Galvanic Deposition of Pt Nanoparticles on Black TiO2 Nanotubes for Hydrogen Evolving Cathodes.

A galvanic deposition method for the in-situ formation of Pt nanoparticles (NPs) on top and inner surfaces of high-aspect-ratio black TiO2 -nanotube electrodes (bTNTs) for true utilization of their total surface area has been developed. Density functional theory calculations indicated that the deposition of Pt NPs was favored on bTNTs with a preferred [004] orientation and a deposition mechanism occurring via oxygen vacancies, where electrons were localized. High-resolution transmission electron microscopy images revealed a graded deposition of Pt NPs with an average diameter of around 2.5 nm along the complete nanotube axis (length/pore diameter of 130 : 1). Hydrogen evolution reaction (HER) studies in acidic electrolytes showed comparable results to bulk Pt (per geometric area) and Pt/C commercial catalysts (per mg of Pt). The presented novel HER cathodes of minimal engineering and low noble metal loadings (µg cm-2 range) achieved low Tafel slopes (30-34 mV dec-1 ) and high stability in acidic conditions. This study provides important insights for the in-situ formation and deposition of NPs in high-aspect-ratio structures for energy applications.

Double Perovskite Cobaltites Integrated in a Monolithic and Noble Metal-Free Photoelectrochemical Device for Efficient Water Splitting.

Water photoelectrolysis has the potential to produce renewable hydrogen fuel, therefore addressing the intermittent nature of sunlight. Herein, a monolithic, photovoltaic (PV)-assisted water electrolysis device of minimal engineering and of low (in the µg range) noble-metal-free catalysts loading is presented for unassisted water splitting in alkaline media. An efficient double perovskite cobaltite catalyst, originally developed for high-temperature proton-conducting ceramic electrolyzers, possesses high activity for the oxygen evolution reaction in alkaline media at room temperatures too. Ba1-xGd1-yLax+yCo2O6-δ (BGLC) is combined with a NiMo cathode, and a solar-to-hydrogen efficiency of 6.6% in 1.0 M NaOH, under 1 sun simulated illumination for 71 h, is demonstrated. This work highlights how readily available earth-abundant materials and established PV methods can achieve high performance and stable and monolithic photoelectrolysis devices with potential for full-scale applications.