Chains Of Octahedra Research Articles

Quasi-1D Oxides as Electrocatalysts for Water-Splitting: Case Study of Sr9M2Mn5O21 (M = Co, Ni, Cu, Zn).

We have demonstrated that multimetal oxides with a quasi-1D structure can be effective electrocatalysts for water electrolysis. Four materials have been systematically investigated, namely, Sr9Co2Mn5O21, Sr9Ni2Mn5O21, Sr9Cu2Mn5O21, and Sr9Zn2Mn5O21, comprising 1D chains of face-sharing MnO6 octahedra and MO6 trigonal prisms (M = Co, Ni, Cu or Zn), which are held together by strontium ions located between the chains. These materials show a consistent trend in electrocatalytic properties for both half-reactions of water-splitting, i.e., oxygen evolution and hydrogen evolution reactions (OER and HER). In particular, Sr9Ni2Mn5O21 has an outstanding performance for OER, with an overpotential of 0.37 V, which is lower than those of many 3D and 2D oxides, and rivals the activity of noble metal catalysts, such as RuO2. This is important given that the OER is considered the bottleneck of the water-slitting process. Chronopotentiometry studies, combined with X-ray photoelectron spectroscopy (XPS) and X-ray diffraction experiments pre- and post-reaction, indicate that Sr9Ni2Mn5O21 is highly stable and retains its structural integrity upon electrocatalytic reactions. This study highlights the potential of quasi-1D oxides as active electrocatalysts for water-splitting.

Cobalt-based pyroxenes: A new playground for Kitaev physics

Recent advances in the study of cobaltites have unveiled their potential as a promising platform for realizing Kitaev physics in honeycomb systems and the Ising model in weakly coupled chain materials. In this manuscript, we explore the magnetic properties of pyroxene SrCoGe[Formula: see text]O[Formula: see text] using a combination of neutron scattering, ab initio methods, and linear spin-wave theory. Through careful examination of inelastic neutron scattering powder spectra, we propose a modified Kitaev model to accurately describe the twisted chains of edge-sharing octahedra surrounding Co[Formula: see text] ions. The extended Kitaev-Heisenberg model, including a significant anisotropic bond-dependent exchange term with [Formula: see text], is identified as the key descriptor of the magnetic interactions in SrCoGe[Formula: see text]O[Formula: see text]. Furthermore, our heat capacity measurements reveal an effect of an external magnetic field (approximately 13 T) which shifts the system from a fragile antiferromagnetic ordering with [Formula: see text] K to a field-induced state. We argue that pyroxenes, particularly those modified by substituting Ge with Si and its less extended [Formula: see text] orbitals, emerge as a platform for the Kitaev model. This opens up possibilities for advancing our understanding of Kitaev physics.

A novel LiMg2P3O10 microwave dielectric ceramic for ultra-wideband dielectric resonant antenna applications

In pursuit of the objective of implementing fifth-generation communication technology, a LiMg2P3O10 microwave dielectric ceramic was developed in this study, and an ultra-wideband dielectric resonant antenna was fabricated. Rietveld refinement confirmed that the monoclinic crystal structure of LiMg2P3O10 ceramics is constituted of MgO6 octahedral chains and shared angle PO4 tetrahedra. The impact of chemical bond characteristics on properties was explored through P-V-L theory. The primary contributions to the intrinsic properties were investigated through infrared spectroscopy. The LiMg2P3O10 ceramics sintered at 830 °C were found to have the best microwave dielectric properties (εr = 6.16, Q × f = 33,573 GHz (at 15.538 GHz), and τf = −35.6 ppm/°C). A novel ultra-wideband dielectric resonant antenna with 53.7 % relative bandwidth, 6.53 dBi maximum gain and 81.7 % radiation efficiency was designed and fabricated. Its wide ultra-wideband characteristics makes it suitable for signal transmission in modern wireless communication systems.

Electrochemically Created Active Centers in a Bimetallic CoNi-Triazole Metal-Organic Framework for Enhanced Oxygen Evolution Reaction Activity.

