2D-network of inorganic-organic hybrid material built on Keggin type polyoxometallate and amino acid: [L-C2H6NO2]3[(PO4)Mo12O36]·5H2O

A new inorganic-organic hybrid material based on polyoxometallate, [L-C₂H₆NO₂]₃[(PO₄)Mo₁₂O₃₆]·5H₂O, has been successfully synthesized and characterized by single-crystal X-ray analysis, elemental analysis, infrared and ultraviolet spectroscopy, proton nuclear magnetic resonance and differential thermal analysis techniques. The title compound crystallizes in the monoclinic space group, P2₁/c_, with a = 12.4938 (8) Å, b = 19.9326 (12) Å, c = 17.9270 (11) Å, β = 102.129 (1)°, V = 4364.8 (5) Å³, Z = 4 and R₁(wR₂) = 0.0513, 0.0877. The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like (2D/∞ [(PO₄)Mo₁₂O₃₆]³⁻) which forming via weak Van der Waals interactions along the z axis. The characteristic band of the Keggin anion [(PO₄)Mo₁₂O₃₆]³⁻ appears at 210 nm in the UV spectrum. Thermal analysis indicates that the Keggin anion skeleton begins to decompose at 520 °C.     

X-ray Rietveld analysis and Fourier transform infrared spectra of the solid solutions [Eu2−xMx][Sn2−xMx]O7−3x/2 (M = Mg or Zn)

Two series of mixed oxides with formula [Eu_2−xM_x][Sn_2−xM_x]O_7−3x/2 (M = Mg or Zn) have been synthesized. The study by X-ray diffraction and Fourier transform infrared spectroscopy shows that the solids obtained are new non-stoichiometric solid solutions with the pyrochlore type structure. For both series a decrease of the cell parameter is observed when the degree of substitution, x, increases. The structural refinements (X-ray studies) were achieved in the space group Fd-3m, no. 227 (origin at center -3m) by using the Fullprof software. The Rietveld refinements show that the divalent cations M²⁺ (Mg²⁺, Zn²⁺) substitute isomorphically for Eu³⁺ and Sn⁴⁺ ions producing vacancies in the anionic sublattice.     

Synthesis and characterization of polymetalate based photochromic inorganic–organic nanocomposites

A novel reversible photochromic nanocomposite film based on a hybrid inorganic–organic matrix in which heteropolyacid H₃PW₁₂O₄₀ (PWA) was entrapped was prepared. The structure, photochromic behaviors and mechanism of the film were investigated by means of infrared (IR) spectroscopy, UV-Vis absorption spectra and electron spin resonance (ESR). The results showed that heteropolyanion, i.e. PW₁₂O₄₀³⁻ (PW₁₂), maintained a Keggin structure in the film and there was a strong interaction between anion PW₁₂ and cation R–NH₃⁺ (R=link of hybrid composite). The photochromic properties of the composite film originated from the reversible charge transfer between the anions and cations. Under ultraviolet (UV) irradiation, the anion would be reduced via one-electron step with simultaneous oxidation of the cation, accompanied by a color change from colorless to blue. Then the bleaching could occur when the film was in contact with ambient air or O₂ in the dark.     

Photocatalytic degradation of dye naphthol blue black in the presence of zirconia-supported Ti-substituted Keggin-type polyoxometalates

