Ultralow Catalytic Loading for Optimised Electrocatalytic Performance of AuPt Nanoparticles to Produce Hydrogen and Ammonia.

The hydrogen evolution and nitrite reduction reactions are key to producing green hydrogen and ammonia. Antenna-reactor nanoparticles hold promise to improve the performances of these transformations under visible-light excitation, by combining plasmonic and catalytic materials. However, current materials involve compromising either on the catalytic activity or the plasmonic enhancement and also lack control of reaction selectivity. Here, we demonstrate that ultralow loadings and non-uniform surface segregation of the catalytic component optimize catalytic activity and selectivity under visible-light irradiation. Taking Pt-Au as an example we find that fine-tuning the Pt content produces a 6-fold increase in the hydrogen evolution compared to commercial Pt/C as well as a 6.5-fold increase in the nitrite reduction and a 2.5-fold increase in the selectivity for producing ammonia under visible light excitation relative to dark conditions. Density functional theory suggests that the catalytic reactions are accelerated by the intimate contact between nanoscale Pt-rich and Au-rich regions at the surface, which facilitates the formation of electron-rich hot-carrier puddles associated with the Pt-based active sites. The results provide exciting opportunities to design new materials with improved photocatalytic performance for demanding sustainable energy applications.

Triple Play of Band Gap, Interband, and Plasmonic Excitations for Enhanced Catalytic Activity in Pd/HxMoO3 Nanoparticles in the Visible Region.

Plasmonic photocatalysis has been limited by the high cost and scalability of plasmonic materials, such as Ag and Au. By focusing on earth-abundant photocatalyst/plasmonic materials (HxMoO3) and Pd as a catalyst, we addressed these challenges by developing a solventless mechanochemical synthesis of Pd/HxMoO3 and optimizing photocatalytic activities in the visible range. We investigated the effect of HxMoO3 band gap excitation (at 427 nm), Pd interband transitions (at 427 nm), and HxMoO3 localized surface plasmon resonance (LSPR) excitation (at 640 nm) over photocatalytic activities toward the hydrogen evolution and phenylacetylene hydrogenation as model reactions. Although both excitation wavelengths led to comparable photoenhancements, a 110% increase was achieved under dual excitation conditions (427 + 640 nm). This was assigned to a synergistic effect of optical excitations that optimized the generation of energetic electrons at the catalytic sites. These results are important for the development of visible-light photocatalysts based on earth-abundant components.

NiMo-NiCu Inexpensive Composite with High Activity for Hydrogen Evolution Reaction.

In this work, the effect of copper addition on NiMo coating is evaluated in regard to the hydrogen evolution reaction (HER). NiMo and NiMo-NiCu composites are prepared by a simple coelectrodeposition process. The effect of Cu on deposit characters were tested by varying it in the range of 0.06-0.20 molar ratio. Copper addition promotes the growth of a new crystalline phase: NiCu. Also, the copper addition changed the composite surface. NiMo-NiCu0.12 shows a surface roughness 30 times higher than the NiMo material. NiMo-NiCu materials present higher activity toward HER, larger electroactive area, and higher stability in continuous water electrolysis than NiMo catalysts, as demonstrated by Tafel curves, electrochemical impedance spectroscopy measurements, and polarization tests. The combination of the large electroactive area due to the copper addition, the synergism between Ni-Mo, and the presence of Ni and Mo oxides on the surface results in catalyst with excellent features for HER application.