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Glassy Na-ion solid-state electrolytes (GNSSEs) are an important group of amorphous SSEs. However, the insufficient ionic conductivity of state-of-the-art GNSSEs at room temperature lessens their promise in the development of all-solid-state Na-ion batteries (ASSNIBs) with high energy density and improved safety. Here we report the discovery of a new sodium superionic glass, 0.5Na2 O2 -TaCl5 (NTOC), based on dual-anion sublattice of oxychlorides. The unique local structures with abundant bridging and non-bridging oxygen atoms contributes to a highly disordered Na-ion distribution as well as low Na+ migration barrier within NTOC, enabling an ultrahigh ionic conductivity of 4.62 mS cm-1 at 25 °C (more than 20 times higher than those of previously reported GNSSEs). Moreover, the excellent formability of glassy NTOC electrolyte and its high electrochemical oxidative stability ensure a favourable electrolyte-electrode interface, contributing to superior cycling stability of ASSNIBs for over 500 cycles at room temperature. The discovery of glassy NTOC electrolyte would reignite research enthusiasm in superionic glassy SSEs based on multi-anion chemistry.

Sodium‐based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid‐state sodium batteries can also provide further safety advantages. However, sodium‐based solid‐state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium‐based oxyhalide electrolytes NaNbCl6‐2xOx with a facile mechanochemical synthesis. The oxyhalide NaNbCl4O exhibits close to two orders of magnitude higher ambient‐temperature sodium‐ion conductivity (1.03×10−4 S cm−1) compared to the halide counterpart NaNbCl6 (3×10−6 S cm−1). Structural motifs unique to the oxygen content in NaNbCl6‐2xOx are identified with 23Na and 93Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x‐ray diffraction (XRD). Solid‐state sodium batteries assembled with NaNbCl4O electrolyte and the cobalt‐ and nickel‐free layered Na0.70Fe0.3Mn0.65Al0.05O2 cathode exhibit a maximum discharge capacity of 155 mAh g−1 with good cycle life at ambient temperature. [ABSTRACT FROM AUTHOR]

In the mid 20th century, type OMTI fire-resistant oil (fire-resistant oil of the thermal engineering institute), whose production technology was developed by specialists of the All-Russian Thermal Engineering Institute (VTI), received wide use at Russian and also at some foreign power plants. Type OMTI oil is distinguished by its high fire-resistant qualities, good lubrication properties, high thermal oxidation and hydrolytic stability, and long service life. Its drawback, as of any phosphorus esters, is sensitivity to the presence of water and increased temperatures, the action of which destructs the fluid with generation of acidic products. This process is "autocatalytic" in nature with a rather quickly reached unacceptable acidic level, at which the replacement of oil may be required. Nowadays, in view of the fact that fire-resistant oils are widely used but have a high cost, matters concerned with supporting the operation of fire-resistant oils and also extending their service life are becoming of much relevance. Another important issue is searching for efficient methods to restore the qualitative characteristics of spent oils that have been accumulated at power industry enterprises with the aim of repeatedly using them as hydraulic fluid or raw material for obtaining new oil. For extending the service life of operating oils and restoring spent oils to the required characteristics, oil purification plants, in which the fluids are subjected to sorption purification and acid destruction products are removed, are required. To ensure the effectiveness of the implemented processes, the sorbent must comply with certain criteria. It should be noted that stable operation of the power industry is essential for the energy security of the state; therefore, it is necessary to commence work on developing the compositions of a new type of fire-resistant oils on the basis of tert-butylphenyls and also elaborating the technology for manufacturing them and estimating the possibility to implement the process at existing industrial chemical sites. The manufacture of the new type of oils must be accompanied by the development of corresponding regulatory documents. [ABSTRACT FROM AUTHOR]

