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LnMnO3+σ (Ln = La, Pr, Nd, Sm, Eu, Gd or Dy) perovskites synthesized by sol-gel method were employed for gaseous elemental mercury (Hg0) removal from coal-fired flue gas. Characterization results revealed the structure of the perovskites presented a phase transition process from rhombohedral system to O- and O'-orthorhombic structure with the change of A-site rare earth elements. The perovskites showed satisfactory Hg0 removal capacity in a narrow temperature range of 100–150°C. NdMnO3+σ with an O-O’ orthorhombic structure presented the best Hg0 removal performance, which markedly depends on four factors: crystal structure, oxygen vacancy density, Mn4+/Mn3+ ratio and surface element segregation. The Hg0 removal mechanism was illustrated based on the mercury temperature programmed desorption experiment and X-ray photoelectron spectroscopy characterization. Both chemisorption and catalytic oxidation played a role in the Hg0 removal process. Chemisorption dominated the Hg0 removal, due to the slow catalytic oxidation rate at low temperature. This work preliminarily established the relation between the structure of rare earth manganese perovskite and Hg0 removal performance.

Perovskite functional ceramics have been widely applied for thermal protection owing to their unique physical properties. However, formation of oxygen vacancies under external stimuli usually limits their performance in practical applications. Therefore, the mechanism of the effect of oxygen vacancy on the layer structure of perovskite La0.9Sr0.1TiO3+δ was investigated by experiments and first-principles simulations. The experimental results showed that the lattice distortion occurred in oxygen-deficient environment to give a longer c-axis, along with a significant adjustment in the modes of A/B–O bond vibration, resulting in lower reflectivity. Advanced transmission electron microscopy studies revealed that oxygen vacancies induced localized atomic rearrangements via [TiO6] layer movements to adapt to the lattice distortion. This eventually restructured a part of the layer interfaces by expanding the overlapping projection of atoms in the c-axial direction. The specific transformation process was described as a compendious process, while geometric phase analysis effectively clarified how oxygen vacancies can inhibit reflectivity on the layer structure. Thus, this study provides effective approaches for researching the effects of oxygen vacancy on the physical properties of orthorhombic layer perovskite structures, which may facilitate the development of perovskite-based functional devices.

In this paper, the crystallization behavior of a novel poly(monothiocarbonate), poly(trimethylene monothiocarbonate) (PTMMTC), was investigated and compared with its polycarbonate analogue, poly(trimethylene carbonate) (PTMC). It is found that PTMMTC exhibits strong crystallizability, while unstretched PTMC is amorphous. DSC and DMA results reveal that PTMMTC possesses higher glass transition temperature (Tg) and β-transition temperature (Tβ) than PTMC. Simulation based on density functional theory (DFT) shows that, the bond angle of C-S-C is evidently smaller than that of C-O-C, and thus a larger dipole moment. This leads to the stronger intermolecular interaction and more rigid chain conformation in PTMMTC, which is the origin of sulfur-substitution enhanced crystallization. The crystal structure of PTMMTC was preliminarily determined for the first time. PTMMTC has an orthorhombic crystal structure with a planar zig-zag chain conformation. The parameters of unit cell are a = 10.74 A, b = 4.79 A, and c (fiber axis) = 7.74 A.

Nanosized Ba1-xBixFe1-xCuxO3 (12–50 nm) with x values of 0, 0.01, 0.05, and 0.1 system was prepared using the Pechini method. Structural, morphological, surface and optical characterizations were performed for the prepared samples. Cubic phase was the predominant phase for the undoped BaFeO3 and Bi and Cu co-doped BaFeO3 samples. Minor phases of monoclinic Ba2Fe2O5, orthorhombic BaFe2O4 and orthorhombic BaCO3 were identified for all the prepared samples. Ba0.95Bi0.05Fe0.95Cu0.05O3 sample has the lowest band gap (2.43 eV). 98.1% paracetamol removal was achieved with 0.75 g/L of Ba0.95Bi0.05Fe0.95Cu0.05O3 at pH 9 after 120 min. The paracetamol degradation follows the pseudo first-order kinetics. HO• is the main oxidative species responsible for the paracetamol degradation. Gas chromatography–mass spectrometry (GC–MS) analysis was performed at the end of the photocatalytic degradation experiment under optimum operating condition using Ba0.95Bi0.05Fe0.95Cu0.05O3 to explain the reaction mechanism and identify the intermediate by-products which is confirmed by ultraviolet/visible (UV/Vis) spectroscopy study at different reaction times.

Cerium (Ce3+) doped strontium, barium orthogermanate samples are prepared by conventional solid state mixing method. In this process, X-ray powder diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy-dispersive X-ray spectroscopy (EDAX) and Photoluminescence (PL) measurements are carried out for the synthesized phosphors. The orthorhombic structure is confirmed by X-ray diffraction of the phosphors. EDAX is confirmed that all the elements are present in the compound such as Sr, Ba, Ge, O and Ce. Photoluminescence studies of Sr2GeO4: Ce3+ and Ba2GeO4: Ce3+ phosphors show intense blue emissions at 438 and 429 nm under ultraviolet excitation respectively. These phosphors are ascribed due to the 5d → 2F5/2, 2F7/2 electronic transitions of cerium ions. Therefore, these phosphors may be applicable in the display devices and lamp industry as blue emitting phosphors.

Li/Ce co-doped BaBi4Ti4O15–Bi4Ti3O12 (BBT-BIT) intergrowth bismuth layer-structured piezoelectric ceramics were prepared by conventional solid-state method. The X-ray diffraction, Raman spectroscopy, and scanning electron microscopy results showed that all the samples had a single orthorhombic phase structure, indicating that Li/Ce dopants had successfully dissolved into the BBT-BIT lattice. Li/Ce co-doping improved the piezoelectric properties of the ceramics: d33 increased from 6.8 pC/N to 21.4 pC/N and the Curie temperature Tc increased from 483 °C to 544 °C. Among all the ceramics investigated, the Ba0.7(Li0.5Ce0.5)0.3Bi8Ti7O27 ceramic showed the best comprehensive properties with d33 = 20.2 pC/N, Tc = 540 °C, tanδ = 0.53%, Ea = 1.13 eV, 2Pr = 10.5 μC/cm2. Meanwhile, the hysteresis loop of the BBT-BIT-0.3(Li0.5Ce0.5) sample sintered in an oxygen atmosphere was asymmetric, which may have been caused by defects produced by the Li/Ce co-doped. Besides, a d33 value of 18.5 pC/N was achieved at 450 °C, which is 91.6% of the value at room temperature, indicating the good thermal stability of the ceramic. The sample showed high resistivity, which can be attributed to the decrease in the concentration of the oxygen vacancies. Our results suggest the great potential of Li/Ce co-doped BBT-BIT intergrowth piezoelectric ceramics for high-temperature applications.

