A Molecular View of the Ionic Liquid Catalyst Interface of SCILLs: Coverage-Dependent Adsorption Motifs of [C4C1Pyr][NTf2] on Pd Single Crystals and Nanoparticles

Schuschke C, Fromm L, Träg J, Stumm C, Hohner C, Eschenbacher R, Grau S, Zahn D, Görling A, Bauer T, Libuda J (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Journal of Physical Chemistry C American Chemical Society

Abstract

Solid catalysts with ionic liquid layers (SCILLs) are heterogeneous catalysts coated with a thin layer of an ionic liquid (IL) to improve their selectivity. In this study, we investigated the interplay of the roomerature IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [C4C1Pyr][NTf2] with transition metal surfaces of both Pd(111) single crystals and Pd nanoparticles (NPs) supported on highly oriented pyrolytic graphite (HOPG). To this end, we combine theoretical insights obtained by density functional theory (DFT) and molecular dynamics (MD) calculations with experimental data acquired via time-resolved infrared reflection absorption spectroscopy (TR-IRAS) performed under ultrahigh vacuum (UHV) conditions. IL monolayer films formed on Pd(111) and Pd NPs are strongly bound to the surface via the SO2 moiety of the [NTf2]- anion. By combination of IRAS, DFT, and MD, we identify the most common adsorption motifs. Most importantly, the binding motif of the anion changes as a function of the IL coverage. On supported Pd NPs, additional effects arise from the particle morphology and from the diffusion of carbon from the support to the Pd NPs. Our results suggest that the effect of the IL film on the catalytic activity should strongly depend on the local coverage and the morphology of the catalyst NPs.

Authors with CRIS profile

Christian Schuschke Lehrstuhl für Katalytische Grenzflächenforschung Lukas Fromm Lehrstuhl für Theoretische Chemie Johannes Träg Lehrstuhl für Theoretische Chemie Corinna Stumm Lehrstuhl für Katalytische Grenzflächenforschung Chantal Hohner Lehrstuhl für Katalytische Grenzflächenforschung Roman Eschenbacher Lehrstuhl für Katalytische Grenzflächenforschung Sebastian Grau Lehrstuhl für Katalytische Grenzflächenforschung Dirk Zahn Professur für Theoretische Chemie Andreas Görling Lehrstuhl für Theoretische Chemie Tanja Retzer Lehrstuhl für Katalytische Grenzflächenforschung Jörg Libuda Lehrstuhl für Katalytische Grenzflächenforschung

How to cite

APA:

Schuschke, C., Fromm, L., Träg, J., Stumm, C., Hohner, C., Eschenbacher, R.,... Libuda, J. (2021). A Molecular View of the Ionic Liquid Catalyst Interface of SCILLs: Coverage-Dependent Adsorption Motifs of [C4C1Pyr][NTf2] on Pd Single Crystals and Nanoparticles. Journal of Physical Chemistry C. https://doi.org/10.1021/acs.jpcc.1c02131

MLA:

Schuschke, Christian, et al. "A Molecular View of the Ionic Liquid Catalyst Interface of SCILLs: Coverage-Dependent Adsorption Motifs of [C4C1Pyr][NTf2] on Pd Single Crystals and Nanoparticles." Journal of Physical Chemistry C (2021).

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