Controlling Electrons and Protons through Theory: Molecular Electrocatalysts to Nanoparticles.

The development of renewable energy sources that are environmentally friendly and economical is of critical importance. The effective utilization of such energy sources relies on catalysts to facilitate the interconversion between electrical and chemical energy through multielectron, multiproton reactions. The design of effective catalysts for these types of energy conversion processes requires the ability to control the localization and movement of electrons and protons, as well as the coupling between them. Theoretical calculations, in conjunction with experimental validation and feedback, are playing a key role in these catalyst design efforts. A general theory has been developed for describing proton-coupled electron transfer (PCET) reactions, which encompass all reactions involving the coupled transfer of electrons and protons, including sequential and concerted mechanisms for multielectron, multiproton processes. In addition, computational methods have been devised to compute the input quantities for the PCET rate constant expressions and to generate free energy pathways for molecular electrocatalysts. These methods have been extended to heterogeneous PCET reactions to enable the modeling of PCET processes at electrode and nanoparticle surfaces. Three distinct theoretical studies of PCET reactions relevant to catalyst design for energy conversion processes are discussed. In the first application, theoretical calculations of hydrogen production catalyzed by hangman metalloporphyrins predicted that the porphyrin ligand is reduced, leading to dearomatization and proton transfer from the carboxylic acid hanging group to the meso carbon of the porphyrin rather than the metal center, producing a phlorin intermediate. Subsequent experiments isolated and characterized the phlorin intermediate, validating this theoretical prediction. These molecular electrocatalysts exemplify the potential use of noninnocent ligands to localize electrons and protons on different parts of the catalyst and to direct their motions accordingly. In the second application, theoretical calculations on substituted benzimidazole phenol molecules predicted that certain substituents would lead to multiple intramolecular proton transfer reactions upon oxidation. Subsequent experiments verified these multiproton reactions, as well as the predicted shifts in the redox potentials and kinetic isotope effects. These bioinspired molecular systems demonstrate the potential use of multiproton relays to enable the transport of protons over longer distances along specified pathways, as well as the tuning of redox potentials through this movement of positive charge. In the third application, theoretical studies of heterogeneous PCET in photoreduced ZnO nanoparticles illustrated the significance of proton diffusion through the bulk of the nanoparticle as well as interfacial PCET to an organic radical in solution at its surface. These theoretical calculations were consistent with prior experimental studies of this system, although theoretical methods for heterogeneous PCET have not yet attained the level of predictive capability highlighted for the molecular electrocatalysts. These examples suggest that theory will play a significant role in the design of both molecular and heterogeneous catalysts to control the movement and coupling of electrons and protons. The resulting catalysts will be essential for the development of renewable energy sources to address current energy challenges.