Single crystal of Sulphamic acid Lithium chloride (SALC), the inorganic nonlinear optical material was synthesized by slow solvent evaporation technique. PXRD analysis confirmed the grown crystal belong to orthorhombic structure to space group of Pbca. The vibrationally assigned frequencies of FTIR were obtained experimentally and compared with theoretical assigned values were calculated by DFT/B3LYP with 6–311++G(d,p) basis set by Gaussian 09 W software. The Vickers micro hardness study led to the evaluation of crystal belongs to hard category. The calculated FMO energy values indicate the charge transfer occurs within the molecule. The hyperpolarizability values of the grown molecule have been computed.

MgNb2-xVx/2O6-1.25x (0.1≤x≤0.6) ceramics with orthorhombic columbite structures were prepared at low-temperature by a solid-phase process. The phase component, microscopic morphology, low-temperature sintering mechanism and microwave dielectric performance of MgNb2-xVx/2O6-1.25x ceramics were comprehensively investigated. Low-temperature sintering densification of dielectric ceramics was achieved via the nonstoichiometric substitution of vanadium (V) at the Nb-site. In contrast to pure MgNb2O6 ceramics, the sintering temperature of MgNb2-xVx/2O6-1.25x (x = 0.2) ceramics was reduced by nearly 300 °C owing to the liquid-phase assisted sintering mechanism. The liquid phase arises from the autogenous low-melting-point phase. Meanwhile, MgNb2-xVx/2O6-1.25x (x = 0.2) samples with nonstoichiometric substitution could achieve a more than 900% improvement in the Q × f value, compared with stoichiometrically MgNb2-xVxO6 (x = 0.1, 0.2) ceramics. Finally, MgNb2-xVx/2O6-1.25x dielectric ceramics possess outstanding microwave dielectric properties: er = 20.5, Q × f = 91000, and τf = -65 ppm/°C when sintered at 1030 °C for x = 0.2, which provides an alternative material for LTCC technology and an effective approach for low-temperature sintering of Nb-based microwave dielectric ceramics.

Semiorganic single crystals of L-Threonine Lithium Chloride were wealthy developed by slow evaporation method at ambient circumstances. The structure was illuminated by single crystal XRD technique and the structure be owned by orthorhombic system. Density functional theory computations using B3LYP/6-311++ G(d,p) base set gives optimized structural parameters of title compound. The Theoretically identified hyperconjugative molecular interactions are accountable for the stabilization of compound are obtain by NBO analysis. Besides, Mulliken atomic charges and molecular electrostatic potential were also executed.

Screening of AgNO3/AgStBu solutions in DMF, DMSO and NMP resulted in an isolation of three novel nanosized silver/thiolate complexes with a torus-like {Ag20(StBu)10} core. The structures of [NO3@Ag20(StBu)10(NO3)9(DMF)6] (1) and [NO3@Ag20(tBuS)10(NO3)8(NMP)8][NO3@Ag19(tBuS)10(NO3)8(NMP)6]2(NO3) (2) were studied by SCXRD. The self-assembly process leading to 1 can be switched to a different outcome by Br–, resulting in [Br@Ag16(StBu)8(NO3)5(DMF)3](NO3)2 (3), which is the one of the few genuine host-guest complex in the silver/thiolate systems. Solutions of the individual complexes in CH3CN were studied by HR-ESI-MS techniques, which revealed a dynamic behavior for each complex, driven by a redistribution of the {AgNO3} units. This dynamics results in the appearance of both cationic and anionic species, based on unchanged silver-thiolate cores. Day light causes degradation of 3 with the formation of a composite material based on defective orthorhombic Ag2S with a porous morfology, as observed with SEM technique. Electrocatalytic HER activity of such material was studied.

An inorganic compound of sodium magnesium tetrachloride (SMGTC) single crystal was effectively grown by slow evaporation technique at room temperature. The powder X-ray diffraction analysis indicated the crystalline nature of the grown SMGTC crystal. The unit cell parameters were determined by single crystal X-ray diffraction analysis which shows that the SMGTC crystal crystallizes in orthorhombic crystal system with non-centrosymmetric space group Pba2. The UV cutoff wavelength of SMGTC was found to be 234 nm from UV–Vis-NIR studies. The second harmonic generation (SHG) efficiency of the SMGTC crystal was found to be 1.29 times greater than the well known KDP crystal. Presence of metal ion was identified by EDAX spectrum.

Current report is based on the synthesis of Gd+3 doped V2O5 nanostructures (GVO) along with fabrication of GVO/MXene binary nanocomposite. As synthesized GVO and GVO/MXene were characterized by XRD (X-ray diffraction), FESEM (Field emission scanning electron microscopy), EDX (Energy dispersive X-ray), BET (Brunauer Emmett Teller technique) and UV–Visible spectroscopy. Diffraction and elemental analysis confirmed the substitution of Gd+3 ions in VO layers. Orthorhombic phase of VO was observed in both GVO and GVO/MXene samples with crystallite size range of 17.02–17.51 nm. FESEM analysis indicated asymmetrical VO particles and sheets distributed on MXene layers, giving out a sponge like appearance. Surface area of GVO and GVO/MXene was enhanced to 20.46 and 23.69 nm, respectively. Effect of Gd+3 contents was significant on optical properties, which reduced the band gap energy of VO to 2.33 eV. The photocatalytic performance of prepared samples was analysed by the degradation of Methylene blue (MB) under direct sunlight. Gd+3 ion doping was found useful to enhance degradation of MB up to ∼71%. Among all samples, GVO/MXene showed maximum degradation (∼92%) within 120 min. Meanwhile, GVO/MXene showed good recyclability for successive five cycles. In addition, GVO and GVO/MXene were effective antibacterial agents against Gram positive (S. aureus) and Gram negative (P. vulgaris) strains of bacteria. The results suggested that the GVO and GVO/MXene could serve as potential candidates for large scale treatment of organic pollutants and pathogens.

Recently, there has been increasing interest in the synthesis and use of refractory oxide ceramics as a high-temperature electrode and also thermo-electric materials. These materials, such as perovskite type oxides, particularly, compounds like lanthanum chromite LaCrO3, usually exhibit hopping-type electrical conductivities approaching 30(Ω.cm)-1. The present work aims to synthesize and characterize rare-earth chromite oxides RECrO3 (RE: La, Yb, Gd, Pr), which have the orthorhombic perovskite structure that is apparently stable at 1000 °C calcination temperature. The synthesis of RECrO3 (RE: La, Yb, Gd, Pr) compounds was made by a citrate gel process, using rare-earth-nitrate salts as cation precursors, and followed by a heat-treatment at various temperatures (400 °C, 600 °C, 800 °C, and 1000 °C) for 4 h. The obtained powders were characterized by X-Ray diffraction (XRD), and scanning electron microscopy (SEM). Results show that all the products, especially calcined at 1000 °C have a high purity degree and good crystallinity and that this latter increases with the calcination temperature increasing which has “in contrast” a great effect on the agglomeration of the powders as is shown in the SEM’s micrographs.

