Near-Ambient Pressure XPS and NEXAFS Study of a Superbasic Ionic Liquid with CO<sub>2</sub>
Jordan Cole, Zoë Henderson, Andrew G. Thomas, Claudia L. Compeán‐González, Adam J. Greer, Christopher Hardacre, Federica Venturini, Wilson Quevedo, Pilar Ferrer, David C. Grinter, Georg Held, Karen L. Syres
Abstract
In situ photoemission and near-edge X-ray absorption fine structure (NEXAFS) techniques have been used to study the interaction of CO2 with an ionic liquid thin film. A thin film of the superbasic ionic liquid (SBIL) trihexyltetradecylphosphonium benzimidazolide ([P66614][benzim]) was prepared on a rutile TiO2 (110) surface and exposed to CO2 at near-ambient pressures. NEXAFS measurements combined with density functional theory calculations indicate a realignment of [benzim]− anions from 27° from the surface normal to 54° upon exposure to CO2. Angle-resolved X-ray photoelectron spectroscopy (AR-XPS) shows evidence of irreversible CO2 absorption in thin films of [P66614][benzim] and a greater concentration of CO2-reacted anions in the deeper layers. These results give a new perspective on CO2 uptake in ionic liquids and fundamental interactions at the liquid–gas interface. Understanding this interfacial behavior is important for developing ILs for gas capture applications and may influence the performance of other IL-based technologies.