DOI: 10.1016/j.jcou.2018.09.012
Scopus记录号: 2-s2.0-85053761098
论文题名: CO2 conversion to cyclic carbonates catalyzed by ionic liquids with aprotic heterocyclic anions: DFT calculations and operando FTIR analysis
作者: Moya C. ; Sabater V. ; Yagüe G. ; Larriba M. ; Palomar J.
刊名: Journal of CO2 Utilization
ISSN: 22129820
出版年: 2018
卷: 28 起始页码: 66
结束页码: 72
语种: 英语
英文关键词: AHA ionic liquids
; CO2 conversion
; FTIR
; Propylene carbonate
; Reaction mechanism
英文摘要: Quantum chemical calculations and in situ infrared spectroscopy were applied to analyze the role of CO2 activation by aprotic heterocyclic anion ionic liquids (AHA-ILs) in its reaction with propylene oxide to form propylene carbonate. Two AHA-ILs with remarkably different behavior as CO2 chemical absorbent were considered: triethyl(octyl)-phosphonium indazole, [P2228][Inda], and triethyl(octyl)-phosphonium 2-cyanopyrrol-1-ide [P2228][2-CNPyr]. The structure and energy of reaction intermediates were predicted by Density Functional Theory (DFT) method, observing that CO2 and AHA-IL reaction form an anionic carbamate that promotes a nucleophilic attack on the propylene oxide, causing the ring opening with negligible energy barrier. Later intramolecular cyclization occurs, followed by the AHA-IL regeneration and propylene carbonate production, both requiring appreciable activation energy. The proposed reaction mechanism were experimentally validated by ATR-FTIR measurements, identifying the characteristic signals of reactants, products and intermediate species. Finally, the reaction using the AHA-ILs [P2228][Inda] and [P2228][2-CNPyr] was followed over time using operando ATR-FTIR technique at different operating conditions (temperature and catalyst concentration). A close relationship between the performance of AHA-IL as CO2 chemical absorbent and CO2 conversion catalyst is revealed, opening opportunities for the efficient application of AHA-ILs in intensified process of CO2 capture and utilization. ©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/111766
Appears in Collections: 气候减缓与适应
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作者单位: Sección de Ingeniería Química, Universidad Autónoma de Madrid, Madrid, 28049, Spain; Departamento de Ingeniería Química y de Materiales, Universidad Complutense de Madrid, Madrid, 28040, Spain
Recommended Citation:
Moya C.,Sabater V.,Yagüe G.,et al. CO2 conversion to cyclic carbonates catalyzed by ionic liquids with aprotic heterocyclic anions: DFT calculations and operando FTIR analysis[J]. Journal of CO2 Utilization,2018-01-01,28