Search

A new solvent free protocol is presented to introduce amide and amine functionalities (N-aliphatic groups) onto graphene oxide in an energy efficient manner. Nitrogen contents of 3.6 wt% are obtained in only 5 minutes at room temperature by using ammonia gas as the nitrogen source for the ammonolysis of graphene oxide. [ABSTRACT FROM AUTHOR]

The topotactic nitridation of cation ordered, tetragonal Sr2FeMoO6 in NH3 at moderate temperatures leads to cubic, Fm3̅m double perovskite oxynitride Sr2FeMoO4.9N1.1 where double-exchange interactions determine ferromagnetic order with TC≈ 100 K. Substitution of oxide by nitride induces bond asymmetries and local electronically driven structural distortions, which combined with Fermi level lowering restricts charge itinerancy to confined regions and preclude spontaneous long-range magnetic order. Under a magnetic field, ferromagnetic correlations expand, favoring charge delocalization and a negative magnetoresistance is observed. [ABSTRACT FROM AUTHOR]

RHfO2N perovskites with R = La, Nd and Sm show a GdFeO3-type structure and are semiconductors with band gaps of 3.35, 3.40 and 2.85 eV and relative dielectric constants of 30, 16 and 28 respectively. These compounds have adequate reduction and oxidation potentials to conduct the overall water splitting reaction, and the analogous perovskite LaZrO2N with a band gap of 2.8 eV shows photocatalytic activity under visible light irradiation for O2 evolution. [ABSTRACT FROM AUTHOR]

Topochemical nitridation in ammonia at moderate temperatures of cation ordered Sr2FeWO6 produces new antiferromagnetic double perovskite oxynitrides Sr2FeWO6−xNx with 0 ＜ x≤ 1. Nitrogen introduction induces the oxidation of Fe2+ to Fe3+ and decreases TN from 38 K (x = 0) to 13 K for Sr2FeWO5N which represents the first example of a double perovskite oxynitride with both high cationic order and nitrogen content. This synthetic approach can be extended to other cation combinations expanding the possibility of new materials in the large group of double perovskites. [ABSTRACT FROM AUTHOR]

LnCrO3−xNx perovskites with Ln = La, Pr and Nd and nitrogen contents up to x = 0.59 have been synthesised through ammonolysis of LnCrO4 precursors. These new materials represent one of the few examples of chromium oxynitrides. Hole-doping through O2−/N3− anion substitution suppresses the magnetic transition far less drastically than Ln3+/M2+ (M = Ca, Sr) cation substitutions because of the greater covalency of metal–nitride bonds. Hence, nitride-doping is a more benign method for doping metal oxides without suppressing electronic transitions. [ABSTRACT FROM AUTHOR]

The solid solution Sr2−xLaxSiO4−xNx (0 ≥x≥ 1), obtained by concomitant substitution of Sr2+ by La3+ and O2− by N3− in Sr2SiO4, has been prepared by solid state reaction at 1500 °C in N2/H2 of mixtures of SrO, La2O3, SiO2 and Si3N4. Synchrotron radiation X-ray diffraction studies show a transition from the monoclinic P21/n symmetry of β-Sr2SiO4 to orthorhombic Pmnbα′,β-K2SO4 type phase for x≥ 0.2. The α′ phase is stabilized as a consequence of the increase in bond valence of the cations induced by nitriding. The activation with Eu2+ and Ce3+ of Sr2−xLaxSiO4−xNx produces luminescent materials with broad emission bands centered up to 650 nm under excitation at 405 nm. The emission wavelengths are tuned by La/N contents in a wide range with emission colours changing from yellow (x = 0.2) to orange-red (x = 1) for Eu2+ phosphors and from blue-green (x = 0.2) to orange-yellow (x = 1) in Ce3+ samples. [ABSTRACT FROM AUTHOR]

A simple crossover from two-dimensional to three-dimensional correlated disorder of O and N atoms on a cubic lattice has been discovered within the Ba1−xSrxTaO2N series of perovskite oxynitrides. The crossover is driven by lattice expansion as x decreases, and provides a rapid increase in entropy due to a change from subextensive to extensive configurational entropy regimes. [ABSTRACT FROM AUTHOR]

The new compounds LaSrSiO3N and LaBaSiO3N activated with Eu2+ are orange-red light-emitting luminescent materials under excitation in the UV-blue range. They represent the first examples of stoichiometric alkaline earth oxynitridosilicates with a β-K2SO4 structure. The isostructural compound LaEuSiO3N is ferromagnetic with a Curie temperature of 3 K and also shows red luminescence (λmax = 705 nm) under excitation at 405 nm. [ABSTRACT FROM AUTHOR]

