Protic vs aprotic ionic liquid for CO2 fixation: A simulation study

doi:10.1016/j.gee.2020.04.004

	Protic vs aprotic ionic liquid for CO2 fixation: A simulation study
	Sun, Wenzhong 1,3; Wang, Meichen 3; Zhang, Yaqin 3; Ding, Weilu 3; Huo, Feng 3; Wei, Li 1; He, Hongyan 2,3
刊名	GREEN ENERGY & ENVIRONMENT
	2020-04-01
卷号	5 期号:2 页码:183-194
关键词	Ionic liquid CO2 conversion Cycloaddition Synergistic catalysis DFT calculations
ISSN号	2096-2797
DOI	10.1016/j.gee.2020.04.004
英文摘要	The cycloaddition of CO2 with epoxides catalyzed by ionic liquids (ILs) has been a widely ongoing studied hot topic over the years. Recent experimental research has shown that the protic ionic liquids (PILs) behave stronger hydrogen proton donating ability than aprotic ionic liquids (APILs), and can effectively catalyze the cycloaddition of CO2. Unfortunately, the mechanistic explanation remains primarily unraveled. Herein, a detailed simulation study on the cycloaddition reaction catalyzed by PIL ([HDBU][Mim]) in comparison with APIL ([MeDBU][Mim]) reaction catalysts was conducted, including the three-step route (ring-opening of PO (propylene oxide), insertion of CO2 and ring-closure of propylene carbonate (PC)) and two-step route (simultaneously ring-opening of PO and addition of CO2, and then ring-closure of PC). Based on the activation energy barrier of the rate-determining step, PIL preferentially activates PO as the optimal route for the reaction with the energy barrier of 23.2 kcal mol(-1), while that of APIL is 31.2 kcal mol(-1). The role of [HDBU](+) in the reaction was also explored and found that the direct formation of intermolecular hydrogen bond (H-bond) between [HDBU](+) and the reactants (PO + CO2) was unfavorable for the reaction, while the cooperation with the anion [Mim](-) to assist indirectly was more conducive. To fully consider the reaction microenvironment of ILs, ONIOM calculation was used to study the solvent effect. At last, the above conclusions were further verified by the analysis of intermediates with charge, non-covalent interaction (NCI), and atoms in molecules (AIM) methods. The computational findings show that ILs studied in this work have dual functions of catalyst and solvent, enabling a microscopic understanding of the ILs catalyst for CO2 utilization as well as providing guidance for the rational design of more efficient ILs-based catalysts. (C) 2020, Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
资助项目	National Science Fund for Excellent Young Scholars[21922813] ; Key Research Program of Frontier Sciences of CAS[QYZDB-SSW-SLH022] ; National Key Projects for Fundamental Research and Development of China[2017YFB0603301] ; DNL Cooperation Fund, CAS[DNL180202] ; Youth Innovation Promotion Association of CAS[2017066]
WOS关键词	CARBON-DIOXIDE ; CHEMICAL FIXATION ; DENSITY FUNCTIONALS ; EFFICIENT CATALYST ; HIGHLY EFFICIENT ; CYCLIC CARBONATE ; CYCLOADDITION ; TRANSFORMATION ; EPOXIDES ; DYNAMICS
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Energy & Fuels ; Engineering
语种	英语
出版者	KEAI PUBLISHING LTD
WOS记录号	WOS:000543284000010
资助机构	National Science Fund for Excellent Young Scholars ; Key Research Program of Frontier Sciences of CAS ; National Key Projects for Fundamental Research and Development of China ; DNL Cooperation Fund, CAS ; Youth Innovation Promotion Association of CAS
内容类型	期刊论文
源URL	[http://ir.ipe.ac.cn/handle/122111/41168]
专题	中国科学院过程工程研究所
通讯作者	Wei, Li; He, Hongyan
作者单位	1.Dalian Polytech Univ, Sch Light Ind & Chem Engn, Dalian 116034, Peoples R China 2.Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China 3.Chinese Acad Sci, Inst Proc Engn, Beijing Key Lab Ion Liquids Clean Proc, CAS Key Lab Green Proc & Engn,State Key Lab Multi, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Sun, Wenzhong,Wang, Meichen,Zhang, Yaqin,et al. Protic vs aprotic ionic liquid for CO2 fixation: A simulation study[J]. GREEN ENERGY & ENVIRONMENT,2020,5(2):183-194.
APA	Sun, Wenzhong.,Wang, Meichen.,Zhang, Yaqin.,Ding, Weilu.,Huo, Feng.,...&He, Hongyan.(2020).Protic vs aprotic ionic liquid for CO2 fixation: A simulation study.GREEN ENERGY & ENVIRONMENT,5(2),183-194.
MLA	Sun, Wenzhong,et al."Protic vs aprotic ionic liquid for CO2 fixation: A simulation study".GREEN ENERGY & ENVIRONMENT 5.2(2020):183-194.