Carbon dioxide adsorption and activation on ionic liquid decorated Au(111) surface: A DFT study

Abstract

We use first principle approaches to study the adsorption and catalytic activation mechanism of CO₂ on ionic liquids (ILs, [C_nMIm]⁺[Cl]^- (n = 0-6)) attached to a Au(111) surface. The adsorption of CO₂ at this liquid-solid model interface occurs via either (i) parallel π-stacking mode or (ii) CO₂ oxygen lone pair (lp)···π interaction. These CO₂ physisorption modes, which depend on the CO₂ landing angle at this interface, are identified as an efficient way to activate CO₂ and its further conversion into value-added products. For illustration, we discuss the conversion of CO₂ into formic acid where the ILs@Au(111) decorated interface allows reduction of the activation energy for the CO₂ + H₂ → HCOOH reaction. In sum, our electrode/electrolyte based interface model provides valuable information to design novel heterogeneous catalysts for CO₂ conversion. Indeed, our work establishes that a suitable interface material is enough to activate CO₂.

Keywords: Au(111) surface; CO(2) activation and conversion; Heterogeneous catalysis; Ionic liquids; Solid-liquid interface.