A series of high-k Ba4Nd28/3Ti18-yGa4y/3O54 (0≤y≤2, BNTG) ceramics with temperature stable and ultra-low dielectric loss were synthesized via the conventional solid-state reaction. The main phase of all BNTG ceramics demonstrated an orthorhombic tungsten-bronze structure, but the impurity phase (gallium-rich phase) was found in BNTG (y = 2) ceramic. Partial substitution of Ga3+ for Ti4+ in B-site was a valid method to improve the temperature stability and dielectric loss of BNTG ceramics. The variation of er values of BNTG ceramics was dominated by the ionic polarizability. The ultra-low dielectric loss (ultra-high Q × f values) was associated with grain size, suppression of Ti3+ and impurity phase. The decrease of TCF values was highly dependent on the tilting of Ti-O octahedra and impurity phase. Finally, outstanding combination dielectric characteristics were achieved for BNTG microwave ceramics at y = 1.5 (er = 72.8, Q × f = 14,600 GHz, TCF=+4.1 ppm/°C) and at y = 2 (er = 70.3, Q × f = 15,500 GHz, TCF=+3.9 ppm/°C).

Present paper reports the study of single crystal X-ray diffraction of the compound 4-Amino-N-(3-chloropyrazin-2yl)benzene-1-sulfonamide which crystallizes in an orthorhombic crystal system with the space group Pbca having precise unit cell parameters a = 11.5260(19)A, b = 9.6270(16)A, c = 22.099(5)A, Z = 8 and V = 2452.1(8)A3. The structure was solved by direct methods and was refined by full-matrix least-squares based on F2. After subsequent cycles of refinement, the structure was converges to the Goodness-of-Fit (S) = 1.33. The molecule was adopted as a non-planar structure with a dihedral angle of 89.95°. In the crystal, molecules are held together through intermolecular N–H…O and C–H…O interactions. The nitrogen (N) atom of pyrazine ring has exhibited trifurcated intramolecular relations through C–H…N, N…C, and N…O incorporating S(5), S(6), and S(7) ring motifs, respectively. The intermolecular interactions were analyzed, and their percentage of contribution towards crystal packing was computed using Hirshfeld surface analysis. Also, interaction energies between the different pairs of molecules were analyzed, visualized and estimated using the energy density model of B3LYP/6-31G(d,p).

Since the breakthrough findings of Goodenough et al. in 1997, extensive research was carried out on olivine-type LiMPO4 (M: Transition metal) cathode materials for lithium ion batteries. This study reports the synthesis of five compounds LiFe1-xMnxPO4 (x = 0, 0.4, 0.6, 0.65, and 1) using sol–gel method at 800 °C. The crystal structure and the electrochemical properties of LiFe1-xMnxPO4 versus Li+/ Li were investigated. LiFe1-xMnxPO4 materials crystallize in the orthorhombic system with Pnma as space group. Moreover, a slight increase in the cell volume was noticed with the increasing amounts of Mn due to its large ionic radii (where Fe2+ ions (0.78 A) and Mn2+ ions (0.80 A). LiFe0.4Mn0.6PO4 shows the best electrochemical performances delivering a reversible discharge capacity of 110 mAh g−1 for 10 cycles at C/20 although no effective carbon coating was performed on the particles of this phosphate.

In the present study, copper (II) complex of 4, 4′-di-tert-butyl-2,2′-bipyridine [Cu (C18H24N2) (NO3)2], 1 is investigated through its synthesis and characterization using elemental analysis technique, infra-red spectroscopy, and single-crystal analysis. The compound 1 crystallizes in orthorhombic space group P212121. The copper atom in the mononuclear complex is hexa coordinated through two nitrogen and four oxygen atoms from bipyridine ligand and nitrate ligands. The thermal analysis depicts the stability of the entitled compound up to 170 °C, and the decomposition takes place in different steps between 170 and 1000 °C. Furthermore, quantum chemical techniques are used to study optoelectronic, nonlinear optical, and therapeutic bioactivity. The values of isotropic and anisotropic linear polarizabilities of compound 1 are calculated as 41.65 × 10−24 and 23.02 × 10−24 esu, respectively. Likewise, the static hyperpolarizability is calculated as 47.92 × 10−36 esu using M06 functional compared with para-nitroaniline (p-NA) and found several times larger than p-NA. Furthermore, the antiviral potential of compound 1 is studied using molecular docking technique where intermolecular interactions are checked between the entitled compound and two crucial proteins of SARS-CoV-2 (COVID-19). Our investigation indicated that compound 1 interacts more vigorously to spike protein than main protease (MPro) due to its better binding energy of −9.60 kcal/mol compared with −9.10 kcal/mol of MPro. Our current study anticipated that the above-entitled coordination complexes could be potential candidates for optoelectronic properties and their biological activity.

This work compares the dielectric properties of two new materials. One was 0.88 bismuth manganite–0.12 lead titanate (noted BM–PT hereafter) ceramics composite obtained by standard high-temperature sintering. The second composite was obtained from powdered ceramics dispersed in epoxy glue (noted BM–PT–epoxy). The occurrence of four phases in the ceramics, using X-ray powder diffraction (XRD), was recognized: orthorhombic Pbam, cubic Pn 3 ‾ m, cubic Pm 3 ‾ m, and monoclinic P2/m phase. Pseudo-Voigt function fitting confirmed significant structural disorder in the BiMn2O5 crystal lattice. Analysis of broadband dielectric spectroscopy data confirmed the applicability of the small polaron model to explain detected relaxation processes. Involvement of oxygen vacancies in relaxation and their correspondence to ordered, uniform potential wells in crystal lattices was deduced. Electric conductivity relaxation times behavior proved the sensitivity of the ceramics’ electrical features to hydrostatic pressure. BM–PT–epoxy composite exhibited dielectric permittivity and losses two orders of magnitude lower than those of BM–PT ceramics that opened new prospects to application. One relaxation process in BM–PT–epoxy composite related to the ceramics fill contribution. Other induced relaxation, observed only in this composite, was attributed to interactions at interfaces between the introduced powdered ceramics and the epoxy glue matrix. We showed that stresses generated either by hydrostatic pressure or through the interfacial interaction of epoxy matrix led to the same results: relaxation times shortening.

Solid polymer electrolytes have been broadly studied due to their wide applications in various electrochemical devices. In the present work, the electrical properties of polyaniline and its composites with BaSO4 have been studied. The polymerization of aniline monomer via the ordinary chemical polymerization process showed an amorphous structure. Whereas, in the presence of BaSO4 as a seed, the aniline is polymerized in an orthorhombic crystalline structure on the BaSO4-surface. Two composite samples of PANI and BaSO4 with different amounts of BaSO4 (1.5 and 2.5 wt%) were prepared and analyzed using XRD, FT-IR, SEM, and XPS techniques. The ac- electrical studies on the composites showed an enhancement in the electrical conductivity of PANI due to the addition of BaSO4. Ac- conductivity at frequency 500 kHz, and 100 °C, showed values of 1.9 × 10−3, 5.4 × 10−4, 1.6 × 10−1, and 1.9 × 10−1 S/cm for PANI, BaSO4, BaSO4/PANI 1.5 wt%, and BaSO4/PANI 2.5 wt%, respectively.