Mixed‐anion compounds widen the chemical space of attainable materials compared to single anionic compounds, but the exploration of their structural diversity is limited by common synthetic paths. Especially, oxychlorides rely mainly on layered structures, which suffer from low stability during photo(electro)catalytic processes. Herein we report a strategy to design a new polar 3D tetrahedral framework with composition Zn4Si2O7Cl2. We use a molten salt medium to enable low temperature crystallization of nanowires of this new compound, by relying on tetrahedral building units present in the melt to build the connectivity of the oxychloride. These units are combined with silicon‐based connectors from a non‐oxidic Zintl phase to enable precise tuning of the oxygen content. This structure brings high chemical and thermal stability, as well as strongly anisotropic hole mobility along the polar axis. These features, associated with the ability to adjust the transport properties by doping, enable to tune water splitting properties for photoelectrocatalytic H2 evolution and water oxidation. This work then paves the way to a new family of mixed‐anion solids [ABSTRACT FROM AUTHOR]

Penetrating sealers are one means to reduce moisture and chemical transport into concrete. However, a large variety of products are available, possessing different functional modes of action. This study investigated representative families of penetrating sealers applied to vertical, sawn faces of properly air-entrained concrete (approximately 6%) to represent field application of sealers to concrete joints. Concrete was characterized for water transport, chloride diffusion, gas permeability, frost resistance in the presence of deicing salts, and potential for oxychloride formation. The results showed that some sealers effectively reduced water absorption, prolonged time to saturation, and reduced chloride penetration. However, delayed time to critical saturation did not always result in improved frost resistance. All sealers significantly reduced the potential of oxychloride formation. The tests used for this study are broadly applicable and provide enhanced characterization for selection and application of new types of sealers and modes of action. [ABSTRACT FROM AUTHOR]

A new compound, Ba3Ga2O5Cl2, isostructural with Ba3Fe2O5Cl2, was synthesized by solid‐state reaction in air. Through single‐crystal and powder X‐ray diffraction analysis, the crystal structure was determined to be cubic with chiral space group I213 and unit‐cell parameter a = 9.928 (1) Å. The Ga3+ ions in Ba3Ga2O5Cl2 are coordinated by O atoms and form GaO4 tetrahedra. Ten neighboring GaO4 tetrahedra are further bridged through corner sharing and rotation along the body diagonal, producing the chiral structure. Magnetization measurements indicate temperature‐independent diamagnetic behavior, which is qualitatively consistent with core diamagnetism from all the constituent elements. [ABSTRACT FROM AUTHOR]

A new compound, Ba3Ga2O5Cl2, isostructural with Ba3Fe2O5Cl2, was synthesized by solid‐state reaction in air. Through single‐crystal and powder X‐ray diffraction analysis, the crystal structure was determined to be cubic with chiral space group I213 and unit‐cell parameter a = 9.928 (1) Å. The Ga3+ ions in Ba3Ga2O5Cl2 are coordinated by O atoms and form GaO4 tetrahedra. Ten neighboring GaO4 tetrahedra are further bridged through corner sharing and rotation along the body diagonal, producing the chiral structure. Magnetization measurements indicate temperature‐independent diamagnetic behavior, which is qualitatively consistent with core diamagnetism from all the constituent elements. [ABSTRACT FROM AUTHOR]

Understanding the properties of transition metal materials requires consideration of the competition between the various types of electrons that comprise the system, whether they be delocalized and metallic, localized and magnetic, or localized and bonded. Here we report the refined crystal structure determination and physical properties of the two-dimensional layered compound TaOCl 2. Within each layer we find a strong in-plane dimerization of Ta atoms perpendicular to the Ta-O-Ta chains, with significant disorder in the positioning of dimers in adjacent layers, suggesting that the free electron of each Ta localizes in Ta-Ta bonds. This is supported by resistivity measurements (ρ 300K = 4.4*108 Ω-cm) as well as featureless, temperature-independent magnetic susceptibility up to T = 750 K. Analysis of the phonon contribution to specific heat shows the presence of a localized Einstein mode with T E = 175 K, attributed to the localized vibrations of the Ta-Ta dimers. Density functional theory calculations show that the magnitude of the Ta displacements (0.24 Å) has a dramatic effect on the electronic structure, changing from a metal with a bandwidth of 3.2 eV to an insulator with a flat band just below E F. Our results show how direct exchange interactions between Ta atoms that are relatively far from each other can still play a central role in the behavior of 5d transition metal compounds, taking advantage of the extended 5d atomic orbitals, and produce localized dimers with a bond distance of approximately 2.84 Å. Illustrating the discovery of and modeling disorder in the crystal structure of TaOCl 2. [Display omitted] • In-plane disorder leading to Ta-Ta dimerization discovered in crystal structure. • Dimerization significantly affects physical properties. • Significant electrical resistance observed, at odds with predicted electronic band structure of undistorted crystal structure. • Significant potential for tuning of crystal structure and properties. [ABSTRACT FROM AUTHOR]