Zirconia-supported Ti-substituted Keggin-type polyoxometalates, Li₅PW₁₁TiO₄₀/ZrO₂ (PW₁₁Ti/ZrO₂) and K₇PW₁₀Ti₂O₄₀/ZrO₂ (PW₁₀Ti₂/ZrO₂), were prepared by incorporating PW₁₁Ti and PW₁₀Ti₂ cluster into a zirconia matrix via a sol-gel technique. These insoluble and readily separable composites were characterized by DR-UV (DR: diffuse reflectance) and FT-IR spectra, MAS NMR, ICP-AES, and nitrogen adsorption determination, indicating that the clusters were chemically attached to the zirconia supports, and the primary Keggin structure remained intact. The photocatalytic activity of the supported PW₁₁Ti and PW₁₀Ti₂ was tested via degradation of an aqueous dye naphthol blue black (NBB). It indicated that the dye NBB can be degraded totally and mineralized into the inorganic products such as CO₂, NH₄⁺, NO₃⁻, and SO₄²⁻ ions by irradiating the composite slurry in the near-UV area. Dropped of PW₁₁Ti or PW₁₀Ti₂ cluster from the zirconia matrix into the reaction system was hardly observed during the photocatalytic tests, attributed to the strong chemical interactions between the Keggin units and the zirconia support.     

Comparative study of photoinduced wettability conversion between [PW12O40]/brookite and [SiW12O40]/brookite hybrid films

Two tungsten-based Keggin-type heteropolyacids (PW₁₂: ([PW₁₂O₄₀]³⁻) and SiW₁₂: ([SiW₁₂O₄₀]⁴⁻)) were hybridized with brookite-type TiO₂. Then photocatalytic decomposition activity, photoinduced hydrophilicity, and sustainability of the hydrophilicity in the dark were evaluated using gaseous 2-propanol (IPA) decomposition and sessile drop method. The obtained films were transparent in the visible wavelength range. Both hybrid films exhibited higher photocatalytic decomposition activity and had higher photoinduced hydrophilicizing rates than pure brookite films under UV illumination. The PW₁₂/TiO₂ film exhibited better photocatalytic performance than the SiW₁₂/TiO₂ film did. Atmosphere dependence, XPS analysis, and electrochemical experiments indicated the cause of these two films' different levels of sustainability of hydrophilicity to be differences in their electron storage capability. Results show that the electron scavenger capability and reoxidation efficiency of the heteropolyacid are key factors affecting the overall performance of wettability conversion of this hybrid film system before and after UV illumination.     

Electrochemical behaviour of self-assembly multilayer films based on iron-substituted α-Keggin polyoxotungstates

Ultrathin multilayer films containing metal-substituted polyoxometalates, [PW₁₁Fe^III(H₂O)O₃₉]⁴⁻ (PW₁₁Fe) or [SiW₁₁Fe^III(H₂O)O₃₉]⁵⁻ (SiW₁₁Fe), and poly(ethylenimine) (PEI) were prepared by the electrostatic layer-by-layer self-assembly method on a glassy carbon electrode. The multilayer films were characterized by cyclic voltammetry and scanning electron microscopy and UV-Vis absorption spectroscopy on a quartz slide was used to monitor film growth. Cyclic voltammetry indicates that the electrochemical properties of the polyoxometalates are completely maintained in the multilayer films, and the influence of scan rate on the voltammetric features showed that the first tungsten reduction process for immobilized PW₁₁Fe and SiW₁₁Fe is a surface-confined process. Studies with [Fe(CN₆)]^3−/4− as electrochemical probe showed that their permeability depends on the thickness of the multilayer films, if the outermost layer is negatively charged. Additionally, the (PEI/SiW₁₁Fe)_n multilayer films showed electrocatalytic properties towards nitrite reduction.     

Studying trivalent/bivalent metal ion doped TiO2 as p-TiO2 in bipolar heterojunction devices

Trivalent/bivalent metal ions doped TiO₂ thin films (M_xTi_1−xO₂, M = Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺, Mn²⁺ and x = 0.01, 0.05, 0.1, 0.15, 0.2) were deposited on Indium–tin oxide (ITO) coated glass substrates by spin coating technique. X-ray photoelectron spectroscopy (XPS) showed Ti⁴⁺ oxidation state of the Ti2p band in the doped p-TiO₂. The homogenous M_xTi_1−xO₂ was used to support n-ZnO thin films with thickness ∼40–80 nm and vertically aligned n-ZnO nanorods (NR) with length ∼300 nm and 1.5 μm. Current (I)–voltage (V) characteristics for the Ag/n-ZnO/M_xTi_1−xO₂/ITO/glass assembly showed rectifying behavior with small turn-on voltages (V₀) < 1 V. The ideality factor (η) and the resistances in both forward and reverse bias were calculated. The temperature dependence performance of these bipolar devices was performed and variation of the parameters with temperature was studied.     

