Surface immobilized catalysts are highly promising candidates for a range of energy conversion reactions, and atomistic mechanistic understanding is essential for their rational design. Cobalt tetraphenylporphyrin (CoTPP) nonspecifically adsorbed on a graphitic surface has been shown to undergo concerted proton-coupled electron transfer (PCET) in aqueous solution. Herein, density functional theory calculations on both cluster and periodic models representing π-stacked interactions or axial ligation to a surface oxygenate are performed. As the electrode surface is charged due to applied potential, the adsorbed molecule experiences the electrical polarization of the interface and nearly the same electrostatic potential as the electrode, regardless of the adsorption mode. PCET occurs by electron abstraction from the surface to the CoTPP concerted with protonation to form a cobalt hydride, thereby circumventing Co(II/I) redox. Specifically, the Co(II) d-state localized orbital interacts with a proton from solution and an electron from the delocalized graphitic band states to produce a Co(III)-H bonding orbital below the Fermi level, corresponding to redistribution of electrons from the band states to the bonding states. These insights have broad implications for electrocatalysis by chemically modified electrodes and surface immobilized catalysts.
© 2023 The Authors. Published by American Chemical Society.