In the current report, pure V2O5, a series of Gd doped V2O5 (1 wt%, 3 wt%, 5 wt% and 10 wt%) and graphene integrated Gd–V2O5 photocatalysts have been prepared using a facile wet chemical approach. The effect of Gd+3 ions substitution and RGO support on V2O5 was studied by the different analytical techniques. X-ray diffraction (XRD) results showed the orthorhombic crystal structure of synthesized samples with crystallize size in range of 22–35 nm. Morphological analysis showed nanorods and nanorod arrays like appearance of V2O5, Gd–V2O5 and GdV-2O5/RGO, respectively. Gd–V2O5 and Gd–V2O5/RGO exhibited enhanced optical response in the visible region along with decrease in the band gap values for Gd doped V2O5 samples. BET surface area of Gd–V2O5 and Gd- V2O5/RGO was calculated as 12.39 g/m2 and 15.35 g/m2 that was found to be higher than pristine V2O5. To study the photocatalytic activity of synthesized photocatalysts, methylene blue (MB) was chosen as model pollutant. Among the Gd doped V2O5 samples, highest photocatalytic activity (45.62%) was achieved by optimal concentration of 5 wt% Gd–V2O5 that is accredited to effective separation of electron-hole pairs. While Gd–V2O5/RGO showed 2.1 times higher dye removal (97.12%) than unsupported Gd–V2O5, under the visible light irradiation. The significantly high photocatalytic activity of Gd–V2O5/RGO is due to the synergistic effect aroused by combined action of Gd+3 ions doping and advantageous properties of highly conductive and large surfaced graphene. Recycling experiments for V2O5 derivatives showed good stability and recyclability of photocatalysts. Additionally, Gd–V2O5/RGO was found to be more potential anti-bacterial agent than V2O5 and Gd–V2O5.

Europium doped (0.1% and 1%) chloroborate BaO–B2O3–BaCl2 glass and glass-ceramic with embedded BaCl2 nanocrystals have been synthesised, investigated, and compared with the corresponding nanocrystalline powder. The structural analysis of the glass evidenced ionic bonds characteristic to the glass host structure and compositional changes during the melting. X-ray diffraction and transmission electron microscopy revealed the formation of orthorhombic BaCl2 nanocrystals of about tens on nm in size and a smaller amount of BaB2O4 nanocrystals. Structural analysis of the Eu2+-doped BaCl2 nanocrystals has shown a distortion of the crystalline cell assigned to the growth process, affected by defects and ionic impurities. Photoluminescence spectra of the glass-ceramic revealed Eu3+ and Eu2+ luminescent ion species, but only Eu2+ is incorporated within the BaCl2 nanocrystalline phase. Electron paramagnetic resonance measurements in X-band sustain the presence of Eu2+ ions. The EPR parameters (g values and hyperfine constants) resulting from the Q-band EPR spectra simulations recorded on glass-ceramic are similar to those in Eu2+-doped BaCl2 and confirmed the partial incorporation of Eu2+ ions within the BaCl2:Eu2+ nanocrystals in the glass-ceramics.

Acta crystallographica / B 77(6), 986 - 995 (2021). doi:10.1107/S2052520621010088, A new six-membered cyclic alkanolamine with chemical formula C$_6$H$_{15}$N$_3$O$_3$ was synthesized by the reaction of glycolaldehyde with gaseous ammonia. The molecular structure, characterized by a hexagonal ring of alternating carbon and nitro��gen atoms with three hy��droxy��methyl groups attached to the carbon atoms, could not be unambiguously determined by elemental analysis and $^1$H/$^{13}$C/$^{15}$N NMR. The molecular structure and conformation were further determined using a combination of vibrational spectroscopy (IR and Raman) and real-space pair distribution function (PDF) analysis. The crystal structure was determined ab initio from laboratory X-ray powder diffraction (XRPD) with orthorhombic space group Ama2 (No. 40) and unit-cell parameters a = 12.1054 (2) ��, b = 13.5537 (2) �� and c = 5.20741 (8) ��. Consistent structure models could be obtained by symmetry-independent PDF and PDF-Rietveld co-refinements. Independent local structure refinements indicate that the most likely deviations from the average structure consist of small tilting and translational distortions of hydrogen-bonded molecular stacks. Thermal analysis (TG/DTA) and temperature-dependent XRPD measurements were also performed to determine the thermal behavior., Published by Wiley-Blackwell, Oxford [u.a.]

Different phases of tungsten trioxide (WO3) nanoparticles were synthesised by hydrothermal method involving the extracts of avverhoea bilimbi, citrus limon and tamarindus indica as capping agents. These synthesized nanomaterials were characterized through X-ray diffraction, Raman spectra, Transmission electron micrographs, diffuse reflectance spectra and photoluminescence spectral techniques. The X-ray diffraction patterns and Raman spectra corroborate the formation of different crystal phases viz., monoclinic (m-WO3), orthorhombic (o-WO3) and hexagonal (h-WO3). The morphological and topographical studies were acquired from SEM and TEM images. The surface parameters were examined from BET isotherms. The absorption spectra reveal that the optical band gap energy is found to be higher for h-WO3. The adsorption of Cu(II) ions were found to be effective provided with optimum conditions and the adsorption capacity was found to be 174.5 mgg−1 by the h-WO3 nanoparticles. A study on Langmuir, Freundlich, D–R and Temkin isotherm models, deviation in D–R model implies that the adsorption is chemisorption process and follows pseudo-second order kinetics. The adsorption process is found to be spontaneous and exothermic from the thermodynamic parameters.

Tin (Sn)-doped orthorhombic gallium oxide (κ-Ga2O3) films were grown on (0001) sapphire by mist chemical vapor deposition. It is known that κ-Ga2O3 is more stable than α-Ga2O3 (corundum) but less stable than β-Ga2O3 (monoclinic). This thermodynamic stability means an optimal growth temperature (Tg) of the κ-phase (600-650 °C) is also in between the two. At first, it was observed that Sn doping induced the κ-phase during the growth of the β-phase (Tg = 700 °C). Interestingly, Sn could also promote the κ-phase even under the growth condition that strongly favors the α-phase (Tg = 450 °C). The postgrowth annealing tests at 800-1000 °C showed that the thermal stability of the κ-phase depends on the Sn concentration. The higher the Sn concentration, the more stable the phase. The one with the highest Sn content showed no phase transition from κ to β after annealing at 800, 900, and 1000 °C for 30 min each. This enhancement of thermal stability promises more reliable high-power and high-frequency devices for which κ-Ga2O3 is suitable. Although there was no correlation between Sn-induced phase stabilization and the crystal quality, cathodoluminescence revealed that increasing Sn concentration led to the strong suppression of the radiative recombination at 340 nm from the vacancy-related donor-acceptor pairs. This observation suggests that the phase stabilization by Sn could be related to a specific Ga site Sn replaces in the orthorhombic structure.