Dysprosium oxychloride, DyOCl, was synthesized using a simple hydrolysis method with DyCl3·6H2O. X-ray powder diffraction (XRD) data was used to determine the crystal structure. The DyOCl compound is isostructural to the matlockite (PbFCl) crystal structure and crystallizes in the tetragonal P4/nmm (#129) space group. The crystal structure contains the alternating cationic layers of (DyO)n and anionic layers of nCl− along the c-axis. The structural data including unit cell, volume, and density of DyOCl were compared to other rare-earth oxychloride data from the Inorganic Crystal Structure Database (ICSD) and our previous study on TbOCl. Fourier-transform infrared spectroscopy was performed on DyOCl and peaks observed at 543 and 744 cm−1 were attributed to Dy–O and Dy–Cl. Scanning electron microscopy analysis showed irregularly shaped crystals. Hot-stage XRD, thermogravimetry, as well as differential scanning calorimetry coupled to a gas chromatograph and a mass spectrometer (evolved gas analysis) were performed on DyCl3·6H2O to understand the phase transformation to DyOCl (and Dy2O3) as a function of temperature and time at temperature. DyOCl compound with the tetragonal P4/nmm space group is composed of the alternating layers of (DyO)n and nCl− along the c-axis. [ABSTRACT FROM AUTHOR]

For the first time, a spinel-type high entropy oxide (Zn0.25Cu0.25Mg0.25Co0.25)Al2O4 as well as its derivative lithiated high entropy oxyfluoride Li0.5(Zn0.25Cu0.25Mg0.25Co0.25)0.5Al2O3.5F0.5 and oxychloride Li0.5(Zn0.25Cu0.25Mg0.25Co0.25)0.5Al2O3.5Cl0.5 are prepared in the nanostructured state via high-energy co-milling of the simple oxide precursors and the halides (LiF or LiCl) as sources of lithium, fluorine and chlorine. Their nanostructure is investigated by XRD, HR-TEM, EDX and XPS spectroscopy. It is revealed that incorporation of lithium into the structure of spinel oxide together with the anionic substitution has significant effect on its short-range order, size and morphology of crystallites as well as on its oxidation/reduction processes. The charge capacity of the as-prepared nanomaterials tested by cyclic voltammetry is found to be rather poor despite lithiation of the samples in comparison to previously reported spinel-type high entropy oxides. Nevertheless, the present work offers the alternative one-step mechanochemical route to novel classes of high entropy oxides as well as to lithiated oxyfluorides and oxychlorides with the possibility to vary their cationic and anionic elemental composition. [ABSTRACT FROM AUTHOR]

Terbium oxychloride, TbOCl, was synthesized via the simple heat-treatment of TbCl3·6H2O and its structure was determined by refinement against X-ray powder diffraction data. TbOCl crystallizes with the matlockite (PbFCl) structure in the tetragonal space group P4/nmm and is composed of alternating (001) layers of (TbO)n and n Cl−. The unit-cell parameters, unit-cell volume, and density were compared to the literature data of other isostructural rare-earth oxychlorides in the same space group and showed good agreement when compared to the calculated trendlines.

