The origin of the metal-to-insulator transition (MIT) in $R{\mathrm{NiO}}_3$ perovskites with $R$ = trivalent $4f$ ion has challenged the condensed matter research community for almost three decades. A drawback for progress in this direction has been the lack of studies combining physical properties and accurate structural data covering the full nickelate phase diagram. Here we focus on a small region close to the itinerant limit $(R$ = Pr, $1.5\text{K}<T<300$ K), where we investigate the gap opening and the simultaneous emergence of charge order in ${\mathrm{PrNiO}}_3$. We combine electrical resistivity, magnetization, and heat capacity measurements with high-resolution neutron and synchrotron x-ray powder diffraction data that, in contrast to previous studies, we analyze in terms of symmetry-adapted distortion modes. Such analysis allow us to identify the contribution of the different modes to the global distortion in a broad temperature range. Moreover, it shows that the structural changes at the MIT, traditionally described in terms of the evolution of the interatomic distances and angles, appear as abrupt increases of $all$ nonzero mode amplitudes at $T_{\mathrm{MIT}}=T_N\sim 130$ K accompanied by the appearance of new modes below this temperature. A further interesting observation is the existence of a nearly perfect linear correlation between the amplitude of the breathing mode associated to the charge order and the staggered magnetization below the MIT. Our data also uncover a previously unnoticed anomaly at $T^{*}\sim 60$ K $\left(\sim 0.4\times T_{\mathrm{MIT}}\right)$, clearly visible in the electrical resistivity, lattice parameters and some mode amplitudes. Since phase coexistence is only observed in a small temperature region around $T_{\mathrm{MIT}}(\sim \pm 10$ K), these observations suggest the existence of a hidden symmetry in the insulating phase. We discuss some possible origins, among them the theoretically predicted existence of polar distortions induced by the noncentrosymmetric magnetic order [Perez-Mato et al., J. Phys.: Condens. Matter 28, 286001 (2016); Giovanetti et al., Phys. Rev. Lett. 103, 156401 (2009)].

SrMo_1−xM_xO_3−δ (M = Fe and Cr, x = 0.1 and 0.2) oxides have been recently described as excellent anode materials for solid oxide fuel cells at intermediate temperatures (IT-SOFC) with LSGM as the electrolyte. In this work, we have improved their properties by doping with aliovalent Mg ions at the B-site of the parent SrMoO₃ perovskite. SrMo_1−xMg_xO_3−δ (x = 0.1, 0.2) oxides have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers near 900 mW/cm⁻² at 850 °C using pure H₂ as fuel. We have studied its crystal structure with an “in situ” neutron power diffraction (NPD) experiment at temperatures as high as 800 °C, emulating the working conditions of an SOFC. Adequately high oxygen deficiencies, observed by NPD, together with elevated disk-shaped anisotropic displacement factors suggest a high ionic conductivity at the working temperatures. Furthermore, thermal expansion measurements, chemical compatibility with the LSGM electrolyte, electronic conductivity and reversibility upon cycling in oxidizing-reducing atmospheres have been carried out to find out the correlation between the excellent performance as an anode and the structural features.

SrCoO_3−δ outperforms as cathode material in solid-oxide fuel cells (SOFC) when the three-dimensional (3C-type) perovskite structure is stabilized by the inclusion of highly-charged transition-metal ions at the octahedral positions. In a previous work we studied the Nb incorporation at the Co positions in the SrCo_1−xNb_xO_3−δ system, in which the stabilization of a tetragonal P4/mmm perovskite superstructure was described for the x = 0.05 composition. In the present study we extend this investigation to the x = 0.10–0.15 range, also observing the formation of the tetragonal P4/mmm structure instead of the unwanted hexagonal phase corresponding to the 2H polytype. We also investigated the effect of Nb⁵⁺ doping on the thermal, electrical, and electrochemical properties of SrCo_1−xNb_xO_3−δ (x = 0.1 and 0.15) perovskite oxides performing as cathodes in SOFC. In comparison with the undoped hexagonal SrCoO_3−δ phase, the resulting compounds present high thermal stability and an increase of the electrical conductivity. The single-cell tests for these compositions (x = 0.10 and 0.15) with La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ (LSGM) as electrolyte and SrMo_0.8Fe_0.2CoO_3−δ as anode gave maximum power densities of 693 and 550 mW∙cm⁻² at 850 °C respectively, using pure H₂ as fuel and air as oxidant.

In the aim to stabilize novel three-dimensional perovskite oxides based upon SrCoO_3−δ, we have designed and prepared SrCo_1−xRe_xO_3−δ phases (x = 0.05 and 0.10), successfully avoiding the competitive hexagonal 2H polytypes. Their performance as cathode materials in intermediate-temperature solid oxide fuel cells (IT-SOFC) has been investigated. The characterization of these oxides included X-ray (XRD) and in situ temperature-dependent neutron powder diffraction (NPD) experiments for x = 0.10. At room temperature, SrCo_1−xRe_xO_3−δ perovskites are defined in the P4/mmm space group, which corresponds to a subtle tetragonal perovskite superstructure with unit-cell parameters a = b ≈ a_o, c = 2a_o (a_o = 3.861 and 3.868 Å, for x = 0.05 and 0.10, respectively). The crystal structure evolves above 380 °C to a simple cubic perovskite unit cell, as observed from in-situ NPD data. The electrical conductivity gave maximum values of 43.5 S·cm⁻¹ and 51.6 S·cm⁻¹ for x = 0.05 and x = 0.10, respectively, at 850 °C. The area specific resistance (ASR) polarization resistance determined in symmetrical cells is as low as 0.087 Ω·cm² and 0.065 Ω·cm² for x = 0.05 and x = 0.10, respectively, at 850 °C. In single test cells these materials generated a maximum power of around 0.6 W/cm² at 850 °C with pure H₂ as a fuel, in an electrolyte-supported configuration with La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ (LSGM) as the electrolyte. Therefore, we propose the SrCo_1−xRe_xO_3−δ (x = 0.10 and 0.05) perovskite oxides as promising candidates for cathodes in IT-SOFC.

NH₄Fe(HPO₄)₂ and its deuterated form have been synthesized as monophasic polycrystalline materials. Their crystal structures, including hydrogen positions, were determined by Rietveld refinement and Fourier synthesis using constant-wavelength neutron powder diffraction data. In addition, the thermal decomposition of NH₄Fe(HPO₄)₂ was found to give mixtures of Fe₄(P₂O₇)₃ and Fe(PO₃)₃via NH₄FeP₂O₇ formation, the crystal structure of which has also been refined from X-ray powder diffraction data.