Disclosed herein are photoelectrodes and methods of making and use thereof. For example, disclosed herein are photo-electrodes comprising: a light absorbing layer; an insulator layer disposed on the light absorbing layer, wherein the insulator layer has an average thickness of 20 nanometers (nm) or more; and a set of protrusions, wherein each protrusion penetrates through the insulator layer to the light absorbing layer, such that each protrusion is in physical and electrical contact with the light absorbing layer; and a plurality of particles disposed on the insulator layer, wherein a least a portion of the plurality of particles are in physical and electrical contact with at least a portion of the set of protrusions; and wherein the plurality of particles and optionally the set of protrusions comprise a catalyst material.