Electrochemical water oxidation utilizing bimetallic CoNi-Tz (Tz = 1,2,4-triazole) framework is explored. Initially, CoNi-Tz possesses active tetrahedral Co center and electron-mediated octahedral Ni chain. After performing an electrochemical activation, the partial structural transformation on the Ni center occurs. This leads to the generation of excessive active centers which can promote catalytic activity of the framework. The activated CoNi-Tz catalyst displays a remarkably low OER overpotential of 293 mV at a current density of 10 mA cm-2 with a small Tafel slope of 49.98 mV dec-1, outperforming the single metal Co-Tz and benchmark IrO2 catalysts.

Average Cubic BaTaO2N Crystal Structure Formed by 50 nm Size Domains with Polar Nanoregions Consisting of cis-TaO4N2 Octahedral Chains

Average Cubic BaTaO₂N Crystal Structure Formed by 50 nm Size Domains with Polar Nanoregions Consisting of <i>cis</i>-TaO₄N₂ Octahedral Chains

Mixed proton and oxide ion conduction, phase stability, and conducting mechanisms in the Sr2CeO4-based materials

Sr2CeO4 possesses structural characteristic of one-dimensional (1D) edge-sharing CeO6 octahedral chains, exhibits superior phase and chemical stability compared to the perovskite SrCeO3. There have been previous attempts to improve electrical conductivity through proton conduction by acceptor-doping of Yb on the Ce site. However, its electrical conductivity remained low, for instance, at 500 °C, the reported value was 3.16 × 10−7 S/cm, hence limiting its practical applications. In this paper, we synthesized four new rare earth doped Sr2Ce0.95M0.05O3.975 (where M = Y, Dy, Er, Tb) by the solid state reaction method. We thoroughly investigated their phases, electrical properties, and stability. Additionally, for the first time, we investigated the proton and oxide ion conduction mechanisms in Sr2CeO4-based materials using a bond-valence-based method. This analysis revealed a clear 1D conduction along the c-axis within the CeO6 tetrahedral chains and 2D conduction within the a-c plane, respectively. The findings revealed that all doped materials showed obvious proton conduction, alongside partial oxide ion conduction. Notably, the Er-, Dy-, and Y-doped samples demonstrated significantly improved conductivity under wet condition (with a water partial pressure of ∼0.03 atm) at 500 °C, reaching approximately ∼ 10−4 S/cm. This is nearly three orders of magnitude higher than the previously reported Yb-doped Sr2CeO4.

Structural, dielectric and magnetic properties of MFeNbO6 materials (M=Ti, Zr, Hf)

We study the structural, magnetic and electronic properties of MFeNbO6 materials (where A = Ti, Zr or Hf). TiFeNbO6 crystallises with the disordered rutile structure with the P42/mnm space group. Increasing the ionic radii of the M4+ cation going from Ti4+ (0.605 Å) to Zr4+ (0.72 Å) and Hf4+ (0.710 Å) results in a buckling of the octahedral chains with these materials crystallising with the disordered α-PbO2 structure (space group Pbcn). In contrast, with previous reports for TiFeNbO6 we find no evidence of relaxor ferroelectric behaviour with all three materials instead exhibiting Maxwell-Wagner-like relaxation. Impedance spectroscopy confirms semiconductor behaviour. Magnetically, all three materials can be described by infinite irregular antiferromagnetic S = 5/2 chains with weak ferromagnetism below 10 K. These chains have random directions of propagation between nearest Fe–Fe neighbours consistent with the disordered nature of these materials. We observed a negative imaginary part of the ac susceptibility related to the defect magnetic topology.

Are Selenides the Same as Sulfides? Structure, Spectroscopy, and Properties of Narrow-Gap Rare-Earth Semiconductors RE2Sn(S1-xSex)5 (RE = La, Ce; x = 0-0.8).

