Enhanced Performance of Si MIS Photocathodes Containing Oxide-Coated Nanoparticle Electrocatalysts.

Electrodepositing low loadings of metallic nanoparticle catalysts onto the surface of semiconducting photoelectrodes is a highly attractive approach for decreasing catalyst costs and minimizing optical losses. However, securely anchoring nanoparticles to the photoelectrode surface can be challenging-especially if the surface is covered by a thin insulating overlayer. Herein, we report on Si-based photocathodes for the hydrogen evolution reaction that overcome this problem through the use of a 2-10 nm thick layer of silicon oxide (SiOx) that is deposited on top of Pt nanoparticle catalysts that were first electrodeposited on a 1.5 nm SiO2|p-Si(100) absorber layer. Such insulator-metal-insulator-semiconductor (IMIS) photoelectrodes exhibit superior durability and charge transfer properties compared to metal-insulator-semiconductor (MIS) control samples that lacked the secondary SiOx overlayer. Systematic investigation of the influence of particle loading, SiOx layer thickness, and illumination intensity suggests that the SiOx layer possesses moderate conductivity, thereby reducing charge transfer resistance associated with high local tunneling current densities between the p-Si and Pt nanoparticles. Importantly, the IMIS architecture is proven to be a highly effective approach for stabilizing electrocatalytic nanoparticles deposited on insulating overlayers without adversely affecting mass transport of reactant and product species associated with the hydrogen evolution reaction.