Molecular electrocatalysts play an essential role in a wide range of energy conversion processes. The objective of electrocatalyst design is to maximize the turnover frequency and minimize the overpotential for the overall catalytic cycle. Typically the catalytic cycle for hydrogen evolution is dominated by key proton-coupled electron transfer (PCET) processes comprised of sequential or concerted electron and proton transfer steps. This talk will focus on theoretical investigations of the mechanisms, thermodynamics, and kinetics of PCET processes in electrocatalytic cycles. Several molecular electrocatalysts for hydrogen production will be discussed, including cobalt complexes with diglyoxime or dithiolene ligands, as well as nickel complexes with pedant amines to facilitate proton relays. The calculations have revealed linear correlations that can be used to predict the impact of modifying the ligands, substituents, or metal centers. These theoretical studies are assisting in the interpretation of experimental data and the design of more effective molecular electrocatalysts.

Theoretical design of hydrogen-evolving molecular electrocatalysts

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.