The ternary rare-earth sulfides RE2SnS5 (RE = La-Nd) and the partial solid solutions RE2Sn(S1-xSex)5 (RE = La, Ce; x = 0-0.8) were prepared in the form of polycrystalline samples by reaction of the elements at 900 °C and as single crystals in the presence of KBr flux. They adopt the La2SnS5-type structure (orthorhombic, space group Pbam, Z = 2) consisting of chains of edge-sharing SnCh6 octahedra separated by RE atoms. Although the cell parameters evolve smoothly in RE2Sn(S1-xSex)5, detailed structural analysis by single-crystal X-ray diffraction revealed a pronounced preference for the Se atoms to occupy two out of the three chalcogen sites, which offers a rationalization for why the all-selenide end-members RE2SnSe5 do not form. Solid-state 119Sn NMR spectra confirmed the nonrandom distribution of SnS6-nSen local environments, which could be resolved into individual resonances. The Raman spectra of RE2SnS5 compounds show an intense peak at 307-320 cm-1 assigned to a symmetric A1g mode, which is dominated by Sn-S bonds; the Raman peak intensities varied with Se substitution in La2Sn(S1-xSex)5. Optical diffuse reflectance spectra, band structure calculations, and electrochemical impedance spectra indicated that these compounds are narrow band gap semiconductors; the optical band gaps are insensitive to RE substitution in RE2SnS5 (0.7 eV) but they gradually decrease with greater Se substitution in RE2Sn(S1-xSex)5 (0.7-0.4 eV).

Compressibility and thermal expansion of magnesium phosphates

Abstract. The ambient-temperature compressibility and room-pressure thermal expansion of two Mg3(PO4)2 polymorphs (farringtonite = Mg3(PO4)2-I, with 5- and 6-fold coordinated Mg, and chopinite = “Mg-sarcopside” = [6]Mg3(PO4)2-II), three Mg2PO4OH polymorphs (althausite, hydroxylwagnerite and ε-Mg2PO4OH, all with [5]Mg and [6]Mg) and phosphoellenbergerite ([6]Mg) were measured on synthetic powders using a synchrotron-based multi-anvil apparatus to 5.5 GPa and a laboratory high-temperature diffractometer, with whole-pattern fitting procedures. Bulk moduli range from 64.5 GPa for althausite to 88.4 GPa for hydroxylwagnerite, the high-pressure Mg2PO4OH polymorph. Chopinite, based on an olivine structure with ordered octahedral vacancies (K0 = 81.6 GPa), and phosphoellenbergerite, composed of chains of face-sharing octahedra (K0 = 86.4 GPa), are distinctly more compressible than their homeotypical silicate (127 and 133 GPa, respectively). The compressibility anisotropy is the highest for chopinite and the lowest for phosphoellenbergerite. First-order parameters of quadratic thermal expansions range from v1 = 2.19×10-5 K−1 for ε-Mg2PO4OH to v1 = 3.58×10-5 K−1 for althausite. Phosphates have higher thermal-expansion coefficients than the homeotypical silicates. Thermal anisotropy is the highest for farringtonite and the lowest for hydroxylwagnerite and chopinite. These results set the stage for a thermodynamic handling of phase-equilibrium data obtained up to 3 GPa and 1000 °C in the MgO–P2O5–H2O and MgO–Al2O3–P2O5–H2O systems.

The multiferroic properties of Pb3Fe2F12

Fluoride ferroelectrics containing 3d transition metal ions are potential multiferroic candidates due to their ionic bonds rather than the covalent bonds in oxide ferroelectrics. In this work, Pb3Fe2F12 ceramics are prepared by solid-state reaction. Rietveld refinement of the x-ray diffraction pattern suggests that Pb3Fe2F12 adopts a crystalline structure similar to that of Pb5Fe3F19, containing FeF6 octahedra chains and isolated FeF6 octahedra. The deficiency of Pb content leads to the mixed valence states of Fe ions and strong distortion among the octahedra, thus, complicating exchange interactions between Fe ions. The antiferromagnetic transition temperature TN1 is observed at 160 K, which is significantly higher than that of stoichiometric Pb5Fe3F19. Various magnetic anomalies are observed at low temperatures due to the onset of different antiferromagnetic exchange interactions between Fe ions of different strengths with TN2 (∼45 K), TN3 (∼37 K), and TN4 (∼10 K). Weak ferromagnetism can be observed below TN2, and significant exchange bias is observed below TN4. Dielectric peaks, together with a magnetic field tunable pyroelectric current peak, are observed at around TN1, suggesting the multiferroic nature and magnetoelectric coupling in Pb3Fe2F12.

β-Phase Yb5Sb3Hx: Magnetic and Thermoelectric Properties Traversing from an Electride to a Semiconductor.