Oxychloride phosphors that contain active ions coordinated with both oxygen and chloride ions have garnered significant attention, but the application of oxychloride phosphors is yet limited because of their demanding synthesis condition of vacuum or reducing atmosphere. Herein, we synthesize a new serial oxychlorides of La 9 W 6 O 30 Cl (LWOC) and Er3+/Yb3+, Ho3+/Yb3+, Tm3+/Yb3+ doped LWOC through molten salt shielding method (MSS) in air, which is more efficient compared to the traditional method in vacuum. The compound of LWOC crystallizes in the tetragonal system space group P 4 2 / nmc (No. 137) with cell parameters a = b = 10.0445(1) Å, c = 12.6826(4) Å, V = 1279.57(5) Å3 and Z = 11. The asymmetric unit of LWOC includes three La atoms, one unique W atom, two disordered W atoms with occupancy factors of 0.16(5) and 0.84(5), respectively, one Cl atom and six O atoms. Under the excitation of 980 nm laser, all the Er3+/Yb3+, Ho3+/Yb3+ and Tm3+/Yb3+ co-doped LWOC phosphors have excellent upconversion (UC) luminescence with bright visible light emission. A fluorescence intensity ratio (FIR) type temperature sensor is developed by using LWOC: Er3+, Yb3+ phosphor as sensing media, which has a maximum relative temperature sensitivity (S r) of 0.90 % K−1 at 300 K. • Oxychloride crystals were synthesized in air by molten salt shielding (MSS) method for the first time. • The effect of oxygen defect on crystal color is explained. • An optical temperature sensing device that can work in real environment is prepared. [ABSTRACT FROM AUTHOR]

The reaction between rare earth oxychloride (REOCl) and water was investigated. X-ray diffractometer, volumetric titrations, FTIR spectrograph and scanning electron microscope were used to determine the reaction process and the reaction products. It was found that the reaction could be concluded as follows: 5REOCl(s) + 5H2O(l) = 2RE2(OH)5Cl(s) + RE3+(aq) + 3Cl−(aq). Based on this reaction, a new method for determining the purity of anhydrous rare earth chloride was proposed. Compared with the conventional method, the maximum absolute error decreased from 22 to < 1% and the maximum relative error decreased from 111 to < 4% under the experimental conditions. [ABSTRACT FROM AUTHOR]

The new oxychloride, Ba 27 Pb 8 O 8 Cl 54 , has been synthesized by a high temperature solution method. It crystallizes as cubic brown block with unit-cell a = 22.547(2), space group Fm 3 ¯ m (No. 225). It features a complicated three-dimensional network composed of [Ba 20 O 4 Cl 92 ] and [Ba 14 O 8 Cl 36 ] units sharing one Ba atom and its coordination atoms, which is inserted by new isolated [Pb 4 O 4 ] clusters. The UV–Vis-IR diffuse reflectance spectrum exhibits that its optical band gap is about 3.9 eV. In this paper, the structural features, thermal behaviors and optical properties were systemically studied. Single crystals of Ba 27 Pb 8 O 8 Cl 54 are obtained for the first time and the structure of Ba 27 Pb 8 O 8 Cl 54 is the first time to be reported. The structure of Ba 27 Pb 8 O 8 Cl 54 can be described as a three-dimensional framework composed of [Ba 20 O 4 Cl 92 ] and [Ba 14 O 8 Cl 36 ] units, which is inserted by new isolated [Pb 4 O 4 ] clusters that is the first time to be found in the Pb-M-O-Cl (M = metal cations) quaternary system. In this paper, the synthesis, crystal structure, thermal behaviors and optical properties of Ba 27 Pb 8 O 8 Cl 54 were systemically studied. Image 1 • Ba 27 Pb 8 O 8 Cl 54 is reported for the first time. • Ba 27 Pb 8 O 8 Cl 54 is the first lead alkaline earth metal oxychloride. [ABSTRACT FROM AUTHOR]

The toxicity of the organic dyes presents in the environment due to polluted discharge from industries is a real dilemma in the world. Here, the problem was addressed with the synthesis of new quaternary mineral cupric antimony oxychloride (CAO) during the study of Cu–Sb–O–Cl system in absence of solvents. The morphological analysis showed that synthesized matrix is rough and uneven with round and cylindrical shapes. The composition of nanomaterial verified the elemental composition as Cu, Sb and Cl. The XRD analysis revealed that synthesized product CAO is crystalline in nature where crystallite size was estimated in the range of 2–8 nm. The bond vibrations were studied through Fourier transforms infrared spectroscopy to confirm the symmetric and asymmetric vibrations in the matrix. The material parameters (grain size, dislocation line density, stresses and miller indices) of the synthesized material CAO were calculated using powder X-ray diffraction analysis. Thermogravimetric analysis was performed to study the decomposition behaviour and stability of the CAO. The copper ternary compound was used to mitigate the effect of organic dyes like Sunset yellow (26%), Methylene blue (23%), Brilliant green (20%), Methyl orange (14%) in the dyes polluted wastewater. [ABSTRACT FROM AUTHOR]

