Bonds over Electrons: Proton Coupled Electron Transfer at Solid–Solution Interfaces

[Image: see text] This Perspective argues that most redox reactions of materials at an interface with a protic solution involve net proton-coupled electron transfer (PCET) (or other cation-coupled ET). This view contrasts with the traditional electron-transfer-focused view of redox reactions at semiconductors, but redox processes at metal surfaces are often described as PCET. Taking a thermodynamic perspective, transfer of an electron is typically accompanied by a stoichiometric proton, much as the chemistry of lithium-ion batteries involves coupled transfers of e(–) and Li(+). The PCET viewpoint implicates the surface–H bond dissociation free energy (BDFE) as the preeminent energetic parameter and its conceptual equivalents, the electrochemical ne(–)/nH(+) potential versus the reversible hydrogen electrode (RHE) and the free energy of hydrogenation, ΔG°(H). These parameters capture the thermochemistry of PCET at interfaces better than electronic parameters such as Fermi energies, electron chemical potentials, flat-band potentials, or band-edge energies. A unified picture of PCET at metal and semiconductor surfaces is presented. Exceptions, limitations, implications, and future directions motivated by this approach are described.