An electride is a compound that contains a localized electron in an empty crystallographic site. This class of materials has a wide range of applications, including superconductivity, batteries, photonics, and catalysis. Both polymorphs of Yb5Sb3 (the orthorhombic Ca5Sb3F structure type (β phase) and hexagonal Mn5Si3 structure type (α phase)) are known to be electrides with electrons localized in 0D tetrahedral cavities and 1D octahedral chains, respectively. In the case of the orthorhombic β phase, an interstitial H can occupy the 0D tetrahedral cavity, accepting the anionic electron that would otherwise occupy the site, providing the formula of Yb5Sb3Hx. DFT computations show that the hexagonal structure is energetically favored without hydrogen and that the orthorhombic structure is more stable with hydrogen. Polycrystalline samples of orthorhombic β phase Yb5Sb3Hx (x = 0.25, 0.50, 0.75, 1.0) were synthesized, and both PXRD lattice parameters and 1H MAS NMR were used to characterize H composition. Magnetic and electronic transport properties were measured to characterize the transition from the electride (semimetal) to the semiconductor. Magnetic susceptibility measurements indicate a magnetic moment that can be interpreted as resulting from either the localized antiferromagnetically coupled electride or the presence of a small amount of Yb3+. At lower H content (x = 0.25, 0.50), a low charge carrier mobility consistent with localized electride states is observed. In contrast, at higher H content (x = 0.75, 1.0), a high charge carrier mobility is consistent with free electrons in a semiconductor. All compositions show low thermal conductivity, suggesting a potentially promising thermoelectric material if charge carrier concentration can be fine-tuned. This work provides an understanding of the structure and electronic properties of the electride and semiconductor, Yb5Sb3Hx, and opens the door to the interstitial design of electrides to tune thermoelectric properties.

Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route.

One-dimensional (1D) Heisenberg antiferromagnets are of great interest due to their intriguing quantum phenomena. However, the experimental realization of such systems with large spin S remains challenging because even weak interchain interactions induce long-range ordering. In this study, we present an ideal 1D S = 5/2 spin chain antiferromagnet achieved through a multistep topochemical route involving dehydration and rehydration. By desorbing three water molecules from (2,2'-bpy)FeF3(H2O)·2H2O (2,2'-bpy = 2,2'-bipyridyl) at 150 °C and then intercalating two water molecules at room temperature (giving (2,2'-bpy)FeF3·2H2O 1), the initially isolated FeF3ON2 octahedra combine to form corner-sharing FeF4N2 octahedral chains, which are effectively separated by organic and added water molecules. Mössbauer spectroscopy reveals significant dynamical fluctuations down to 2.7 K, despite the presence of strong intrachain interactions. Moreover, results from electron spin resonance (ESR) and heat capacity measurements indicate the absence of long-range order down to 0.5 K. This controlled topochemical dehydration/rehydration approach is further extended to (2,2'-bpy)CrF3·2H2O with S = 3/2 1D chains, thus opening the possibility of obtaining other low-dimensional spin lattices.

Influence of the Rare Earth Cation on the Magnetic Properties of Layered 12R-Ba4M4+Mn3O12 (M = Ce, Pr) Perovskites.

Material design is increasingly used to realize desired functional properties, and the perovskite structure family is one of the richest and most diverse: perovskites are employed in many applications due to their structural flexibility and compositional diversity. Hexagonal, layered perovskite structures with chains of face-sharing transition metal oxide octahedra have attracted great interest as quantum materials due to their magnetic and electronic properties. Ba4MMn3O12, a member of the "12R" class of hexagonal, layered perovskites, contains trimers of face-sharing MnO6 octahedra that are linked by a corner-sharing, bridging MO6 octahedron. Here, we investigate cluster magnetism in the Mn3O12 trimers and the role of this bridging octahedron on the magnetic properties of two isostructural 12R materials by systematically changing the M4+ cation from nonmagnetic Ce4+ (f0) to magnetic Pr4+ (f1). We synthesized 12R-Ba4MMn3O12 (M= Ce, Pr) with high phase purity and characterized their low-temperature crystal structures and magnetic properties. Using substantially higher purity samples than previously reported, we confirm the frustrated antiferromagnetic ground state of 12R-Ba4PrMn3O12 below TN ≈ 7.75 K and explore the cluster magnetism of its Mn3O12 trimers. Despite being atomically isostructural with 12R-Ba4CeMn3O12, the f1 electron associated with Pr4+ causes much more complex magnetic properties in 12R-Ba4PrMn3O12. In 12R-Ba4PrMn3O12, we observe a sharp, likely antiferromagnetic transition at T2 ≈ 12.15 K and an additional transition at T1 ≈ 200 K, likely in canted antiferromagnetic order. These results suggest that careful variation of composition within the family of hexagonal, layered perovskites can be used to tune material properties using the complex role of the Pr4+ ion in magnetism.