A novel mixed-anion oxychloride, KBi(SeO 4)(IO 3)Cl, has been hydrothermally synthesized and structurally characterized. The compound crystallizes in the monoclinic space group of P 2 1 /c with cell parameters of a = 7.8802(2) Å; b = 10.8088(2) Å, c = 10.1364(2) Å, β = 112.849(1)°, V = 795.62(3) Å3, and Z = 4. KBi(SeO 4)(IO 3)Cl exhibits a three-dimensional tunnel framework that is composed of three types of atomic groups, i.e., tetrahedral SeO 4 , trigonal pyramidal IO 3 , and polyhedral BiO 6 Cl. Both IO 3 pyramid and BiO 6 Cl polyhedron are in strongly acentric coordination due to the influence of I5+ and Bi3+ lone electron pairs. The measurement of UV–vis–NIR spectra for powder KBi(SeO 4)(IO 3)Cl indicates that the material is a wide band gap semiconductor with E g = 3.9 eV. Theoretical analysis shows that the electron transition from Bi 6p to O 2p states in the BiO 6 Cl unit dominates the optical absorption edge. Thermal stability and IR spectrum were also analyzed for the material. A novel oxychloride KBi(SeO 4)(IO 3)Cl was hydrothermally synthesized and structurally determined for the first time. The compound shows a 3D tunnel framework composed of three functional units SeO 4 tetrahedron, IO 3 trigonal pyramid, and BiO 6 Cl polyhedron. [Display omitted] • A novel mixed-anion oxychloride KBi(SeO 4)(IO 3)Cl was hydrothermally synthesized and structurally determined. • KBi(SeO 4)(IO 3)Cl shows a 3D tunnel framework composed of three functional units. • KBi(SeO 4)(IO 3)Cl is a wide band gap semiconductor with E g = 3.9 eV. [ABSTRACT FROM AUTHOR]

Glassy Na-ion solid-state electrolytes (GNSSEs) are an important group of amorphous SSEs. However, the insufficient ionic conductivity of state-of-the-art GNSSEs at room temperature lessens their promise in the development of all-solid-state Na-ion batteries (ASSNIBs) with high energy density and improved safety. Here we report the discovery of a new sodium superionic glass, 0.5Na 2 O 2 -TaCl 5 (NTOC), based on dual-anion sublattice of oxychlorides. The unique local structures with abundant bridging and non-bridging oxygen atoms contributes to a highly disordered Na-ion distribution as well as low Na + migration barrier within NTOC, enabling an ultrahigh ionic conductivity of 4.62 mS cm -1 at 25 °C (more than 20 times higher than those of previously reported GNSSEs). Moreover, the excellent formability of glassy NTOC electrolyte and its high electrochemical oxidative stability ensure a favourable electrolyte-electrode interface, contributing to superior cycling stability of ASSNIBs for over 500 cycles at room temperature. The discovery of glassy NTOC electrolyte would reignite research enthusiasm in superionic glassy SSEs based on multi-anion chemistry., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The full characterisation of the high-pressure-synthesised, metastable layered oxyhalide Sr 2 NiO 2 Cl 2 is reported. It is comprised of infinite NiO 2 layers along with double rock salt Sr 2 Cl 2 layers and is closely related to the n = 1 Ruddlesden-Popper phases. At ambient temperature, it crystallises in the tetragonal space group I 4/ mmm with 2 formula units per unit cell with the basal lattice parameters a = b = 4.03417(2) Å and the stacking direction lattice parameter, c = 15.1058(1) Å. A tiny cusp in the temperature dependence of the magnetic susceptibility in a previous report suggested that this oxyhalide underwent long-range magnetic order and therefore contained high-spin Ni2+ ions. Powder neutron diffraction has confirmed that Sr 2 NiO 2 Cl 2 is a localised-moment oxyhalide, adopting the high-spin S = 1 configuration with fully occupied d xz , d yz and d xy orbitals and partially occupied d z2 and d x2-y2 orbitals. The Ni2+ magnetic moments order antiferromagnetically below ≈ 180 K in a G-type arrangement on a √2 a × √2 a × c expansion of the nuclear cell with the propagation vector (½, ½, 0) and with a saturated long-range ordered magnetic moment of 1.57(7) μ B per Ni2+ cation which is in line with previously calculated computational results and showing that the ligand field around the Ni2+ cation is not sufficiently anisotropic to drive it into the low-spin, diamagnetic configuration found for this d 8 cation in square planar or highly elongated octahedral coordination. [Display omitted] • Layered oxyhalide • Introduction of multiple anions can fine-tune properties • Ni2+ spin-state spectrum shows a crossover as a function of Ni–O length • This metastable phases requires a high-pressure synthesis • Antiferromagnetic G-type ordering indexed on a √2 a × √2 a × c expansion of the nuclear cell. [ABSTRACT FROM AUTHOR]

