Theoretical Insights into the Effect of Cations, Anions, and Water on Fixation of CO(2)Catalyzed by Different Ionic Liquids
文献类型：期刊论文
| 作者 | Xia, Yangfeng1,2; Zhang, Yanqiang2; Su, Qian2; Dong, Kun2 |
| 刊名 | CHEMSUSCHEM
 |
| 出版日期 | 2020-08-21 |
| 页码 | 11 |
| ISSN号 | 1864-5631 |
| 关键词 | CO2-epoxide cycloaddition Density functional calculations ELF (Electron Localization Function) Ionic liquids |
| DOI | 10.1002/cssc.202001447 |
| 英文摘要 | Chemical fixation of CO(2)is an efficient means for decreasing amount of CO(2)in the atmosphere. One of promising technologies is the cycloaddition of CO(2)with epoxides to synthesize cyclic carbonates. In this reaction, ionic liquid (IL) catalysts show versatile and unique advantages. However, the reaction mechanism using ILs is not clear. In this work, a detailed theoretical investigation was performed by DFT calculations. The energetic profile shows that the reaction consists of three steps, with the ring-opening step being the rate-determining step. Based on the results, effects of cations, anions and water were calculated. Cations show strong hydrogen bonding interactions with epoxides, which decreases the energy barrier of the ring-opening step, indicating that hydrogen bonds play a positive role in promoting the reaction. The effect of anions was evaluated by nucleophilicity index (N-Nu); anions with a largerN(Nu)(stronger nucleophilicity) value show lower energy barriers. The influence of water was investigated by implicit and explicit models. Compared with the solvent-free case, water as an implicit solvent decreases the energy barriers through polarization with epoxides. In the explicit solvent model, the water molecules form new hydrogen bonds with epoxides and cations, which can efficiently reduce the energy barriers. The result indicates that there is a new synergic catalytic mechanism, in which the water acts not only as solvent but also as a catalyst in the reaction. Supporting experiments further confirm the calculation results. |
| WOS关键词 | CARBON-DIOXIDE ; CYCLIC CARBONATES ; CHEMICAL FIXATION ; CO2 ; EPOXIDES ; CATALYST ; DENSITY |
| 资助项目 | National Key R&D Program of China[2016YFB0600903] ; National Natural Science Foundation of China[91534116] ; National Natural Science Foundation of China[21878296] |
| WOS研究方向 | Chemistry ; Science & Technology - Other Topics |
| 语种 | 英语 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| WOS记录号 | WOS:000561082200001 |
| 资助机构 | National Key R&D Program of China ; National Natural Science Foundation of China |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/41805]  |
| 专题 | 中国科学院过程工程研究所 |
| 通讯作者 | Dong, Kun |
| 作者单位 | 1.Univ Chinese Acad Sci, Sch Chem Engn, Beijing 100049, Peoples R China 2.Chinese Acad Sci, Inst Proc Engn, Beijing Key Lab Ion Liquids Clean Proc, Key Lab Green Proc & Engn,State Key Lab Multiphas, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Xia, Yangfeng,Zhang, Yanqiang,Su, Qian,et al. Theoretical Insights into the Effect of Cations, Anions, and Water on Fixation of CO(2)Catalyzed by Different Ionic Liquids[J]. CHEMSUSCHEM,2020:11. |
| APA | Xia, Yangfeng,Zhang, Yanqiang,Su, Qian,&Dong, Kun.(2020).Theoretical Insights into the Effect of Cations, Anions, and Water on Fixation of CO(2)Catalyzed by Different Ionic Liquids.CHEMSUSCHEM,11. |
| MLA | Xia, Yangfeng,et al."Theoretical Insights into the Effect of Cations, Anions, and Water on Fixation of CO(2)Catalyzed by Different Ionic Liquids".CHEMSUSCHEM (2020):11. |
入库方式： OAI收割
来源：过程工程研究所
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