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%0 Thesis
%A Cheong, Oskar
%T Computational investigation of solvation phenomena at metal-electrolyte interfaces
%V 631
%I RWTH Aachen University
%V Dissertation
%C Jülich
%M RWTH-2024-06567
%@ 978-3-95806-759-2
%B Schriften des Forschungszentrums Jülich. Reihe Energie & Umwelt = Energy & environment
%P xvii, 142 Seiten : Illustrationen
%D 2024
%Z Druckausgabe: 2024. - Onlineausgabe: 2024. - Auch veröffentlicht auf dem Publikationsserver der RWTH Aachen University
%Z Dissertation, RWTH Aachen University, 2024
%X The interplay between metal catalyst surfaces and its surrounding solvent environment has a considerable impact on interfacial electrochemical processes, affecting both activity and selectivity of electrochemical reactions, e.g., the carbon dioxide (CO2) reduction reaction. While atomistic simulations are useful to gain advanced insight into the metal-electrolyte interface, many challenging problems exist for a realistic, computational description of the complex electrochemical interface. Especially, a computationally feasible scheme for description of solvation effects at the metal-electrolyte interface has yet to be established. This thesis explores several computational improvements that enable accounting for solvation effects when modelling a metal-electrolyte interface. The first part of the thesis focuses on testing the ability of a classical molecular dynamics (CMD) simulation approach based on the interface force field (IFF) to efficiently model water structures on metal surfaces, using the lead (Pb) surface as a test case. While ab initio molecular dynamics (AIMD) calculations are considered to be more accurate than CMD calculations, the latter allows for exploration of much longer time- and length- scales, which results in better equilibrated water structures. This work demonstrates the potential of using IFF-based CMD simulations for statistically complete sampling water structures on metal surfaces. In the second part of the thesis the impact of different solvation models on the CO2 reduction reaction on both silver (Ag) and lead (Pb) catalysts towards formic acid (HCOOH) and carbon monoxide (CO) products are investigated. The systematic analysis indicates that accounting for explicit solvation has a crucial impact on the CO2 reduction reaction, correctly predicting primary products on both metal catalysts, which was not achieved by simplified computation assuming vacuum environment. Furthermore, the performance of implicit, explicit and hybrid solvation schemes are discussed in that subproject. Another problem investigated in this thesis is to account for solvation entropy effects on surface chemical reactions. In that context, the Two Phase Thermodynamic (2PT) model is applied and tested to evaluate solute entropy effects in bulk solvent and at the metal-electrolyte interface. Since entropy contributions to Gibbs energies of chemical reactions at the metal-solvent interface are usually either neglected or modeled using the ideal gas approximation, solvent effects on the reaction free energies are often insufficiently or incorrectly accounted for. The 2PT method offers a solution to obtain computationally efficient and accurate estimates of solvent entropy effects, resulting in a more realistic description of chemical reactions at metal-electrolyte interfaces. The presented research aims to pave the way towards efficient computation of electrochemical interfaces under realistic conditions, which is an essential ability in the context of accelerating computer-aided design of novel and efficient electrocatalysts.
%F PUB:(DE-HGF)11 ; PUB:(DE-HGF)3
%9 Dissertation / PhD ThesisBook
%R 10.18154/RWTH-2024-06567
%U https://publications.rwth-aachen.de/record/989043