Bipolar Energetics and Bifunctional Catalytic Activity of a Nanocrystalline Ru Thin-Film Enable High-Performance Photoelectrochemical Water Reduction and Oxidation.

Photoelectrochemical (PEC) cells, which represent a promising technology for the production of hydrogen fuel through water splitting reactions, must meet two criteria to achieve high-performance operation: (i) a high thermodynamic open-circuit potential and (ii) a low kinetic overpotential. Herein, we achieved these criteria in both an oxygen-evolving n-Si photoanode and hydrogen-evolving p-Si photocathode by simple electrodeposition of a nanocrystalline thin film of Ru. The bifunctional electrocatalytic activity of the nanocrystalline Ru led to low overpotentials in both the acidic oxygen evolution reaction (0.27 V) and alkaline hydrogen evolution reaction (0.04 V). In addition, the nanocrystalline Ru/Si junctions influenced the interface energetics via the induction of an extrinsic electrochemical potential on the surface of the Ru nanocrystals through a redox reaction rather than the chemical potential of the electrons (work function) of bulk Ru. The nanocrystalline Ru film exhibited bipolar applicability, enabling both Ru/n-Si and Ru/p-Si junctions with high Voc values of 0.63 and 0.5 V, respectively. As a result, the n-Si photoanode in the acidic electrolyte and the p-Si photocathode in the alkaline electrolyte generated a photocurrent of 10 mA/cm2 at record values of 0.87 and 0.42 V versus the reversible hydrogen electrode, respectively. These results provide insight into the development of high-performance PEC cells based on a nanocrystalline electrocatalyst.