Synthesis and Oxygen Evolution Reaction Application of a Co-Cd Based Bimetallic Metal-Organic Framework.

In the realm of renewable energy technologies, the development of efficient and durable electrocatalysts is paramount, especially for applications like electrochemical water splitting. This research focuses on synthesizing a novel bimetallic metal-organic framework (BMMOF11) using earth-abundant elements, cobalt (Co) and cadmium (Cd). BMMOF11 showcases a distinctive structure with distorted octahedral chains of CoO and CdO, linked by benzene tricarboxylic acid (BTC). Our study primarily investigates the electrocatalytic efficiency of BMMOF11, particularly in water oxidation reactions. For practical analysis, BMMOF11 was anchored onto nickel foam, forming BMMOF11/NF, to evaluate its electrocatalytic properties. Electrochemical testing revealed that BMMOF11/NF begins water oxidation at an onset potential of 1.62 V versus RHE, demonstrating high activity with a lower overpotential of 0.4 V to achieve a current density of 10 mA/cm2 . Moreover, BMMOF11/NF maintained stable water splitting performance, sustaining a current density of approximately 70 mA/cm2 under a voltage of 1.9 V relative to RHE. These findings indicate that BMMOF11/NF is a promising candidate for large-scale electrochemical water splitting, offering a blend of high activity and stability.

Synthesis, Structure, and Properties of 2O-BaPtO3, a Phase Derived from Hexagonal Perovskite.

We have made the compound 2O-BaPtO3 by high-pressure, high-temperature synthesis, determined its structure, and tested its catalytic activity. Compounds of the same stoichiometry have been reported and tentatively identified as hexagonal perovskites, and although no structural model was ever established, 2O-BaPtO3 is clearly different and, to the best of our knowledge, unique. It features continuous chains of face-sharing PtO6 octahedra, like the well-known 2H hexagonal perovskite type, but with a staggered offset between the chains that breaks hexagonal symmetry and disrupts the close-packed array of A = Ba and X = O that is a defining characteristic of ABX3 perovskites. We investigated this structure and its stability vs the conventional 2H form using X-ray and neutron diffraction, X-ray absorption spectroscopy, and ab initio calculations. Catalytic testing of 2O-BaPtO3 showed that it is active for hydrogen evolution.

High dielectric permittivity and relaxation-induced dielectric pulsing effect-like in [1,3-bis(1-methylimidazolium)propane][Pb2I6] crystal

Herein, a new hybrid, [1,3-bis(1-methylimidazolium)propane][Pb2I6] (1), was synthesized and thoroughly characterized using microanalysis, thermogravimetric analysis (TG), differential scanning calorimetry (DSC), and powdered X-ray diffraction (PXRD) techniques. The crystal structure of 1 reveals one-dimensional face-sharing PbI6 octahedral chains composed of Pb2+ and I− ions, with the disordered 1,3-bis(1-methylimidazolium)propane dications positioned between these inorganic chains. Remarkably, 1 exhibits high dielectric permittivity (∼200) across a wide temperature range of 123–423 K. Moreover, it demonstrates a relaxation-induced dielectric pulsing effect-like, characterized by a broad and temperature-independent dielectric anomaly peak around 263 K in ε'−T plots. The mechanisms responsible for the high dielectric permittivity and the origin of the relaxation-induced dielectric pulsing effect-like are further discussed through a comprehensive analysis of the variable-temperature crystal structure.

Polymorphism and Red Photoluminescence Emission from 5s2 Electron Pairs of Sb(III) in a New One-Dimensional Organic-Inorganic Hybrid Based on Methylhydrazine: MHy2SbI5.