Present paper reports the study on luminescence and optical behaviour of samarium doped lanthanum oxychloride (LaOCl:Sm ^3+ ) nanophosphor for their potentiality in display devices. The conventional solid state route was employed to synthesize the phosphor La _1-x Sm _x OCl (x = 0, 0.01, 0.03, 0.05, 0.07 and 0.09). Tetragonal phase of the prepared compound was confirmed by PXRD. An agglomerated and spherical like structure were seen of the samples from FE-SEM analysis. The Wood and Tauc relation was employed to find out band gap energy and is around 4.23 eV. At an excitation wavelength of 408 nm, a high intense peak of emission was observed at 608 nm for transitions ( ^4 G _5/2 → ^6 H _7/2 ) of Sm ^3+ ions in the PL spectra. Colour co-ordinates (X̄,Ȳ) were used for the analysis of measured photoluminescence spectra. For the optimized concentration of Sm ^3+ (La _1-x Sm _x OCl with x = 0.05), the intensity parameters (Ω _2 , Ω _4 and Ω _6 )were determined. The trend of Ω _6 > Ω _4 > Ω _2 was observed. An emission cross section and Branching ratio are found to be 3.98 × 10 ^−22 cm ^2 and 59% respectively for ^4 G _5/2 → ^6 H _7/2 transition that makes it suitable for laser designs and application. The obtained results reveal that the LaOCl phosphor doped with samarium can be used on the screens of optical electronic systems and also is suitable for emission of reddish orange colour.

Mixed-anion compounds widen the chemical space of attainable materials compared to single anionic compounds, but the exploration of their structural diversity is limited by common synthetic paths. Especially, oxychlorides rely mainly on layered structures, which suffer from low stability during photo(electro)catalytic processes. Herein we report a strategy to design a new polar 3D tetrahedral framework with composition Zn 4 Si 2 O 7 Cl 2 . We use a molten salt medium to enable low temperature crystallization of nanowires of this new compound, by relying on tetrahedral building units present in the melt to build the connectivity of the oxychloride. These units are combined with silicon-based connectors from a non-oxidic Zintl phase to enable precise tuning of the oxygen content. This structure brings high chemical and thermal stability, as well as strongly anisotropic hole mobility along the polar axis. These features, associated with the ability to adjust the transport properties by doping, enable to tune water splitting properties for photoelectrocatalytic H 2 evolution and water oxidation. This work then paves the way to a new family of mixed-anion solids., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The reaction between GdO(s) and Cl(g) was studied in a high-resolution thermogravimetric system. The reaction product was GdOCl, which was the unique solid phase produced in all the temperature range studied. The GdOCl is subsequently chlorinated producing GdCl for temperatures above 1123 K. The system is under chemical control for temperatures below 723 K. It was found that the reaction order with respect to the chorine partial pressure is 0.77 and the activation energy is 132 kJ mol for the temperature range of 623-723 K. The global rate equation was developed. The GdOCl obtained was characterized by X-ray diffraction, scanning electron microscopy and magnetic measurements. The structure of GdOCl was refined with the Rietveld method, and it crystallized in a tetragonal form of REOX possessing the Matlockite-type (PbFCl) structure. The magnetic measurements indicated that the sample is paramagnetic at all the measurement ranges. The parameters of the Curie-Weiss law obtained were as follows: θ = −12.0 K, C = 7.9592 emu K mol and µ = 7.98 µ. [ABSTRACT FROM AUTHOR]

