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Induced Protic Behaviour in Aprotonic Ionic Liquids by Anion Basicity for Efficient Carbon Dioxide Capture.
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-06-03 , DOI: 10.1002/cphc.202000320 Darius J Yeadon 1, 2 , Johan Jacquemin 1, 2, 3 , Natalia V Plechkova 1 , Manuel Maréchal 4 , Kenneth R Seddon 1
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-06-03 , DOI: 10.1002/cphc.202000320 Darius J Yeadon 1, 2 , Johan Jacquemin 1, 2, 3 , Natalia V Plechkova 1 , Manuel Maréchal 4 , Kenneth R Seddon 1
Affiliation
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The interactions between aprotonic tetrabutylphosphonium carboxylate ionic liquids (ILs), [P4 4 4 4][CnCOO] (n=1, 2 and 7), and water were investigated. The cation‐anion interactions occur via the α‐1H on [P4 4 4 4]+ and the carboxylate headgroup of the anion. Upon addition, H2O localises around the carboxylate headgroups, inducing an electron inductive effect towards the oxygens, leading to ion‐pair separation. Studies with D2O and [P4 4 4 4][CnCOO] revealed protic behaviour of the systems, with proton/deuterium exchange occurring at the α‐1H of the cation, promoted by the basicity of the anion, forming an intermediate ylide. The greater influence of van der Waals forces of the [P4 4 4 4][C7COO] system allows for re‐orientation of the ions through larger interdigitation. The protic behaviour of the neat ILs allows for CO2 to be chemically absorbed on the ylide intermediate, forming a phosphonium‐carboxylate zwitterion, signifying proton exchange occurs even in the absence of H2O. The absorption of CO2 in equimolar IL‐H2O mixtures forms a hydrogen carbonate, through a proposed reaction of the CO2 with an intermediate hydroxide, and carboxylic acid.
中文翻译：
阴离子碱性可在非质子离子液体中诱导质子行为，从而有效捕获二氧化碳。
研究了质子化四丁基羧酸carboxy离子液体（ILs），[P 4 4 4 4 ] [C n COO]（n = 1、2和7）与水之间的相互作用。阳离子与阴离子的相互作用是通过[P 4 4 4 4 ] +上的α - 1 H和阴离子的羧酸根首基发生的。加完后，H 2 O定位在羧酸根首基周围，对氧产生电子感应效应，导致离子对分离。D 2 O和[P 4 4 4 4 ] [C n的研究COO]揭示了系统的质子行为，用质子/氘交换发生在α- 1个的阳离子的H，通过阴离子的碱性促进，形成中间叶立德。[P 4 4 4 4 ] [C 7 COO]系统的范德华力的较大影响允许通过较大的叉指重新定位离子。纯净ILs的质子行为允许CO 2被化学吸收到叶立德中间体上，形成a-羧酸盐两性离子，表明即使在没有H 2 O的情况下也会发生质子交换。等摩尔IL-H中CO 2的吸收2 O混合物通过拟议的CO反应形成碳酸氢盐2用中间体氢氧化物和羧酸。
更新日期：2020-06-03
中文翻译：
阴离子碱性可在非质子离子液体中诱导质子行为，从而有效捕获二氧化碳。
研究了质子化四丁基羧酸carboxy离子液体（ILs），[P 4 4 4 4 ] [C n COO]（n = 1、2和7）与水之间的相互作用。阳离子与阴离子的相互作用是通过[P 4 4 4 4 ] +上的α - 1 H和阴离子的羧酸根首基发生的。加完后，H 2 O定位在羧酸根首基周围，对氧产生电子感应效应，导致离子对分离。D 2 O和[P 4 4 4 4 ] [C n的研究COO]揭示了系统的质子行为，用质子/氘交换发生在α- 1个的阳离子的H，通过阴离子的碱性促进，形成中间叶立德。[P 4 4 4 4 ] [C 7 COO]系统的范德华力的较大影响允许通过较大的叉指重新定位离子。纯净ILs的质子行为允许CO 2被化学吸收到叶立德中间体上，形成a-羧酸盐两性离子，表明即使在没有H 2 O的情况下也会发生质子交换。等摩尔IL-H中CO 2的吸收2 O混合物通过拟议的CO反应形成碳酸氢盐2用中间体氢氧化物和羧酸。
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