Violet Emission in ZnO Nanorods Treated with High-Energy Hydrogen Plasma

Violet photoluminescence was observed in high-energy hydrogen-plasma-treated ZnO nanorods at 13 K. The photoluminescence spectrum is dominated by a strong violet emission and a shoulder attributed to excitonic emission. The violet emission shows normal thermal behavior with an average lifetime of about 1 μs at 13 K. According to the time-resolved and excitation density-dependent photoluminescence, it was found that the violet emission is determined by at least two emitting channels, which was confirmed by annealing experiments. Evidence was also given that the violet emission is related to hydrogen. We suggested that the hydrogen-related complex defects formed under high-energy hydrogen plasma treatment are responsible for this violet emission

Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions

The development of transition metal intermetallic compounds, in which active sites are incorporated in lattice frameworks, has great potential for modulating the local structure and the electronic properties of active sites, and enhancing the catalytic activity and stability. Here we report that a new copper-based intermetallic electride catalyst, LaCu_0.67Si_1.33, in which Cu sites activated by anionic electrons with low work function are atomically dispersed in the lattice framework and affords selective hydrogenation of nitroarenes with above 40-times higher turnover frequencies (TOFs up to 5084 h^–1) than well-studied metal-loaded catalysts. Kinetic analysis utilizing isotope effect reveals that the cleavage of the H–H bond is the rate-determining step. Surprisingly, the high carrier density and low work function (LWF) properties of LaCu_0.67Si_1.33 enable the activation of hydrogen molecules with extreme low activation energy (<i>E</i>_a = 14.8 kJ·mol^–1). Furthermore, preferential adsorption of nitroarenes via a nitro group is achieved by high oxygen affinity of LaCu_0.67Si_1.33 surface, resulting in high chemoselectivity. The present efficient catalyst can further trigger the hydrogenation of other oxygen-containing functional groups such as aldehydes and ketones with high activities. These findings demonstrate that the transition metals incorporated in the specific lattice site function as catalytically active centers and surpass the conventional metal-loaded catalysts in activity and stability

Water Durable Electride Y₅Si₃: Electronic Structure and Catalytic Activity for Ammonia Synthesis

We report an air and water stable electride Y₅Si₃ and its catalytic activity for direct ammonia synthesis. It crystallizes in the Mn₅Si₃-type structure and confines 0.79/f.u. anionic electrons in the quasi-one-dimensional holes. These anionic electrons strongly hybridize with yttrium 4d electrons, giving rise to improved chemical stability. The ammonia synthesis rate using Ru­(7.8 wt %)-loaded Y₅Si₃ was as high as 1.9 mmol/g/h under 0.1 MPa and at 400 °C with activation energy of ∼50 kJ/mol. Its strong electron-donating ability to Ru metal of Y₅Si₃ is considered to enhance nitrogen dissociation and reduce the activation energy of ammonia synthesis reaction. Catalytic activity was not suppressed even after Y₅Si₃, once dipped into water, was used as the catalyst promoter. These findings provide novel insights into the design of simple catalysts for ammonia synthesis