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Theoretical Studies on the Adsorption of 1-Butyl-3-methyl-imidazolium-hexafluorophosphate (BMI/PF\(_6\)) on Au(100) Surfaces

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Abstract

In order to gain a systematic understanding of electrode/electrolyte interface between gold electrodes and ionic liquids, the adsorption of 1-butyl-3-methyl-imidazolium-hexafluorophosphate (BMI/PF\(_6\)) on Au(100) was determined for a wide range of surface coverages using density functional theory (DFT) calculations. At low coverages BMI is exceptionally mobile (translational and rotational barriers of \(<\)0.06 eV) and lies flat on the surface. For higher coverages the repulsive interactions between neighboring BMI adsorbates are minimized as much as possible, while attractive interactions between oppositely charged BMI and PF\(_6\) are maximized by coordinating PF\(_6\) with positively charged carbons in the imidazole rings. At coverages up to 1/20 monolayers (ML per Au surface atoms) this results in adsorbate islands with an internal coverage of 1/20 ML in a checkerboard pattern of BMI and PF\(_6\), all lying in a plane parallel to the surface. For coverages between 1/20 and 2/35 ML the BMI ions are twisted out of this plane. Beyond 2/35 ML a new strategy is needed to accommodate excess BMI/PF\(_6\) on the surface and a second checkerboard plane of BMI/PF\(_6\) forms above the first. This strategy is successful until the coverage reaches 1/10 ML, at which the BMI adsorbates stand end on in order to squeeze even more adsorbates onto the surface.

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Acknowledgments

The authors gratefully acknowledge support from the BMBF (Ministry of Education and Research) and the Deutsche Forschungsgemeinschaft (DFG) through the project KO 576/28-1 as well as the European Research Council through the ERC-StartingGrant THEOFUN (Grant Agreement No. 259608)

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Authors and Affiliations

  1. Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081, Ulm, Germany

    Johannes Plöger, Jonathan E. Mueller, Timo Jacob & Josef Anton

  2. Helmholtz-Institute-Ulm (HIU), Helmholtzstraße 11, 89081, Ulm, Germany

    Jonathan E. Mueller, Timo Jacob & Josef Anton

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  1. Johannes Plöger
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Correspondence to Josef Anton.

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Plöger, J., Mueller, J.E., Jacob, T. et al. Theoretical Studies on the Adsorption of 1-Butyl-3-methyl-imidazolium-hexafluorophosphate (BMI/PF\(_6\)) on Au(100) Surfaces. Top Catal 59, 792–801 (2016). https://doi.org/10.1007/s11244-016-0552-8

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