Improved Photoelectrocatalytic Performance for Water Oxidation by Earth-Abundant Cobalt Molecular Porphyrin Complex-Integrated BiVO₄ Photoanode

An earth-abundant, low-cost cobalt porphyrin complex (CoTCPP) is designed as a molecular catalyst to work on three-dimensional BiVO4 film electrode for water oxidation for the first time. Under illumination of a 100 mW cm(-2) Xe lamp, the CoTCPP-functionalized BiVO4 photoanode exhibits a 2-fold enhancement in photocurrent density at 1.23 V vs RHE and nearly a 450 mV cathodic shift at 0.5 mA cm(-2) photocurrent density relative to bare BiVO4 in 0.1 M Na2SO4 (pH = 6.8). Simultaneously, stoichiometric oxygen and hydrogen are generated with a faradic efficiency of 80% over 4 h. The activity and stability of the BiVO4 photoanode are dramatically increased by molecular CoTCPP, giving rise to higher performance than previously reported noble metal ruthenium complex-modified BiVO4 photoanode. By using hydrogen peroxide as the hole scavenger, we demonstrate that molecular CoTCPP catalyst greatly suppresses the hole-electron recombination on the surface of BiVO4 semiconductor, which offers a promising route toward high efficiency, low cost, practical solar fuel generation device.