Computational Approaches to Photoelectrode Design through Molecular Functionalization for Enhanced Photoelectrochemical Water Splitting.

Photoelectrochemical water splitting is a promising carbon-free approach to produce hydrogen from water. A photoelectrochemical cell consists of a semiconductor photoelectrode in contact with an aqueous electrolyte. Its performance is sensitive to properties of the photoelectrode/electrolyte interface, which may be tuned through functionalization of the photoelectrode surface with organic molecules. This can lead to improvements in the photoelectrode's properties. This Minireview summarizes key computational investigations on using molecular functionalization to modify photoelectrode stability, barrier height, and catalytic activity. It is discussed how first-principles density functional theory, first-principles molecular dynamics, and device modeling simulations can provide predictive insights and complement experimental investigations of functionalized photoelectrodes. Challenges and future directions in the computational modeling of functionalized photoelectrode/electrolyte interfaces within the context of experimental studies are also highlighted.