A new mayenite-type strontium oxy-chloride, Sr 12 Al 3.44 Fe 8.16 Ge 2.38 O 32 Cl 4.34 , was grown from a SrCl 2 flux at 1000 ​°C. The compound crystallizes in the complex three-dimensional chloromayenite structure type, a rare calcium aluminum oxide mineral of cubic symmetry, exhibiting nanocages that contain Sr and Cl ions. The lattice framework is composed of corner-sharing, three-component Al/Fe/Ge site-mixed tetrahedra. The compound crystallizes in the cubic space group I -43 d with lattice parameter a ​= ​12.6126(3) Å. [Display omitted] • Single crystals of Sr 12 Al 3.44 Fe 8.16 Ge 2.38 O 32 Cl 4.34 (SAFGOC) were grown out of molten SrCl 2 flux. • The crystal structure of the compound was solved using single crystal X-ray diffraction. • SAFGOC crystallizes in mayenite structure type and exhibits three-component site mixing. [ABSTRACT FROM AUTHOR]

Abstract: A new oxychloride Pb5Fe3TiO11Cl has been synthesized using the solid state method. Its crystal and magnetic structure was investigated in the 1.5–550K temperature range using electron diffraction, high angle annular dark field scanning transmission electron microscopy, atomic resolution energy dispersive X-ray spectroscopy, neutron and X-ray powder diffraction. At room temperature Pb5Fe3TiO11Cl crystallizes in the P4/mmm space group with the unit cell parameters a=3.91803(3)Å and c=19.3345(2)Å. Pb5Fe3TiO11Cl is a new n=4 member of the oxychloride perovskite-based homologous series A n+1 B n O3n−1Cl. The structure is built of truncated Pb3Fe3TiO11 quadruple perovskite blocks separated by CsCl-type Pb2Cl slabs. The perovskite blocks consist of two layers of (Fe,Ti)O6 octahedra sandwiched between two layers of (Fe,Ti)O5 square pyramids. The Ti4+ cations are preferentially located in the octahedral layers, however, the presence of a noticeable amount of Ti4+ in a five-fold coordination environment has been undoubtedly proven using neutron powder diffraction and atomic resolution compositional mapping. Pb5Fe3TiO11Cl is antiferromagnetically ordered below 450(10)K. The ordered Fe magnetic moments at 1.5K are 4.06(4)μB and 3.86(5)μB on the octahedral and square-pyramidal sites, respectively. [Copyright &y& Elsevier]

Abstract: The electrochemistry of chloride in water-containing hydrophobic ([Emim][NTf2] and [BmPyrr][NTf2]) and hydrophilic ([Emim][OAc]) ionic liquids (ILs) has been described in detail for the first time. Cyclic voltammetric studies at a glassy carbon electrode note the significant effect of ambient water on the electrochemistry of chloride, with different outcomes based upon the hydrophilicity (c.f. water content) of the hygroscopic ILs. Added hydroxide highlighted this as a reactive species. Evaluation of chloride, hypochlorite, chlorite, chlorate and perchlorate electrochemistry (chlorine oxidation states −1, +1, +3, +5 and +7) was performed. Ultimately, the electrochemically formed chlorine (Cl2) was determined to react with water or hydroxide to yield higher oxidation state species via oxychloride intermediates (e.g. hypochlorite) through multiple EC steps, likely resulting in chlorate as the final product. [Copyright &y& Elsevier]

A new compound, Ba 3 Ga 2 O 5 Cl 2 , isostructural with Ba 3 Fe 2 O 5 Cl 2 , was synthesized by solid-state reaction in air. Through single-crystal and powder X-ray diffraction analysis, the crystal structure was determined to be cubic with chiral space group I2 1 3 and unit-cell parameter a = 9.928 (1) Å. The Ga 3+ ions in Ba 3 Ga 2 O 5 Cl 2 are coordinated by O atoms and form GaO 4 tetrahedra. Ten neighboring GaO 4 tetrahedra are further bridged through corner sharing and rotation along the body diagonal, producing the chiral structure. Magnetization measurements indicate temperature-independent diamagnetic behavior, which is qualitatively consistent with core diamagnetism from all the constituent elements.