Adsorption Motifs and Molecular Orientation at the Ionic Liquid/Noble Metal Interface: [C₂C₁Im][NTf₂] on Pt(111)

In solid catalysts with ionic liquid layers (SCILLs), ionic liquid (IL) thin films are used to modify the activity and selectivity of catalytic materials. In this work, we investigated the adsorption behavior of the IL 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [C₂C₁Im][NTf₂] on Pt(111) by combining experimental and theoretical studies. Under ultrahigh vacuum (UHV) conditions, the IL was deposited onto a Pt(111) single crystal surface by physical vapor deposition (PVD) at different surface temperatures (200, 300, and 400 K). The adsorption process was monitored by in situ infrared reflection absorption spectroscopy (IRAS). Complementary to the IRAS studies, we performed density functional theory (DFT) calculations and analyzed the adsorption motifs and orientation of the IL ions. In total, we calculated four different systems: (a) [C₂C₁Im]⁺ and [NTf₂]^- ions in the gas phase; [NTf₂]^- anions in (b) small (4 × 4) and (c) large (6 × 6) Pt(111) supercells; and (d) a complete ion pair of [C₂C₁Im][NTf₂] in a (6 × 6) Pt(111) supercell. Based on DFT, we simulated IR spectra and compared them to the experimental data. Our results suggest that the binding motif and orientation of the IL is strongly dependent on the actual IL coverage. In the monolayer (ML), [NTf₂]^- interacts strongly with the metal surface and adopts a specific orientation in which it interacts with the Pt surface via the SO₂ groups. Also the [C₂C₁Im]⁺ cations adopt a preferential orientation up to coverages of 1 ML. Upon transition to the multilayer region, the specific orientation of the ions is gradually lost.