We explore the crystal structure and luminescent properties of a new 1D organic-inorganic hybrid, MHy2SbI5, based on methylhydrazine. The compound reveals the red photoluminescence (PL) originating from the 5s2 electron pairs of Sb(III) as well as complex structural behavior. MHy2SbI5 crystalizes in two polymorphic forms (I and II) with distinct thermal properties and structural characteristics. Polymorph I adopts the acentric P212121 chiral space group confirmed by SHG, and, despite a thermally activated disorder of MHy, does not show any phase transitions, while polymorph II undergoes reversible low-temperature phase transition and high-temperature reconstructive transformation to polymorph I. The crystal structures of both forms consist of 1D perovskite zig-zag chains of corner-sharing SbI6 octahedra. The intriguing phase transition behavior of II is associated with the unstable arrangement of the [SbI5]2-∞ chains in the structure. The energy band gap (Eg) values, estimated based on the UV-Vis absorption spectra, indicate that both polymorphs have band gaps, with Eg values of 2.01 eV for polymorph I and 2.12 eV for polymorph II.

The Phosphidosilicates AE2 Li4 SiP4 (AE=Ca, Sr, Eu) Ba4 Li16 Si3 P12.

The quaternary phosphidosilicates AE2 Li4 SiP4 (AE=Ca, Sr, Eu) and Ba4 Li16 Si3 P12 were synthesized by heating the elements and Li3 P under argon atmosphere. Their crystal structures were determined by single crystal X-ray diffraction. AE2 Li4 SiP4 crystallize in a new layered structure type (P21 /m, Z=2) with CdI2 -analoguos layers. Edge sharing CaP6 octahedra are separated by layers of vertex-sharing SiP4 and LiP4 tetrahedra, which contain additional chains of LiP6 octahedra. Ba4 Li16 Si3 P12 forms likewise a new structure type (P21 /c, Z=16) with a three-dimensional network of SiP4 , Si2 P6 and LiP4 entities as well as one phosphorus site not bonded to silicon. Barium is located in capped trigonal prisms of phosphorus which form strongly corrugated layers. 31 P and 29 Si solid-state NMR spectra confirm the crystal structures of the compounds AE2 Li4 SiP4 . 7 Li spectra show only one signal in spite of quite different crystallographic positions, which indicate possible Li+ mobility. However, this signal is much broader compared to the known Li+ conducting phosphidosilicates. Accordingly, electrochemical impedance measurements show low Li+ conductivities.

Ferromagnetic Coupling in Quasi-One-Dimensional Hybrid Iron Chloride Hexagonal Perovskites.

We synthesize four novel quasi-one-dimensional organic-inorganic hybrid iron chloride compounds (CH3NH3FeCl3, CH(NH2)2FeCl3, C(NH2)3FeCl3, and C3H5N2FeCl3) and characterize their structural and magnetic properties. These materials crystallize in a hexagonal perovskite-type structure, constituting a triangular array of face-sharing iron chloride octahedra chains running along the c-axis, isolated from one another by the organic cation. Through magnetization and heat capacity measurements, we find that the intrachain coupling is weakly ferromagnetic for each variant. Importantly, this work underscores the utility of solid-state chemistry approaches in synthesizing new organic-inorganic hybrid materials.

Lamellar Crystal Structure and Haldane Magnetism in NH4 VPO4 OH.

A novel vanadium hydroxide-phosphate, NH4 VPO4 OH, was synthesized hydrothermally in V2 O5 -NH4 H2 PO4 -citric acid system at 230 °C. It was characterized by XRD, TG-DSC, SEM-EDX, FTIR and NMR spectroscopy. NH4 VPO4 OH is isostructural with NH4 GaPO4 OH and features edge-sharing chains of VO6 octahedra. These chains running along [010] direction of the unit cell are connected by phosphate tetrahedra to form infinite layers parallel to the (100) plane. Ammonium cations are embedded between the heteropolyhedral layers. According to the thermodynamic and NMR measurements supported by the first-principles calculations, NH4 VPO4 OH presents a rare case of Haldane spin system with spin S=1 based on V3+ ions.