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While using hydride precursors, such as TiH2, can promote the formation of some MAX phases, the mechanism for this stabilization effect by hydrogen has been unsolved. Herein, we report a facile synthesis method of Ti2AC (A = Zn, Al, In, and Ga) MAX phases using hydrogen as the phase stabilizer at their crystallographic voids. DFT calculations revealed that hydrogen could be incorporated in the center of the Ti3A (A = Zn, Al, Ga, and In) cages of Ti2AC MAX phases. The hydrogen is accommodated as an anion as a result of electron transfer from the surrounding Ti and A to H, leading to the stabilized state through Coulomb interaction between (Ti3A)δ+ and H-. Consequently, high-purity Ti2AC (A = Zn, Al, Ga, and In) was directly synthesized under pressure-less and milder temperature conditions by simply employing TiH2 as the precursor. These findings indicate that utilizing hydrogen could be one of the experimental parameters to facilitate the formation of materials having crystallographic voids.

Ammonia is one of the most important industrial intermediates due to the mass-demand for the production of various chemicals. Since the development of the Haber–Bosch process, most ammonia producti...

The Suzuki cross-coupling reaction, which is generally catalyzed by Pd-based materials, is a practical approach to create C–C bonds. Although heterogeneous catalysts, including metal-loaded and int...

We describe the synthesis of the new ternary compound CaRuSi whose chemical and physical properties help draw a clear picture of how electronic structure controls the behavior of an isostructural series of intermetallics. DFT calculations reveal that an electronic pseudogap arises near the Fermi level (EF), corresponding to 14 valence electrons per RuSi unit. The closed-shell-like character is further investigated by comparisons with the electronic structures of CaCoSi (15 electrons), where the EF lies above the corresponding pseudogap, and its hydride CaCoSiH, where formation of H anions restores the 14-electron count on the metal sublattice, returning the EF to the pseudogap. The chemical origin of the 14-electron pseudogap is interpreted with a reversed approximation Molecular Orbital analysis. Here, the pseudogap is shown to coincide with the filling of Ru 16 electron configurations isolobal to the d8 square planar complexes of coordination chemistry (but where 4 electron pairs are shared covalently b...

In this work, g-C3N4@TiO2 nanostructures with hollow sphere morphology, small grain size, high crystalline quality, and high surface area are successfully synthesized by the annealing method using melamine and hollowsphere precursor, which could be a universal method to synthesis hollow sphere nanoheterojunction. Excellent photocatalytic property was observed from the as-prepared g-C3N4@TiO2 nanostructure with 466.43 μmol·g–1·h–1 hydrogen generation rate under visible light irradiation (>420 nm), which was 5.5 times as much as the control couple, nanoparticle nanoheterojunction g-C3N4@TiO2. No apparent deactivation was found during the follow-up cycle performance test. The special morphology and the heterojunction construction contribute to both visible light absorption and photogenerated electron–hole pair separation efficiency and finally to the photocatalytic property. The content of g-C3N4 was proved to be an important parameter for the promotion of the photocatalytic property. Overlarge content may l...

We report the successful synthesis of LaCu0.67Si1.33 and Y5Si3 electride nanoparticles (NPs) using the Ar/H2 arc evaporation technique. The obtained particle sizes are 10–50 nm in diameter, and their surface areas are enhanced by orders of magnitude compared with hand-milled samples. Their catalytic performances were indeed improved by a factor of 60 for the hydrogenation of nitrobenzene (LaCu0.67Si1.33) and 3 for ammonia synthesis (Ru-loaded Y5Si3). This marked difference in the enhancement of catalytic activities between each system can be attributed to the geometric structure of active sites. These results show that the Ar/H2 arc evaporation technique offers wide versatility for the preparation of rare-earth-based electride NPs with enhanced catalytic activities.

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.

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.