Proton-coupled electron transfer in molecular and material catalysis

Proton-coupled electron transfer (PCET) plays an important role in a variety of electrochemical and photo-excited reactions occurring in molecular, material, and biological systems. In this thesis, the role of PCET in hydrogen evolution molecular electrocatalysts, and iron-doped nickel-oxyhydroxide thin films used for oxygen evolution reaction, are explored by means of quantum chemistry. Detailed electronic structural analysis performed using density functional theory is used to provide atomic level understanding of these catalytic systems. The electron-proton nonadiabaticity of PCET process is investigated for the phenoxyl/phenol self-exchange reaction, and the results show that the vibronic coupling is dependent on the molecular geometry. This diagnostic is important for the calculation of PCET rate constants. The rate constants and kinetic isotope effects for concerted PCET in a set of hydroquinone derivatives are calculated and analyzed in comparison with experimental data