A potassium salt of the N2S2O2-coordination Fe(III) anion K[Fe(5Cl-thsa)2] (1) (5Cl-thsa - 5-chlorosalicylaldehyde thiosemicarbazone) is synthesized and characterized structurally and magnetically over a wide temperature range. Two polymorphs of salt 1 characterized by the common 2D polymer nature and assigned to the same orthorhombic Pbcn space group have been identified. The molecular structure of the minor polymorph of 1 was solved and refined at 100, 250, and 300 K is shown to correspond to the LS configuration. The dominant polymorph of 1 features K+ cations disordered over a few crystallographic sites, while the minor polymorph includes fully ordered K+ cations. The major polymorph exhibits a complete three-step cooperative spin-crossover transition both in the heating and cooling modes: The first step occurs in a temperature range from 2 to 50 K; the second abrupt hysteretic step occurs from 200 to 250 K with T1/2 = 230 K and a 6 K hysteresis loop. The third gradual step occurs from 250 to 440 K. According to 57Fe Mossbauer, XRPD, and EXAFS data, the spin-crossover transition for the dominant polymorph is quite peculiar. Indeed, the increase in the HS concentration by 57% at the second step does not result in the expected significant increase in the iron(III)-ligand bond lengths. In addition, the final step of the spin conversion (ΔγHS = 26%) is associated with a structural phase transition with a symmetry lowering from the orthorhombic (Pbcn) to the monoclinic (P21/n) space group. This nontrivial phenomenon was investigated in detail by applying magnetization measurements, electron spin resonance, 57Fe Mossbauer spectroscopy, and DFT calculations. These results provide a new platform for understanding the multistep spin-crossover character in the Fe(III) thsa-complexes and related compounds.

Inorganic metal-halide perovskites hold a lot of promise for solar cells, light-emitting diodes, and lasers. A thorough investigation of their optoelectronic properties is ongoing. In this study, the accurate modified Becke Johnson generalized gradient approximation (mBJ-GGA) method without/with spin orbital coupling (SOC) implemented in the WIEN2k code was used to investigate the effect of mixed I/Br and Br/Cl on the electronic and optical properties of orthorhombic CsPb(I1-x Br x )3 and CsPb(Br1-x Cl x )3 perovskites, while the Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA) method was used to investigate their structural properties. The calculated band gap (Eg) using the mBJ-GGA method was in good agreement with the experimental values reported, and it increased clearly from 1.983 eV for CsPbI3 to 2.420 and 3.325 eV for CsPbBr3 and CsPbCl3, respectively. The corrected mBJ + SOC Eg value is 1.850 eV for CsPbI3, which increased to 2.480 and 3.130 eV for CsPbBr3 and CsPbCl3, respectively. The calculated photoabsorption coefficients show a blue shift in absorption, indicating that these perovskites are suitable for optical and optoelectronic devices.

Optimization of materials exhibiting high-temperature superconductivity for producing controllable nano-devices is crucial for industrial applications. Herein we report a comprehensive study of the diffusion process between YBa2Cu3O7−δ (YBCO) and iron particles. Fe diffusion into the YBCO matrix could be fundamental for multilayer systems with YBCO/Fe-alloy interfaces. We have found that the orthorhombic YBCO structure adopts to 3 wt% Fe, while for higher Fe content, a formation of BaFeO3−δ and iron oxides was observed. Complementary measurements confirmed the strong superconductivity suppression in YBCO-Fe materials containing more than 7 wt% Fe. The YBCO with diffused Fe material retain the unit cell orthorhombicity (max. 3 wt% Fe), and their superconducting properties follow the principle of critical scaling with different exponents (γ). The critical current density (Jc), pinning fields (HP) exhibit γ = 1, the first critical field (Hc1) shows γ = 1/2, and critical temperature (Tc) demonstrates γ = 7/4.

Perovskite Solar Cells (PSC) based on cesium lead triiodide (CsPbI3) perovskite have received great attention. However, the quality and thickness of perovskite active layers are still far from the level of perfection due to the limited solubility of the perovskite materials for PSC. Here, eco-friendly methylammonium acetate (MAAc) solution was used for stirring the CsPbI3 perovskite to transform from the yellow (orthorhombic) phase to the black (cubic) phase without additives. The high performance of CsPbI3 PSC has been achieved by annealing at low temperature with multiple coating, without any additives and anti-solution treatment, based on the combination of good film morphology, low-defect surface and longer carrier diffusion length reported for fabrication of good quality perovskite films in full air conditions. CsPbI3 perovskite film changes from yellow to black phase at low temperature on MAAc solution. Increasing thickness can improve the absorption of incident light and consequently improve the Power Conversion Efficiency (PCE) of 14.4% by significantly elevated device parameters of inverted planar PSC. The results reveal that the multiple coatings of CsPbI3 on MAAc solution without additives is a promising choice for good-stability and effective PSC.

LiCoPO4 is an attractive cathode material, but it undergoes poor electronic conductivity and electrochemical performance. This performance is enhanced by substituting iron antisite Cobalt to reduce the direct interaction between the cathode and the electrolyte. Thus, LiCoPO4 doped with Fe was synthesized by the microwave-assisted solvothermal route at 220 °C. According to X-ray diffraction analysis, a single orthorhombic Pn21a phase (a = 10.02 A, b = 6.71 A and c = 4.96 A) was obtained, which transited to Pnma phase (a = 10.21 A b = 5.92 A and c = 4.76 A) after annealing at 700 °C in air. The morphology and particle size of the sample changed after annealing, as shown by TEM. The electrochemical cycling of an annealed sample showed the initial discharge capacity of 125mAh g−1 compared to 12 mAh g−1 for the non-annealed sample, which can be regarded as a partial coating by FePO4 as obtained from X-ray absorption spectroscopy analysis.

For the first time, AA h boron nitride (BN) crystal, assigned to an orthorhombic space group (No. 31, Pm21), is reported. The structure of BN nanotubes is reinterpreted as a helix, resulting from texture and helical growth of the AA h BN crystal used., AA h boron nitride (BN) crystal, assigned to an orthorhombic space group (No. 31, Pm21), is reported here. This new AA h BN crystal exhibits a ‘linear’ morphology for high-resolution transmission electron microscopy (HRTEM) and a (non-hexagonal) ‘diagonal’ electron-diffraction pattern, which have been experimentally demonstrated in this article. It is also demonstrated that this new crystal is the basic structure of multi-walled BN nanotubes (BNNTs) existing in the form of a helix. The helical AA h BNNTs exist in a metastable phase owing to 〈200〉 texture growth of the orthorhombic crystal, where the energy is ∼15 meV higher than that of stable AB or AA′ BN. It is shown that the typical scanning electron microscope ‘fluffy cotton-like’ morphology of BNNTs is due to secondary growth of diverse BN sheets (including mono-layers) on incoherently scrolled wall strands of BNNTs, providing further evidence for the helical structure with HRTEM evidence for a left-handed helix.