Preparation,characterization and photocatalytic applications of amine-functionalized mesoporous silica impregnated with transition-metal-monosubstituted polyoxometalates

Amine-functionalized mesoporous silica materials impregnated with transition-metal-monosubstituted polyoxometalates, K₅[M(H₂O)PW₁₁O₃₉]–(EtO)₃SiCH₂CH₂CH₂NH₂–MCM-48 (M = Co/Ni), were prepared by coordination of nickel/cobalt centers in the clusters with the amine surface groups in amine-functionalized mesoporous silica supports. The materials obtained were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis-DR), infrared (IR) spectra, magic-angle spinning ³¹P MAS NMR, transmission electron microscopy (TEM) and nitrogen adsorption measurements, indicating that the primary Keggin structures remained intact in as-prepared composites, and the composites possessed mesoporous structures. The composites exhibited UV-photocatalytic activity to degrade dye rhodamine B (RB), and the pesticides including hexachlorobenzene (HCB) and methylparathion (MPT). Leakage of K₅[M(H₂O)PW₁₁O₃₉] from the support was hardly observed during the photocatalytic tests, attributed to strong coordination interactions between the Keggin units and the amine-functionalized silica surface.     

Luminescence characterization of (Ca1−xSrx)(S1−ySey):Eu,M (M = Sc and Y) for high color rendering white LED

The highly efficient red phosphors (Ca_1−xSr_x)(S_1−ySe_y):Eu²⁺,M³⁺ (M = Sc and Y) were prepared, starting from CaCO₃, SrCO₃, Eu₂O₃, Sc₂O₃, Y₂O₃, S, and SeO₂ with a flux, by a conventional solid-state reaction. The optimized red phosphors converted 11.8% (Sc³⁺) and 11.7% (Y³⁺) of the absorbed blue light into luminescence. These quantum values are much higher than Q = 3.0% of CaS:Eu²⁺. For the fabrication of light-emitting diodes (LEDs), the prepared phosphors were coated with MgO from non-aqueous solution to overcome their weakness against moisture. White LEDs were fabricated by pasting the prepared red phosphors and the yellow YAG:Ce³⁺ phosphor on an InGaN blue chip (λ_ems = 446.5 nm). The incorporation of the red phosphor to the YAG:Ce³⁺ phosphor resulted in an improved color rendering index (Ra) from 70 to 80.     

Enhanced multiferroic properties and tunable magnetic behavior in multiferroic BiFeO3-Bi0.5Na0.5TiO3 solid solutions

A series of multiferroic (1−x)BiFeO₃−x(Bi_0.5Na_0.5)TiO₃ (BF-BNT) (x = 0 − 0.6) solid solution ceramics were prepared by a sol-gel method. The XRD results show that increasing BNT content induce a gradual phase transformation from rhombohedral to pseudocubic structure near x = 0.4. Compared with pure BiFeO₃, superior multiferroic properties are obtained for x = 0.3 with remnant polarization P_r = 1.49 μC/cm² and saturated magnetization M_s = 0.51 emu/g. Importantly, the paramagnetic (PM) to ferromagnetic (FM) transition is observed for the solutions, and the Curie temperature (T_C) can be tuned by varying the content of BNT. This observed FM ordering is discussed in terms of the possible existence of the long-range superexchange interaction of Fe³⁺-O-Ti-O-Fe³⁺ in the chemically ordered regions.     

