The photoelectrochemical splitting of water into hydrogen and oxygen requires a semiconductor to absorb light and generate electron-hole pairs, and a catalyst to enhance the kinetics of electron transfer between the semiconductor and solution. A crucial question is how this catalyst affects the band bending in the semiconductor, and, therefore, the photovoltage of the cell. We introduce a simple and inexpensive electrodeposition method to produce an efficient n-Si/SiOx/Co/CoOOH photoanode for the photoelectrochemical oxidation of water to oxygen. The photoanode functions as a solid-state, metal-insulator-semiconductor photovoltaic cell with spatially non-uniform barrier heights in series with a low overpotential water-splitting electrochemical cell. The barrier height is a function of the Co coverage; it increases from 0.74 eV for a thick, continuous film to 0.91 eV for a thin, inhomogeneous film that has not reached coalescence. The larger barrier height leads to a 360 mV photovoltage enhancement relative to a solid-state Schottky barrier.