eprintid: 1474806
rev_number: 24
eprint_status: archive
userid: 608
dir: disk0/01/47/48/06
datestamp: 2016-02-17 16:13:02
lastmod: 2021-09-19 23:46:55
status_changed: 2016-02-17 16:13:02
type: article
metadata_visibility: show
creators_name: Mercy, M
creators_name: Taylor, SF
creators_name: Jacquemin, J
creators_name: Hardacre, C
creators_name: Bell, RG
creators_name: De Leeuw, NH
title: The addition of CO₂ to four superbase ionic liquids: a DFT study
ispublished: pub
divisions: UCL
divisions: B04
divisions: C06
divisions: F56
note: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
abstract: The addition of carbon dioxide to four superbase ionic liquids, [P3333][Benzim], [P3333][124Triz], [P3333][123Triz] and [P3333][Bentriz] was studied using a molecular DFT approach involving anions alone and individual ion pairs. Intermolecular bonding within the individual ion pairs is characterised by a number of weak hydrogen bonds, with the superbase anion geometrically arranged so as to maximize interactions between the heterocyclic N atoms and the cation. The pairing energies show no correlation to the observed CO2 adsorption capacity. Addition of CO2 to the anion alone clearly resulted in the formation of a covalently-bound carbamate function with the strength of binding correlated to experimental capacity. In the ion pair however the cation significantly alters the nature of the bonding such that the overall cohesive energy is reduced. Formation of a strong carbamate function occurs at the expense of weakening the interaction between anion and cation. In the more weakly absorbing ion pairs which contain [123Triz](-) and [Bentriz](-), the carbamate-functionalised systems are very close in energy to adducts in which CO2 is more weakly bound, suggesting an equilibrium between the chemi- and physisorbed CO2.
date: 2015-11-21
date_type: published
official_url: http://dx.doi.org/10.1039/c5cp05153c
oa_status: green
full_text_type: pub
language: eng
primo: open
primo_central: open_green
article_type_text: Journal Article
verified: verified_manual
elements_id: 1086604
doi: 10.1039/c5cp05153c
language_elements: eng
lyricists_name: Bell, Robert
lyricists_name: De Leeuw, Nora
lyricists_id: RGBEL28
lyricists_id: NHDEL32
actors_name: Gibson, Alice
actors_id: AGIBS47
actors_role: owner
full_text_status: public
publication: Physical Chemistry Chemical Physics
volume: 17
number: 43
pagerange: 28674-28682
event_location: England
issn: 1463-9084
citation:        Mercy, M;    Taylor, SF;    Jacquemin, J;    Hardacre, C;    Bell, RG;    De Leeuw, NH;      (2015)    The addition of CO₂ to four superbase ionic liquids: a DFT study.                   Physical Chemistry Chemical Physics , 17  (43)   pp. 28674-28682.    10.1039/c5cp05153c <https://doi.org/10.1039/c5cp05153c>.       Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/1474806/1/c5cp05153c%281%29.pdf