Electronic Structure Engineering of Pt-Ni Alloy NPs by Coupling of Gold Single Atoms on N-Doped Carbon for Highly Efficient Oxygen Reduction Reaction and Hydrogen Evolution Reaction.

Improving the catalytic activity and durability of platinum-based alloy catalysts remains a formidable challenge in the context of renewable energy electrolysis applications. Herein, a facile and rapid photochemical deposition strategy for the synthesis of gold single atoms (Au SAs) anchored on N-doped carbon is presented. These Au SAs serve as a charge redistribution support for Pt-Ni alloy nanoparticles (PtNiNPs/AuSA-NDC), creating an extended electron-donating interface with Pt-Ni alloy sites. Consequently, the PtNiNPs/AuSA-NDC hybrid catalyst manifests exceptional catalytic performance and durability in both the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) under acidic conditions. Specifically, in ORR, it exhibits a half-wave potential (0.92 V vs RHE), with a mass activity 20.4 times superior to Pt/C at 0.9 V. In HER, PtNiNPs/AuSA-NDC demonstrates a notably reduced overpotential of 19.1 mV vs RHE at 10 mA cm-2 and a mass activity 38 times higher than Pt/C (at 0.25 mV). Furthermore, this hybrid catalyst displays outstanding durability, with only an 8.0 mV decay observed for ORR and a 6.9 mV decay for HER after 10 000 cycles. Theoretical calculations provide insight into the mechanism, demonstrating that isolated Au sites effectively modulate the electronic structure of Pt-Ni alloy sites, facilitating intermediate adsorption and enhancing reaction kinetics.

Observation of inherited plasmonic properties of TiN in titanium oxynitride (TiOxNy) for solar-drive photocatalytic applications.

This study demonstrates the synthesis of titanium oxynitride (TiOxNy) via a controlled step-annealing of commercial titanium nitride (TiN) powders under normal ambience. The structure of the formed TiOxNy system is confirmed via XRD, Rietveld refinements, XPS, Raman, and HRTEM analysis. A distinct plasmonic band corresponding to TiN is observed in the absorption spectrum of TiOxNy, indicating that the surface plasmonic resonance (SPR) property of TiN is being inherited in the resulting TiOxNy system. The prerequisites such as reduced band gap energy, suitable band edge positions, reduced recombination, and enhanced carrier-lifetime manifested by the TiOxNy system are investigated using Mott-Schottky, XPS, time-resolved and steady-state PL spectroscopy techniques. The obtained TiOxNy photocatalyst is found to degrade around 98% of 10 ppm rhodamine B dye in 120 min and produce H2 at a rate of ∼1546 µmolg-1h-1 under solar light irradiation along with consistent recycle abilities. The results of cyclic voltammetry, linear sweep voltammetry, electrochemical impedance and photocurrent studies suggest that this evolved TiOxNy system could be functioning via plasmonic Ohmic interface rather than the typical plasmonic Schottky interface due to their amalgamated band structures in the oxynitride phase.