Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)
DOI: https://doi.org/10.29363/nanoge.matsusfall.2024.184
Publication date: 28th August 2024
Adsorption of ions and hydrophobic solutes are key processes in electrochemistry. The former regulates the Electric Double Layer and dictates important quantities, e.g. capacitance. The latter has major implications for heterogeneous catalysis, where small hydrophobic molecules are commonly involved as reactants and products. Despite solvation of charged and hydrophobic species are remarkably different, I will show in this presentation that the exotic way hydrophobicity arises at electrified metal-water interfaces influences both of them with a common underlying molecular mechanism.1-3
I will first show from classical molecular dynamics1 that the peculiar molecular arrangement of electrified gold/water interfaces induces atypical fluctuations of the liquid water density, resulting in a hydrophobic water-water interface formed close to the metal. I will then illustrate how such hydrophobicity dictates solvation free energy and regulates the accumulation of hydrophobic solutes (e.g. CO)1,3, as well as some ions (e.g. Cl-)2, at the interface. I will finally discuss some implication of these findings for electrochemical reactions involving hydrophobic molecules, with examples for CO2 and N2 reduction, as well as acid-base chemistry.1,5
[1] A. Serva, M. Salanne, M. Havenith, S. Pezzotti. PNAS 2021,118, e2023867118.
[2] S. R. Alfarano, S. Pezzotti, C. Stein, et al. PNAS 2021, 118, e2108568118.
[3] A. Serva, S. Pezzotti, J. Chem. Phys. 2024, 160, 9.
[4] A. Serva, M. Havenith, S. Pezzotti. J. Chem. Phys. 2021, 155, 204706.
[5] S. Murke, W. Chen, S. Pezzotti, M. Havenith. J. Am. Chem. Soc 2024, 146, 12423.
This work is funded by the European Research Council (ERC, ELECTROPHOBIC, Grant Agreement No. 101077129).
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