Earth-Abundant Oxygen Evolution Catalysts Coupled onto ZnO Nanowire Arrays for Efficient Photoelectrochemical Water Cleavage

ZnO has long been considered as a model UVdriven photoanode for photoelectrochemical water splitting, but its performance has been limited by fast charge-carrier recombination, extremely poor stability in aqueous solution, and slow kinetics of water oxidation. These issues were addressed by applying a strategy of optimization and passivation of hydrothermally grown 1D ZnO nanowire arrays. The length and diameter of bare ZnO nanowires were optimized by varying the growth time and precursor concentration to achieve optimal photoelectrochemical performance. The addition of earth-abundant cobalt phosphate (Co-Pi) and nickel borate (Ni-B) oxygen evolution catalysts onto ZnO nanowires resulted in substantial cathodic shifts in onset potential to as low as about 0.3 V versus the reversible hydrogen electrode (RHE) for Ni-B/ZnO, for which a maximum photocur- rent density of 1.1 mAcm(-2) at 0.9V (vs. RHE) with applied bias photon-to-current efficiency of 0.4% and an unprecedented near-unity incident photon-to-current efficiency at 370 nm. In addition the potential required for saturated photocurrent was dramatically reduced from 1.6 to 0.9V versus RHE. Furthermore, the stability of these ZnO nanowires was significantly enhanced by using Ni-B compared to Co-Pi due to its superior chemical robustness, and it thus has additional functionality as a stable protecting layer on the ZnO surface. These remarkable enhancements in both photocatalytic activity and stability directly address the current severe limitations in the use of ZnO-based photoelectrodes for watersplitting applications, and can be applied to other photoanodes for efficient solar-driven fuel synthesis.