0–5% Pd-doped Bi2MoO6 nanoplates as visible-light-driven photocatalysts were successfully prepared in this research. The XRD patterns of as-prepared Pd-doped Bi2MoO6 samples were indexed to pure orthorhombic Bi2MoO6 phase with no impurity detection. The Raman and FTIR wavenumbers of Pd-doped Bi2MoO6 nanoplates were significantly shifted by the change of energy bonds in Bi2MoO6 nanoplates, including the TEM characterization of the growth of nanoplates through the exposure {020} facet. Main symmetric stretching vibration of MoO6 containing in Pd-doped Bi2MoO6 nanoplates were also detected. XPS of 3% Pd-doped Bi2MoO6 nanoplates revealed the binding energies of Pd 3d5/2 and Pd 3d3/2 core levels, which are indicative of incorporated Pd2+ ions in Bi2MoO6 lattice. The photocatalytic activities of Bi2MoO6 with and without being loaded with Pd dopant monitored through the degradation of rhodamine B were increased from 38.36% for Bi2MoO6 to 97.12% for 3% Pd-doped Bi2MoO6 photodegraded by h+ and ·O2− main active radicals. The 3% Pd-doped Bi2MoO6 nanoplates were very stable and reusable for wastewater treatment.

This manuscript is discussing the growth of a new class semi-organic nonlinear crystal l-Lysine hydrogen chloride (LLHC) was grown by slow evaporation method using a mixed solvent of deionized water + ethanol and pure deionized water. The crystal crystallizes in orthorhombic space group of P212121. Lattice parameters were revealed by single crystal X-ray diffraction analysis. The FT-IR spectral analysis was performed on the grown crystal LLHC to identify its functional groups. The position of protons and carbons was determined by the NMR technique. The grown crystal was characterized by optical transparency through UV–Vis range with a short cutoff wavelength of 212nm. Thermal and physiochemical stability of the title crystal was found out through the TG-DTA analysis, which proves the crystal stability up to 251.4 °C. Brewster’s point method was used to find out the refractive index of the grown compound LLHC. Vickers’s microhardness test was performed on LLHC to find out its mechanical stability. The second harmonic generation (SHG) of the grown crystal LLHC was confirmed by the Kurtz-perry powder method and the SHG efficiency was compared with the known Potassium Dihydrogen phosphate (KDP) standard. By using a minimal bactericidal concentration (MBC) benchmark, their antibacterial activity was evaluated. The grown crystal shows long-term and outstanding antibacterial activity against E.coli and S.aureus.

We present a study on the structural and phonon properties of cobalt-doped orthorhombic molybdenum trioxide (α-MoO3:xCo) hierarchical microrods. The samples were synthesized by solid-state reaction with molar concentrations of 0%, 1%, 3%, and, 5% cobalt. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and Fourier transformed infrared spectroscopy (FTIR) were used to confirm the orthorhombic phase and the structural properties of each sample. The infrared and Raman spectra of the samples show that doping alters the ratio of relative intensities, linewidth, and the shift of the wavenumber of the modes, and a correlation is established between the stretching force constant and wavenumber. Experimental temperature-dependent Raman scattering studies were performed on samples of α-MoO3:xCo over a temperature range of 298–813 K. The Raman spectra showed a phase transition at around 373 K to a self-similar structure, indicating a possible isostructural phase transition (IPT) for samples with 0% and 1% cobalt, a phenomenon rarely reported in the literature. Nevertheless, this phase transition was not observed for samples containing 3% and 5% cobalt, indicating an increase in material stability.

Layered oxyhalides containing double or triple fluorite layers are promising visible-light-responsive water-splitting photocatalysts with unique band structures. Herein, we report on the synthesis, structure, and photocatalytic property of Bi4BaO6Cl2 (I4/mmm) with alternating double (Bi2O2) and triple (Bi2BaO4) fluorite layers, which was extracted from the crystallographic database on the basis of Madelung potential calculations. Rietveld refinements from powder X-ray and neutron diffraction data revealed the presence of cationic disorder between Bi2O2 and Bi2BaO4 layers, leading to electrostatic stabilization. DFT calculations suggested that photogenerated electrons and holes flow through the double and triple layers, respectively, which may suppress electron-hole recombination. We expanded this double-triple system to include Bi4CaO6Cl2 and Bi4SrO6Cl2 with orthorhombic distortions and different degrees of cationic disorder, which allow band gap tuning. All the double-triple compounds Bi4AO6Cl2 showed stable water-splitting photocatalysis in the presence of a sacrificial reagent.

K0.5Na0.5NbO3 (KNN) particles were prepared by a solid–state method. X–ray diffraction, scanning electron microscopy, UV–visible spectrophotometry, and electrochemical impedance spectroscopy were used to study the structure, morphology, and properties of the samples. The obtained KNN is a ferroelectric material with orthorhombic perovskite structure at room temperature. The KNN particles can be used as piezo/photo–bicatalysts for degrading organic pollutants by utilizing vibrational and solar energy; the catalytic activity of the particles can be significantly improved owing to their polarization under an applied electric field. Poled KNN particles show a bicatalytic degradation ratio of rhodamine B (RhB) dye reaching 92% after 60 min. The results indicate that the KNN particles can be applied as attractive ferroelectric catalysts for organic pollutant degradation.

The volatization of cesium at high temperatures makes its immobilization challenging to the nuclear scientists. Present work reports the feasibility of cesium incorporation into an orthorhombic langbeinite phosphosilicate. The structural flexibility, leachability and thermal expansion of K2-xCsxZr2P2SiO12 (x = 0, 0.5, 1.0, 1.5, 2.0) have been investigated. Powder X-ray results authenticates the accommodation of cesium into a single phasic orthorhombic langbeinite structure up to 29.17 wt %. Morphological study reveals the particle agglomeration and poor crystallinity, and vibrational spectral analysis shows peak broadening and peak shift upon increasing the cesium concentration. The static leach test has been performed on the pellet sample and the normalized leaching of Cs is found to be in the order of 101 g/m2. The average coefficient of thermal expansion for K0.5Cs1.5Zr2P2SiO12 is registered as 7.45 × 10−6/K between 303 and 873 K. Cesium insertion into K2Zr2P2SiO12 displays a large deviation in thermal expansion due to the size effect as observed by several researchers for other phosphate and phosphosilicate members.

