Energy Sciences

Charge separation is one of the most critical factors for generating solar fuels via photoelectrochemical water splitting, but it is still not well understood. This work reveals the fundamental role of charge transfer in photoanodes for achieving high charge separation efficiency. Specifically, we fabricated a particulate Ta₃N₅ photoanode by a bottom-up method. By improving the charge separation with refined necking treatment, the photocurrent is increased by two orders of magnitude. The charge separation efficiency (η_sep) is analyzed by dividing it into charge generation efficiency (Φ_gene) and transportation efficiency (Φ_trans). Necking treatment is found to substantially improve the electron transfer. Transient photovoltage (TPV) measurements based on the Dember effect is used to confirm the benefit of necking treatment in improving the charge transportation. The superior electron transfer in the necked-Ta₃N₅ electrode is further evidenced by the facile electron exchange reaction with the ferri/ferrocyanide redox couple. Moreover, cobalt phosphate is found to promote both charge separation and surface reaction, resulting in a photocurrent of 6.1 mA cm^-2 at 1.23 V vs. RHE, which is the highest response for a particulate photoanode.