| 胡奕明,汪海有.铑催化转化合成气活性中间体的量子化学研究[J].分子催化,1993,(2): |
| 铑催化转化合成气活性中间体的量子化学研究 |
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| DOI： |
| 中文关键词: 铑催化剂,DV-Xα-SCC方法,甲酰基,金属氧卡宾结构 |
| 英文关键词: |
| 基金项目: |
| 胡奕明 汪海有 |
厦门大学化学系 厦门361005
(胡奕明)
，厦门大学化学系 厦门361005(汪海有)
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| 中文摘要: |
| 采用DV-Xα-SCC方法研究用铑催化剂在有助剂MnO和无助剂两种情况下转化合成气产生的甲酰基中间体,讨论了它在催化剂表面的稳定状态、电子结构及成键性质.结果表明,吸附态甲酰基在催化剂表面形成金属氧卡宾结构,稳定了体系.与无助剂的情况相比,助催剂MnO可使体系更稳定,并使C-O键受到更大程度的削弱,同时它还对中间体的反应行为产生影响. |
| 英文摘要: |
| Formyl intermediate is studied by DV-Xa-SCC method as an active species formed in the process of syngas conversion to ethanol over the Rh/SiO2 and Rh-MnO/SiO2 catalysts. The stable states and the electronic structures as well as the bond properties of formyl on the surface of catalysts studied are discussed. HC = O adsorbed on the catalyst surface is stablized by forming a metal-oxygen carbene structure. This new structure keeps high activity as an intermediate in syngas conversion reactions, with stronger Rh-C bond and weaker C-O bond than its former Rh-CHO structure. Compared with the formyl formed over unpromoted Rh-catalyst, the formyl formed over MnO-promoted Rh-catalyust is more stable, and not only has the C-O bond weakened more markedly but also behaves in a slightly different way in the reaction tendency. |
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