The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound 1·H2O crystallizes in the orthorhombic crystal system (space group Pbca) with unit cell parameters a = 23.2139(4) A, b = 25.2962(4) A, с = 32.5478(6) A, V = 19112.8(6) A3, R = 0.0592. The electronic structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] complexes are investigated by X-ray spectroscopy techniques and compared with the structures of polymeric chalcogenides Nb2S4Br4 and Nb2Se4Br4. By XPS it is shown that effective charges on atoms of the {Nb2(μ-Q2)2}4+ (Q = S, Se) core do not change when passing from Br– to NCS– ligands. The HOMO and LUMO structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] are analyzed by XPS and XANES techniques. The largest contributions of S 3p states of NCS– ligands to the occupied molecular orbitals are found to be near the upper boundary of the valence band while the contributions from dichalcogenide bridging ligands have a more uniform distribution. For the conduction band, the contributions of S 3p states of NCS– ligands are located deeper whereas the contributions from dichalcogenide bridging ligands are near the lower boundary of the conduction band. The interaction of Nb 4d and S 3p/Se 4p states of dichalcogenide bridges for the HOMO has an antibonding character, which is bonding for all the other occupied molecular orbitals and antibonding for all unoccupied molecular orbitals.

The quaternary selenide Ba4GeSb2Se11 was prepared by a high-temperature solid state reaction method. Ba4GeSb2Se11 crystallizes in an acentric orthorhombic space group Cmc21 with the lattice constants a = 9.370(11) A, b = 25.850(0) A, and c = 8.798(10) A. The compound is composed of a [SbSe3]3- trigonal pyramid, [GeSbSe5]3- dimers, V-shaped Se32-, and the adjacent Ba2+ ions. It has indirect band gap of 1.35 eV and exhibits a second harmonic generation intensity of about 0.2 times that of the benchmark compound AgGaS2 at the same particle size. Interestingly, theoretical analyses show that the central Se atom of Se32- has the largest contribution (8.1%) to d31 compared to that of other Se atoms, which may be due to its easy swing in the a-axis direction.

We provide the material synthesis method, crystal structure information, and characterization of a novel mixed-valent metal oxide KIn0.33IIITe0.67VITe2IVO7, closely related to zirconolite (CaZrTi2O7), a radioactive waste immobilized material, having a 3D framework. The reported metal oxide containing an alkali-metal cation (K+), main-group cation (In3+), tellurate, and tellurite has been synthesized as both single crystals and a pure polycrystalline phase through a hydrothermal synthesis method. Single-crystal X-ray diffraction indicates that KIn0.33Te2.67O7 crystallizing in the orthorhombic space group Cmcm (No. 63) reveals a 3D framework structure with a 1D channel consisting of Te/InO6 octahedra and TeO4 polyhedra. An interesting transition reaction from KIn0.33Te2.67O7 to KIn(TeO3)2 under hydrothermal conditions at 230 °C is discussed.

The crystal and electronic structure properties of Ni-B (nickel-boron) alloy coatings produced by an electrodeposition method have been investigated. The crystal structures of the alloy coatings were determined by x-ray diffraction patterns and supported by extended x-ray absorption fine structure (EXAFS) spectroscopy. The local atomic structure around the Ni atom was obtained from EXAFS studies at the Ni K-edge, and the EXAFS data were fitted with theoretical calculations. With the addition of boron atoms in the nickel environment, NiB composite alloys were formed in the crystals with an orthorhombic "Cmcm" structure. The analysis revealed a limited effect of boron doping in the electronic structure of the nickel atoms. Boron atoms were determined as sitting between the Ni atoms and causing a disturbance in the crystal structure due to providing inhomogeneous interstitial potential and defects.

Two alkali tin(II) phosphates, namely, Rb[SnF(HPO4)] and Rb(Sn3O)2(PO4)3, were synthesized through mild hydrothermal methods. They belong to the orthorhombic Pnma and Pbcn space groups, respectively. Rb[SnF(HPO4)] features a layered structure based on 1D [SnF(HPO4)]∞ chains interconnected by hydrogen bonds, with Rb+ cations located at the interlayer space. For Rb(Sn3O)2(PO4)3, each pair of [Sn3O]4+ clusters is bridged by a pair of [P(1)O4]3- tetrahedra to build a 1D [Sn-P-O]∞ chain. These 1D [Sn-P-O]∞ chains are further cross-linked though [P(2)O4]3- tetrahedra to construct a 3D network with 7- and 10-membered-ring channels. The tin(II) ions in Rb[SnF(HPO4)] and Rb(Sn3O)2(PO4)3 with stereochemically active lone pairs (SCALPs) significantly enhance the birefringences of metal phosphates: Δn = 0.147@1064 nm for Rb[SnF(HPO4)] and 0.082@1064 nm for Rb(Sn3O)2(PO4)3.

Oxide crystals have been widely used in the nonlinear optical (NLO) field in the ultraviolet-visible and near-infrared region. Most of the traditional oxide crystals are restricted in the mid-infrared region due to their narrow transmission window. Hence, attempting to extend infrared cutoff wavelength of oxide has attracted much attention. In our work, we reported two new tellurate Li 2 TiTeO 6 (LTT) and Li 2 SnTeO 6 - (LST) with broad transparent region 0.38-6.72 and 0.38-6.86 μm, respectively, which could be excellent candidates for the mid-infrared NLO application. Both LTT and LST are crystallized in the orthorhombic space group P nn 2. The LTT crystal exhibits intense powder second-order generation efficiency (26×KDP) under the fundamental wavelength of 1064 nm. The first-principles calculations and dipole moments were used to illustrate the results of the powder second-harmonic generations based on the crystal structures. Our results provide a novel oxide NLO crystal with a strong SHG and wide transparency range. It also paves a way to design new oxide mid-IR NLO crystals.

In this work, we report the sol–gel spin-coated novel thin film Aurivillius Phase Layered Bismuth titanate (Bi4Ti3O12, BTO) thin film coated on FTO glass substrate annealed at 700 °C was prepared and its detection of mercury ion. The structural orientation, surface morphology, chemical composition, vibrational, and optical properties of the prepared thin film were characterized using XRD, SEM, XPS, Raman, UV–Vis, and PL, respectively. From the XRD analysis, the crystal growth is well preferred in (117) plane corresponding to the orthorhombic structure of BTO. SEM images of the prepared thin film exhibited an anisotropic plate-like grained structure. Photoluminescence spectra showed a good optical emission peak at 545 nm. In Raman spectra, the observed phonon modes are well correlated to the orthorhombic phase of BTO thin films. XPS confirmed the oxidation states of Bi4Ti3O12 thin film. The electrocatalytic activity of the prepared BTO thin film electrode concerns mercury detection using cyclic voltammetry (CV) and linear sweep voltammetry (LSV) technique. CV analysis disclosed that the prepared thin film electrode is very active in the electrochemical performance of heavy metal (Hg) detection. LSV result reveals that the prepared thin film exhibits enhanced sensitivity and lower detection limit of electrochemical Hg detection. From the electro-oxidation studies, the BTO thin film electrode acts as a favorable candidate for the application of heavy metal detection.

