Metal/water interfaces catalyze a large variety of chemical reactions, which often involve small hydrophobic molecules. In the present theoretical study, we show that hydrophobic hydration at the Au(100)/water interface actively contributes to the reaction free energy by up to several hundreds of meV. This occurs either in adsorption/desorption reaction steps, where the vertical distance from the surface changes in going from reactants to products, or in addition and elimination reaction steps, where two small reactants merge into a larger product and vice versa. We find that size and position effects cannot be captured by treating them as independent variables. Instead, their simultaneous evaluation allows us to map the important contributions, and we provide examples of their combinations for which interfacial reactions can be either favored or disfavored. By taking a N2 and a CO2 reduction pathway as test cases, we show that explicitly considering hydrophobic effects is important for the selectivity and rate of these relevant interfacial processes.
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28 November 2021
Research Article|
November 30 2021
The role of hydrophobic hydration in the free energy of chemical reactions at the gold/water interface: Size and position effects
Special Collection:
The Chemical Physics of the Electrode-Electrolyte Interface
Alessandra Serva
;
Alessandra Serva
a)
1
Sorbonne Université, CNRS, Physico-Chimie des Electrolytes et Nanosystèmes Interfaciaux, PHENIX
, F-75005 Paris, France
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Martina Havenith
;
Martina Havenith
2
Department of Physical Chemistry II, Ruhr University Bochum
, 44780 Bochum, Germany
3
Department of Physics, Technische Universität Dortmund
, 44227 Dortmund, Germany
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Simone Pezzotti
Simone Pezzotti
a)
2
Department of Physical Chemistry II, Ruhr University Bochum
, 44780 Bochum, Germany
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Note: This paper is part of the JCP Special Topic on The Chemical Physics of the Electrode–Electrolyte Interface.
J. Chem. Phys. 155, 204706 (2021)
Article history
Received:
August 31 2021
Accepted:
November 05 2021
Citation
Alessandra Serva, Martina Havenith, Simone Pezzotti; The role of hydrophobic hydration in the free energy of chemical reactions at the gold/water interface: Size and position effects. J. Chem. Phys. 28 November 2021; 155 (20): 204706. https://doi.org/10.1063/5.0069498
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