Atomically manipulated proton transfer energizes water oxidation on silicon carbide photoanodes

Surmounting the sluggish water oxidation kinetics beyond the hole-dominated thermodynamic effect is a topic of great scientific interest to establish fully renewable hydrogen technology from solar-powered water splitting. Herein, we demonstrate that the bottleneck of photoelectrochemical water oxidation can be overcome via atomic manipulation of proton transfer on the polar surfaces of silicon carbide (SiC) photoanodes. On the typical carbon-face SiC, where proton-coupled electron transfer governed the interfacial hole transfer for water oxidation, substantial energy loss was inevitable due to the highly activated proton-transfer steps. Via preferentially exposing the silicon-face, we enabled surface-catalyzed barrierless O–H breaking with a facile proton exchange and migration character. This mechanistically shifted the rate limiting step of water oxidation from sluggish proton-coupled electron transfer to a more energy-favorable electron transfer. The proof-of-concept study introduced here may open up new possibilities to design sophisticated photoelectrodes for an unbiased solar water splitting cell via surface engineering.