Demands for IR birefringent materials are increasing due to the rapid developments of IR laser applications. Herein, two new chain tellurides β-BaGa2Te4 and Ba5Ga2Ge3Te12 have been discovered. β-BaGa2Te4 crystallizes in the orthorhombic space group Imma (no. 74) with unit cell constants of a = 23.813(3) A, b = 11.9673(19) A, and c = 6.7215(9) A, while Ba5Ga2Ge3Te12 crystallizes in the monoclinic space group P21/c (no. 14) with unit cell constants of a = 13.6540(3) A, b = 9.6705(2) A, and c = 23.1134(7) A. The structure of β-BaGa2Te4 can be considered to be the antiparallel arrangement of one-dimensional (1D) [GaTe2] chains formed by edge-sharing GaTe4 tetrahedra, which are separated by Ba2+ cations. In the crystal structure of Ba5Ga2Ge3Te12, two kinds of 1D chains, namely chain 1 ∞1[(GaGe)3Te8] and chain 2 ∞1[(GaGe)2Te4], are stacked alternately and put together by the coulomb force with Ba2+ cations. In addition, First-principles calculations indicate that β-BaGa2Te4 has a large birefringence, ∼0.325 at 2050 nm, derived from the superposition of the polarizabilities of GaTe4 tetrahedra, implying that it has potential as an IR birefringent material. This work may provide some guidance for exploring new IR birefringent crystals.

A new alkali metal-rare earth metal anhydrous sulfate, KTb(SO4)2 (KTSO), was synthesized by a hydrothermal method. It crystallized in the non-centrosymmetric (NCS) orthorhombic space group P212121 with cell parameters a = 5.43950(10), b = 8.8579(3), c = 13.3962(4), Z = 2. Its structure is composed of [KO11], [TbO8], and [SO4] groups, which are interconnected to constitute a one-dimensional (1D) chain, and then further linked to construct a three-dimensional (3D) network structure through [SO4] units. The results of the powder frequency doubling test show that KTb(SO4)2 has a phase-matching second-order nonlinear optical effect of 0.3 times that of KH2PO4 (KDP). The measured birefringence of the crystal (0.01) agrees well with the calculated value (0.019). Meanwhile, its infrared and ultraviolet spectrum and thermal properties were studied, respectively. Its optical properties and band gap structure are studied by theoretical calculation. This work provides a NCS structure of anhydrous sulfates and offers guidance for further exploration of new anhydrous sulfates.

We have synthesized the orthocarbonate Sr3[CO4]O in a laser-heated diamond anvil cell at 20 and 30 GPa by heating to ≈3000 (300) K. Afterward, we recovered the orthocarbonate with [CO4]4- groups at ambient conditions. Single-crystal diffraction shows the presence of [CO4]4- groups, i.e., sp3-hybridized carbon tetrahedrally coordinated by covalently bound oxygen atoms. The [CO4]4- tetrahedra are located in a cage formed by corner-sharing OSr6 octahedra, i.e., octahedra with oxygen as a central ion, forming an antiperovskite-type structure. At high pressures, the octahedra are nearly ideal and slightly rotated. The high-pressure phase is tetragonal (I4/mcm). Upon pressure release, there is a phase transition with a symmetry lowering to an orthorhombic phase (Pnma), where the octahedra tilt and deform slightly.

An X-ray diffraction study aimed at establishing the subtle details of the electron density and anharmonicity of the atomic vibrations in a stoichiometric monodomain single crystal of potassium niobate, KNbO3, has been conducted at room temperature (orthorhombic ferroelectric phase Amm2). The cation and anion displacements obtained from the experiment are weakly anharmonic without any manifestation of structural disorder. The chemical bond and interatomic interactions inside and between crystal substructures at the balance of intracrystalline forces are characterized in detail. The role of each of the ions in the formation of the ferroelectric phase was studied and the features of the electron-density deformation in the niobium and oxygen substructures, and the role of each of them in the occurrence of spontaneous polarization are established. The position-space distribution of electrostatic and quantum forces in KNbO3 is restored. It is emphasized that for the completeness of the analysis of the nature of the ferroelectric properties it is necessary to consider both static and kinetic electronic factors, which are of a quantum origin. The experimental results and theoretical estimations by the Kohn–Sham calculation with periodic boundary conditions are in reasonable agreement, thus indicating the physical significance of the findings of this study.

Transition-metal containing halides with Ruddlesden-Popper (RP) perovskite structures have received extensive attention owing to their emerging and anisotropic photoelectric functionalities. Among them, A2 CuX4 (A=alkali metal or organic cations, X=Cl, Br, I) series are particular, because of the Jahn-Teller distortion of Cu2+ sensitive to external stimuli such as temperature and pressure. In this article, we report the structure evolution and physical property responses of RP perovskites Rb2 CuCl4-x Brx (x=1, 2) to external pressure. Dramatic structural phase transitions from orthorhombic to monoclinic occur around 3.0 GPa in both materials regardless of their distinct compositions. Structure analyses reveal the suppression and final vanishing of the Jahn-Teller distortion of Cu2+ cations under compression and crossing the phase transition, respectively. Rb2 CuCl4-x Brx perovskites exhibit abrupt bandgap narrowing (from reddish-brown to black) along with the structural phase transition, and an overall bandgap narrowing of 75% up to ∼27 GPa but still keeping semiconductive. During the compression processes, the resistances of Rb2 CuCl4-x Brx have been greatly reduced by 5-orders of magnitude. Moreover, all of the pressure-induced phenomena in Rb2 CuCl4-x Brx perovskites are reversible upon decompression and no obvious difference is observed for the pressure responses between [CuCl4 Br2 ] and [CuCl4 (Cl,Br)2 ] coordination environments. The impact of pressure on the structural and physical properties in two-dimensional Rb2 CuCl4-x Brx provides in-depth understanding on the structure design of functional halide perovskites at ambient conditions.

The novel α-BaZn2P2 structural polymorph has been synthesized and structurally characterized for the first time. Its structure, elucidated from single crystal X-ray diffraction, indicates that the compound crystallizes in the orthorhombic α-BaCu2S2 structure type, with unit cell parameters a = 9.7567(14) A, b = 4.1266(6) A, and c = 10.6000(15) A. With β-BaZn2P2 being previously identified as belonging to the ThCr2Si2 family and with the precedent of structural phase transitions between the α-BaCu2S2 type and the ThCr2Si2 type, the potential for the pattern to be extended to the two different structural forms of BaZn2P2 was explored. Thermal analysis suggests that a first-order phase transition occurs at ∼1123 K, whereby the low-temperature orthorhombic α-phase transforms to a high-temperature tetragonal β-BaZn2P2, the structure of which was also studied and confirmed by single-crystal X-ray diffraction. Preliminary transport properties and band structure calculations indicate that α-BaZn2P2 is a p-type, narrow-gap semiconductor with a direct bandgap of 0.5 eV, which is an order of magnitude lower than the calculated indirect bandgap for the β-BaZn2P2 phase. The Seebeck coefficient, S(T), for the material increases steadily from the room temperature value of 119 μV/K to 184 μV/K at 600 K. The electrical resistivity (ρ) of α-BaZn2P2 is relatively high, on the order of 40 mΩ·cm, and the ρ(T) dependence shows gradual decrease upon heating. Such behavior is comparable to those of the typical semimetals or degenerate semiconductors.