DOI: 10.1016/j.jcou.2018.09.027
Scopus记录号: 2-s2.0-85054506612
论文题名: A quantum-chemical insight on chemical fixation carbon dioxide with epoxides co-catalyzed by MIL-101 and tetrabutylammonium bromide
作者: Hu T.-D. ; Sun Y.-W. ; Ding Y.-H.
刊名: Journal of CO2 Utilization
ISSN: 22129820
出版年: 2018
卷: 28 起始页码: 200
结束页码: 206
语种: 英语
英文关键词: CO2 conversion
; DFT calculations
; Ionic liquid
; Metal-organic frameworks
; Synergistic catalysis
Scopus关键词: Activation energy
; Carbon dioxide
; Carbonation
; Catalysts
; Chromium compounds
; Crystalline materials
; Cycloaddition
; Design for testability
; Ionic liquids
; Organometallics
; Quantum chemistry
; Cyclic carbonates
; Cycloaddition reaction
; DFT calculation
; Metal organic framework
; Metalorganic frameworks (MOFs)
; Organic carbonates
; Synergistic catalysis
; Tetrabutylammonium bromide
; Catalysis
英文摘要: The fixation of CO2 with epoxides catalyzed by metal-organic frameworks (MOFs) has been the ongoing hot topic investigated extensively in experiment throughout the years. Recent experimental studies have revealed that the MIL-101(Cr) can effectively catalyze the cycloaddition conversion of CO2 with the aid of the tetrabutylammonium bromide(TBAB). However, the mechanistic details remain largely unraveled. In this work, we undertook a detailed DFT study on the cycloaddition reaction catalyzed by the binary system MIL-101/TBAB in comparison with the non-catalyzed, MIL-101-catalyzed alone and TBAB-catalyzed alone reactions. The three-step route involving the consecutive ring-opening of PO (propylene oxide), insertion of carbon dioxide, and ring-closure of cyclic carbonate was found to be kinetically more favorable than the two-step route (ring-opening of PO and ring-closure of cyclic carbonate). Based on the rate-determining activation energy barrier, the cycloaddition of CO2 to PO proceeds in a much easier way in the presence of MIL-101/TBAB (18.11 kcal mol-1) than the non-catalyzed (57.67 kcal mol-1), MIL-101-catalyzed (46.89 kcal mol-1) and TBAB-catalyzed (26.86 kcal mol-1) alone reactions. The computational findings can satisfactorily explain the available experimental observations, enabling a molecular-level understanding of congener catalysts for organic carbonate production as well as the rational design of more powerful MOF-orientated catalysts. © 2018 Elsevier Ltd. All rights reserved. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/111759
Appears in Collections: 气候减缓与适应
There are no files associated with this item.
作者单位: Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, China
Recommended Citation:
Hu T.-D.,Sun Y.-W.,Ding Y.-H.. A quantum-chemical insight on chemical fixation carbon dioxide with epoxides co-catalyzed by MIL-101 and tetrabutylammonium bromide[J]. Journal of CO2 Utilization,2018-01-01,28