摘要: The optimization of “green” electrochemical processes is one of the most important challenges in the transition toward renewable energy technologies. In many of these processes, including, e.g., CO2 and N2 reduction, small hydrophobic molecules are formed and react at the interface, and their hydration free energy modulates the associated thermodynamics. Here, we use molecular dynamics simulations to elucidate the mechanisms and energetics of hydrophobic hydration at an electrified gold/water interface. We propose an adaptation of the Lum–Chandler–Weeks theory that maps the changes in hydration free energies at the interface as a function of solute size and applied potential. Input files and raw data used for the figures have been deposited in Zenodo () and GitLab [https://gitlab.com/ampere2/serva\_-arxiv\_2011.08825_2020][1]). [1]: https://gitlab.com/ampere2/serva_-arxiv_2011.08825_2020