge density Descriptor Density functional calculations |
| 英文摘要 | density functional calculations were performed to study the active sites of m4+-substituted zeolites (m = ti, zr, ge, sn, pb) and find a descriptor to correlate the olefin structures and epoxidation activities. the active-site formation is the most thermodynamically favorable for m = ti. transition elements (ti and zr) form the bidentate m(eta(2)-ooh) active sites whereas main group elements (ge, sn and pb) are apt to form the monodentate m(eta(1)-ooh) species. the charge density of the c=c double bond (q(cc)) was found to be closely correlated with the activation free energy (delta g(not equal)), and the linear functions were fitted as delta g(not equal) = 32.5 * q(cc) + 54.4 (r-2 = 0.89) and delta g(not equal) = 41.2 * q(cc) + 55.5 (r-2 = 0.95) for the ethylene- and styrene-related systems, respectively. several exceptions to these functions have been detected suggesting the presence of other influencing factors. nonetheless, the q(cc) descriptor proves to be applicable not only for the common electrophilic reactions, but also for those that may fall outside the scope of "electrophilic" as discussed in this work. (c) 2013 elsevier b.v. all rights reserved. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | chemistry, physical |
| 研究领域[WOS] | chemistry |
| 关键词[WOS] | titanium-based epoxidation ; active-site ; ethylene epoxidation ; hydrogen-peroxide ; functional theory ; oniom method ; ti ; silicalite ; ts-1 ; adsorption |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000322297300015 |
| 公开日期 | 2015-11-10 |
| 源URL | [http://159.226.238.44/handle/321008/137934]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | 1.Northeast Forestry Univ, Engn Res Ctr Forest Biopreparat, Minist Educ, Harbin 150040, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China 3.Eindhoven Univ Technol, Dept Chem Engn & Chem, NL-5600 MB Eindhoven, Netherlands |
| 推荐引用方式 GB/T 7714 | Wu, Xiaomin,Yang, Gang,Zhou, Lijun,et al. How significant the charge density of olefins to their epoxidation reactions over M4+-substituted zeolitic catalysts: A DFT investigation[J]. computational and theoretical chemistry,2013,1017:109-116. |
| APA | Wu, Xiaomin,Yang, Gang,Zhou, Lijun,&Han, Xiuwen.(2013).How significant the charge density of olefins to their epoxidation reactions over M4+-substituted zeolitic catalysts: A DFT investigation.computational and theoretical chemistry,1017,109-116. |
| MLA | Wu, Xiaomin,et al."How significant the charge density of olefins to their epoxidation reactions over M4+-substituted zeolitic catalysts: A DFT investigation".computational and theoretical chemistry 1017(2013):109-116. |
入库方式： OAI收割
来源：大连化学物理研究所
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