Experiments have suggested that photoreduced ZnO nanocrystals transfer an electron and a proton to organic radicals through a concerted proton-coupled electron transfer (PCET) mechanism. The kinetics of this process was studied by monitoring the decay of the absorbance that reflects the concentration of electrons in the conduction bands of the nanocrystals. Interestingly, this absorbance exhibited nonexponential decay kinetics that could not be explained by heterogeneities of the nanoparticles or electron content. To determine if proton diffusion from inside the nanocrystal to reactive sites on the surface could lead to such nonexponential kinetics, herein this process is modeled using kinetic Monte Carlo simulations. These simulations provide the survival probability of a proton hopping among bulk, subsurface, and surface sites within the nanocrystal until it reaches a reactive surface site where it transfers to an organic radical. Using activation barriers predominantly obtained from periodic density functional theory, the simulations reproduce the nonexponential decay kinetics. This nonexponential behavior is found to arise from the broad distribution of lifetimes caused by different types of subsurface and surface sites. The longer lifetimes are associated with the proton becoming temporarily trapped in a subsurface site that does not have direct access to a reactive surface site due to capping ligands. These calculations suggest that movement of the protons rather than the electrons dominate the nonexponential kinetics of the PCET reaction. Thus, the impact of both bulk and surface properties of metal-oxide nanoparticles on proton conductivity should be considered when designing heterogeneous catalysts.
Keywords: density functional theory; kinetic Monte Carlo; nanocrystal; nanoparticle; proton conductivity; proton diffusion; proton-coupled electron transfer.