Tailored NiO_<i>x</i>/Ni Cocatalysts on Silicon for Highly Efficient Water Splitting Photoanodes via Pulsed Electrodeposition

Converting solar energy by photoelectrochemical water splitting has been regarded as a promising way to resolve the global energy crisis and alleviate environmental pollution. Silicon, which is earth-abundant and has a narrow band gap, is an attractive material for photoelectrochemical water splitting. However, Si-based photoelectrodes suffer from photocorrosion, which leads to instability in electrolytes and high overpotential. Herein, we have fabricated a metal–insulator–semiconductor structure of NiOx/Ni/n-Si photoanodes for highly efficient water splitting. NiOx/Ni nanoparticles, which act as well-known oxygen evolution catalysts, are deposited on the surface of silicon by facile pulsed electrodeposition. Light absorption and catalytic activity are greatly affected by the coverage of Ni nanoparticles, and the highly efficient NiOx/Ni catalyst structure is induced by simple annealing. The NiOx/Ni nanoparticles show highly enhanced charge separation and transport efficiency, which are vital factors for photoelectrochemical water splitting, leading to ∼100% Faradaic efficiency and incident photon-to-current efficiency. A low onset potential of 1.08 V versus a reversible hydrogen electrode for 1 mA/cm2 and a high photocurrent density of 14.7 mA/cm2 at 1.23 V are obtained.