Synthesis and methane cracking activity of a silicon nitride supported vanadium nitride nanoparticle composite

The co-ammonolysis of V(NMe2)4 and Si(NHMe)4 with ammonia in THF and in the presence of ammonium triflate ([NH4][CF3SO3]) leads to the formation of monolithic gels. Pyrolysing these gels produces mesoporous composite materials containing nanocrystalline VN and amorphous silicon imidonitride. Elemental mapping indicated a thorough distribution of VN with no evidence of large cluster segregation. Whilst not active for ammonia synthesis, the silicon nitride based materials were found to possess activity for the COx-free production of H2 from methane, which makes them candidates for applications in which the presence of low levels of CO in H2 feedstreams is detrimental

Redox supercapacitor performance of nanocrystalline molybdenum nitrides obtained by ammonolysis of chloride- and amide-derived precursors

Reactions of MoCl5 or Mo(NMe2)4 with ammonia result in cubic ?-Mo2N or hexagonal ?1-MoN depending on reaction time and temperature. At moderate temperatures the cubic product from Mo(NMe2)4 exhibits lattice distortions. Fairly high surface areas are observed in the porous particles of the chloride-derived materials and high capacitances of up to 275 F g?1 are observed when electrodes made from them are cycled in aqueous H2SO4 or K2SO4 electrolytes. The cyclic voltammograms suggest charge is largely stored in the electrochemical double layer at the surface of these materials. Amide-derived molybdenum nitrides have relatively low surface areas and smaller capacitances, but do exhibit strong redox features in their cyclic voltammograms, suggesting that redox capacitance is responsible for a significant proportion of the charge stored

Nitrogen-rich transition metal nitrides

The solid state chemistry leading to the synthesis and characterization of metal nitrides with N:M ratios >1 is summarized. Studies of these compounds represent an emerging area of research. Most transition metal nitrides have much lower nitrogen contents, and they often form with non- or sub-stoichiometric compositions. These materials are typically metallic with often superconducting properties, and they provide highly refractory, high hardness materials with many technological applications. The higher metal nitrides should achieve formal oxidation states (OS) attaining those found among corresponding oxides, and they are expected to have useful semiconducting properties. Only a very few examples of such high OS nitrogen-rich compounds are known at present. The main group elements typically form covalently bonded nitride ceramics such as Si3N4, Ge3N4 and Sn3N4, and the early transition metals Zr and Hf produce Zr3N4 and Hf3N4. However, the only main example of a highly nitrided transition metal compound known to date is Ta3N5 that has a formal oxidation state +5 and is a semiconductor with visible light absorption leading to applications as a pigment and in photocatalysis. New synthesis routes are being explored to study the possible formation of other N-rich materials that are predicted to exist by ab initio calculations. There is a useful interplay between theoretical predictions and experimental synthesis studies at ambient and high pressure conditions, as we explore and establish the existence and structure–property relations of these new nitride compounds and polymorphs. Here we review the state of current investigations and indicate possible new directions for further work

Performance of nanocrystalline Ni3N as a negative electrode for sodium-ion batteries

Nickel nitride is synthesised by high temperature ammonolysis of nickel(II) hexamine and tris(ethylenediamine) salts. Its electrochemical characteristics are examined in half-cells vs. lithium and sodium. Samples with high surface area are found to have significant reversible charge storage capacity in sodium cells and hence to be a promising negative electrode material for sodium-ion batteries

Matched-filter study and energy budget suggest no detectable gravitational-wave 'extended emission' from GW170817

Van Putten & Della Valle (2018) have reported a possible detection of gravitational-wave 'extended emission' from a neutron star remnant of GW170817. Starting from the time-frequency evolution and total emitted energy of their reported candidate, we show that such an emission is not compatible with the current understanding of neutron stars. We explore the additional required physical assumptions to make a full waveform model, for example, taking the optimistic emission from a spining-down neutron star with fixed quadrupolar deformation, and study whether even an ideal single-template matched-filter analysis could detect an ideal, fully phase-coherent signal. We find that even in the most optimistic case an increase in energy and extreme parameters would be required for a confident detection with LIGO sensitivity as of 2018-08-17. The argument also holds for other waveform models following a similar time-frequency track and overall energy budget. Single-template matched filtering on the LIGO data around GW170817, and on data with added simulated signals, verifies the expected sensitivity scaling and the overall statistical expectation.Comment: 9 pages, 6 figures, updated version as accepted by MNRA

High-pressure annealing of a prestructured nanocrystalline precursor to obtain tetragonal and orthorhombic polymorphs of Hf3N4

Transition metal nitrides containing metal ions in high oxidation states are a significant goal for the discovery of new families of semiconducting materials. Most metal nitride compounds prepared at high temperature and high pressure from the elements have metallic bonding. However amorphous or nanocrystalline compounds can be prepared via metal-organic chemistry routes giving rise to precursors with a high nitrogen:metal ratio. Using X-ray diffraction in parallel with high pressure laser heating in the diamond anvil cell this work highlights the possibility of retaining the composition and structure of a metastable nanocrystalline precursor under high pressure-temperature conditions. Specifically, a nanocrystalline Hf3N4 with a tetragonal defect-fluorite structure can be crystallized under high-P,T conditions. Increasing the pressure and temperature of crystallization leads to the formation of a fully recoverable orthorhombic (defect cottunite-structured) polymorph. This approach identifies a novel class of pathways to the synthesis of new crystalline nitrogen-rich transition metal nitrides

Structural transformations and disordering in zirconolite (CaZrTi2O7) at high pressure

There is interest in identifying novel materials for use in radioactive waste applications and studying their behavior under high pressure conditions. The mineral zirconolite (CaZrTi2O7) exists naturally in trace amounts in diamond-bearing deep-seated metamorphic/igneous environments, and it is also identified as a potential ceramic phase for radionuclide sequestration. However, it has been shown to undergo radiation-induced metamictization resulting in amorphous forms. In this study we probed the high pressure structural properties of this pyrochlore-like structure to study its phase transformations and possible amorphization behavior. Combined synchrotron X-ray diffraction and Raman spectroscopy studies reveal a series of high pressure phase transformations. Starting from the ambient pressure monoclinic structure, an intermediate phase with P21/m symmetry is produced above 15.6 GPa via a first order transformation resulting in a wide coexistence range. Upon compression to above 56 GPa a disordered metastable phase III with a cotunnite-related structure appears that is recoverable to ambient conditions. We examine the similarity between the zirconolite behavior and the structural evolution of analogous pyrochlore systems under pressure.<br/

In situ phase behaviour of a high capacity LiCoPO4 electrode during constant or pulsed charge of a lithium cell

The phase changes that occur during lithium extraction from LiCoPO4 in lithium half-cells were studied using synchrotron X-ray diffraction. The existence of two two-phase regions with an intermediate phase present was observed. Significant variations in the composition of the phases of nominal stoichiometry LiCoPO4, Li2/3CoPO4 and CoPO4 resulted in unit cell volume variations. On current pulsing, lattice parameter shifts and phase recovery were directly observed

The reactivity of lattice nitrogen within the Ni2Mo3N and NiCoMo3N phases

In this study, the reactivity of bulk lattice nitrogen within the filled β-Mn structured Ni2Mo3N phase has been investigated by application of powder neutron diffraction and heterolytic nitrogen isotopic exchange measurements. In contrast to Co3Mo3N, despite the similarity in the N immediate local environment comprising NMo6 octahedra, its reactivity is found to be limited and this lower reactivity was maintained upon the introduction of a significant proportion of cobalt to yield its filled β-Mn structured CoNiMo3N quaternary nitride counterpart