The rare earth vanadium oxynitride perovskites RVO3−xNx (R = La, Pr, Nd; 0 ≤x≤ 1) have been prepared by treatment of RVO4 precursors in NH3. The ammonolysis reactions proceed through an initial reduction of RVO4 precursors to RVO3 perovskites that are progressively nitrided and reoxidised to RVO3−xNx materials with varying proportions of V4+/V3+. Variable temperature neutron diffraction studies show that NdVO2N and PrVO2.24N0.76 have orthorhombic Pbnm symmetry between 3.5 and 300 K, but LaVO2.11N0.89 undergoes a broad Pbnm to R3̅c structural transition over this temperature range. In LaVO3−xNx samples the proportion of the R3̅c phase at room temperature increases with the nitrogen content. The partial anion order indicative of planes of cis-VN2 chains found in NdVO2N is also present in PrVO2.24N0.76, and is thus robust to the disorder created by non-stoichiometry. Magnetic measurements reveal spin freezing transitions at low temperatures in LaVO2.09N0.91 and PrVO2.24N0.76, but NdVO2N is paramagnetic. [ABSTRACT FROM AUTHOR]

The correlated anion order in the oxynitride perovskite NdVO2N, where disordered zig-zag VN chains segregate into planes within a pseudo-cubic lattice, is similar to that in materials such as SrTaO2N containing d0 transition metal cations. However, NdVO2N has 3d1 V4+ cations and the 3d-electrons are itinerant, showing that the anion chain order in oxynitride perovskites is robust to electron-doping. [ABSTRACT FROM AUTHOR]

The topotactic nitridation of cation ordered, tetragonal Sr2FeMoO6 in NH3 at moderate temperatures leads to cubic, Fm3̅m double perovskite oxynitride Sr2FeMoO4.9N1.1 where double-exchange interactions determine ferromagnetic order with TC≈ 100 K. Substitution of oxide by nitride induces bond asymmetries and local electronically driven structural distortions, which combined with Fermi level lowering restricts charge itinerancy to confined regions and preclude spontaneous long-range magnetic order. Under a magnetic field, ferromagnetic correlations expand, favoring charge delocalization and a negative magnetoresistance is observed. [ABSTRACT FROM AUTHOR]

The topotactic nitridation of cation ordered, tetragonal Sr2FeMoO6 in NH3 at moderate temperatures leads to cubic, Fm3[combining macron]m double perovskite oxynitride Sr2FeMoO4.9N1.1 where double-exchange interactions determine ferromagnetic order with TC ≈ 100 K. Substitution of oxide by nitride induces bond asymmetries and local electronically driven structural distortions, which combined with Fermi level lowering restricts charge itinerancy to confined regions and preclude spontaneous long-range magnetic order. Under a magnetic field, ferromagnetic correlations expand, favoring charge delocalization and a negative magnetoresistance is observed.

Topochemical nitridation in ammonia at moderate temperatures of cation ordered Sr 2 FeWO 6 produces new antiferromagnetic double perovskite oxynitrides Sr 2 FeWO 6-x N x with 0 < x ≤ 1. Nitrogen introduction induces the oxidation of Fe 2+ to Fe 3+ and decreases T N from 38 K (x = 0) to 13 K for Sr 2 FeWO 5 N which represents the first example of a double perovskite oxynitride with both high cationic order and nitrogen content. This synthetic approach can be extended to other cation combinations expanding the possibility of new materials in the large group of double perovskites.

The new compounds LaSrSiO3N and LaBaSiO3N activated with Eu(2+) are orange-red light-emitting luminescent materials under excitation in the UV-blue range. They represent the first examples of stoichiometric alkaline earth oxynitridosilicates with a β-K2SO4 structure. The isostructural compound LaEuSiO3N is ferromagnetic with a Curie temperature of 3 K and also shows red luminescence (λmax = 705 nm) under excitation at 405 nm.

The correlated anion order in the oxynitride perovskite NdVO(2)N, where disordered zig-zag VN chains segregate into planes within a pseudo-cubic lattice, is similar to that in materials such as SrTaO(2)N containing d(0) transition metal cations. However, NdVO(2)N has 3d(1) V(4+) cations and the 3d-electrons are itinerant, showing that the anion chain order in oxynitride perovskites is robust to electron-doping.

Oxynitrides constitute a vast class of emerging solids to explore new or improved properties analogous to those of oxides. In this perspective we will show recent developments in this area, discussing different groups of structures and materials such as colossal magnetoresistive (CMR), pigments, phosphors, photocatalysts for water splitting and organic molecule degradation, dielectrics, and anodes for lithium batteries, in connection with their preparative methods and crystal chemistry.

A new phase has been observed during the sodium intercalation of hafnium nitride chloride as intermediate between the host beta-HfNCl and the already reported Na(0.29)HfNCl with Tc of 24 K; the new intermediate shows interlayer spacings ranging from 9.48 to 9.67 A, corresponds to a second stage intercalate of HfNCl and is superconducting with a critical temperature of 20 K.