Interaction of CO2 with metal cluster-functionalized ionic liquids

Abstract Metal cluster-functionalized ionic liquids (ILs) exhibit promising characteristics for CO 2 conversion, however, progress in this area is currently limited due to the lack of understanding of the underlying reaction mechanisms involved. In this article the interaction of CO 2 with metal cluster-functionalized ILs is studied and provides key insights into the initial stages of CO 2 activation and subsequent conversion. The interaction of CO 2 with Au-Pd cluster-functionalized ILs is investigated using density functional theory (DFT) calculations based on the DFT-B3LYP approach and the mixed basis sets of 6-31+G (d, p) and LANL2DZ. It is found that single Au or Pd atoms can interact with ILs and results in a significantly stronger interaction of Au with ILs than that of Pd. More broadly it is also found that Au-Pd cluster-functionalized ILs can significantly enhance the interaction of CO 2 with ILs. Interestingly the interaction of CO 2 with Au-Pd cluster-functionalized IL is found to be highly dependent on the size and composition of the cluster. Among the systems studied, Au 1 Pd 2 -functionalized IL yields the strongest interaction with CO 2 . Our results highlight a non-monotonous behavior for the composition- and size-dependent interaction of CO 2 with Au-Pd cluster-functionalized ILs. It is proposed that these findings can provide a new roadmap for the design and development of metal cluster-functionalized ILs for CO 2 conversion applications.