Mechanistic Pathways for Methylcyclohexane Hydrogenolysis over Supported Ir Catalysts
文献类型：期刊论文
| 作者 | Shi, Hui1,2; Gutierrez, Oliver Y.1,2; Zheng, Anmin3; Haller, Gary L.1,2; Lercher, Johannes A.1,2 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY C
 |
| 出版日期 | 2014-09-11 |
| 卷号 | 118期号:36页码:20948-20958 |
| 英文摘要 | H/D isotope effects on methylcyclohexane hydrogenolysis over Ir/Al2O3 catalysts were examined by combining measured rates with theoretical estimates provided by partition function based analyses. Normal H/D isotope effects (r(H)/r(D) > 1) were observed for endocyclic and exocyclic C-C bond hydrogenolysis. Hydrogenolysis is concluded to occur via stepwise dehydrogenation followed by cleavage of the C-C bond and subsequent hydrogenation of the cleaved entities. The so-called multiplet mechanism (i.e., the C-C bond of a flat-lying physisorbed cyclic molecule is cleaved upon the attack of a coadsorbed H atom) is unequivocally excluded. For ring-opening, either C-C bond cleavage or C-H(D) bond reformation may be rate-determining, due to their indistinguishable isotope effects under the studied conditions. C-H(D) bond dissociation does not control the rate of C-C bond hydrogenolysis. For the exocyclic cleavage of the methyl group, a higher degree of unsaturation of the surface intermediate and the potential impact of mobile H atoms on large Ir particles are noted. |
| WOS标题词 | Science & Technology ; Physical Sciences ; Technology |
| 类目[WOS] | Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary |
| 研究领域[WOS] | Chemistry ; Science & Technology - Other Topics ; Materials Science |
| 关键词[WOS] | CARBON BOND ACTIVATION ; RING-OPENING REACTIONS ; C-C BONDS ; ETHANE HYDROGENOLYSIS ; TRANSITION-METALS ; 1ST-PRINCIPLES CALCULATIONS ; KINETIC ASSESSMENT ; NI(100) SURFACE ; ADSORPTION ; METHYLCYCLOPENTANE |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000341619500025 |
| 公开日期 | 2015-07-14 |
| 源URL | [http://ir.wipm.ac.cn/handle/112942/1425]  |
| 专题 | 武汉物理与数学研究所_磁共振应用研究部 |
| 作者单位 | 1.Tech Univ Munich, Dept Chem, D-85747 Garching, Germany 2.Tech Univ Munich, Catalysis Res Ctr, D-85747 Garching, Germany 3.Chinese Acad Sci, Wuhan Inst Phys & Math, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan 430071, Peoples R China |
| 推荐引用方式 GB/T 7714 | Shi, Hui,Gutierrez, Oliver Y.,Zheng, Anmin,et al. Mechanistic Pathways for Methylcyclohexane Hydrogenolysis over Supported Ir Catalysts[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2014,118(36):20948-20958. |
| APA | Shi, Hui,Gutierrez, Oliver Y.,Zheng, Anmin,Haller, Gary L.,&Lercher, Johannes A..(2014).Mechanistic Pathways for Methylcyclohexane Hydrogenolysis over Supported Ir Catalysts.JOURNAL OF PHYSICAL CHEMISTRY C,118(36),20948-20958. |
| MLA | Shi, Hui,et al."Mechanistic Pathways for Methylcyclohexane Hydrogenolysis over Supported Ir Catalysts".JOURNAL OF PHYSICAL CHEMISTRY C 118.36(2014):20948-20958. |
入库方式： OAI收割
来源：武汉物理与数学研究所
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