Fabrication of a 12-tungstophosphate and cadmium oxide composite film and its properties

A multilayer composite film of the 12-tungstophosphate H₃[PW₁₂O₄₀]³⁻ (PW₁₂) and cadmium oxide nanoparticles (CdO) was fabricated on quartz and silicon by the layer-by-layer (LBL) self-assembly method. The film was characterized by UV–vis spectroscopy, atomic force microscopy (AFM) and luminescence spectra. The proposed composite film exhibits higher photocatalytic activity toward methyl orange (MO) solution at pH 3.5, compared to single PW₁₂ and CdO films. The degradation rate was affected by initial concentration of PW₁₂, pH value of MO solution, inorganic ions concentration and type in MO solution. In addition, the composite film displays luminescent property and reversible electrochromic property with fast response time.     

Synthesis, structure refinement and characterisation of a new oxyphosphate Mg0.50TiO(PO4)

A new titanium oxyphosphate Mg_0.50TiO(PO₄) has been synthesized and characterized by several physical techniques: X-ray diffraction, ³¹P MAS-NMR, Raman diffusion, infrared absorption and diffuse reflectance spectroscopy. It crystallizes in the monoclinic system with unit cell parameters: a = 7.367(9), b = 7.385(8), c = 7.373(9) Å, β = 120.23(1), with the space group P2₁/c (no. 14), Z = 4. The crystal structure has been refined by the Rietveld method using X-ray powder diffraction. The conventional R indices obtained are R_wp = 0.138, R_p = 0.096 and R_B = 0.0459. The structure of Mg_0.50TiO(PO₄) consists of infinite chains of corner-shared [TiO₆] octahedra parallel to the c-axis, crosslinked by corner-shared [PO₄] tetrahedra. These infinite chains have alternating short (1.74 Å) and long (2.26 Å) TiO bonds and are similar to those found in titanium oxyphosphate M^II_0.50TiO(PO₄) (M²⁺ = Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺). The magnesium atom is located in an antiprism between two [TiO₆] octahedra. ³¹P MAS NMR showed only a single ³¹P resonance line, in a good agreement with the crystal structure. Raman and IR spectra show strong bands respectively at 765 and 815 cm⁻¹, attributed to the vibration of TiOTiO bonds in the infinite chains. The gap due to the Oxygen-Titanium(IV) charge transfer is 3.37 eV.     

Nd2[MoC2] and RE2[WC2], RE=Ce, Pr, Nd: New carbometalates with Pr2[MoC2] structure type

Four new ternary rare-earth-metal carbometalates, Nd₂[MoC₂] and RE₂[WC₂] with RE=Ce, Pr, Nd, have been synthesized by argon arc melting and subsequent heat treatment at 1170 K for 30 days. They crystallize with the Pr₂[MoC₂] structure type with isolated C⁴⁻ species and are typical carbometalates with (i) low metal-to-carbon ratio, (ii) tetrahedral coordination of the transition metals (T) by carbon, and (iii) a polyanionic network . According to resistivity measurements the compounds are bad metals. Volume chemistry and magnetic susceptibility measurements indicate Pr³⁺, Nd³⁺, and Ce⁴⁺ species, respectively. In the latter case, the additional electron is not transferred to the polyanionic network, instead it mainly populates the Ce partial structure.     

Room temperature ferromagnetism in Zn0.99La0.01O and pure ZnO nanoparticles

Room temperature ferromagnetism (RTFM) was observed in both La-doped and pure ZnO nanoparticles synthesized by the sol–gel method. RTFM is intrinsic according to the results of X-ray diffraction and X-ray photoelectron spectroscopy. The saturation magnetization (M_S), the remnant magnetization at zero field and coercive field are 5 × 10⁻³, 7 × 10⁻⁴ emu g⁻¹, 100 Oe for Zn_0.99La_0.01O nanoparticles and 1.5 × 10⁻⁴, 1 × 10⁻⁵ emu g⁻¹, 50 Oe for pure ZnO nanoparticles, respectively. The magnetization is enhanced greatly by doping of La. Furthermore, the M_S of Zn_0.99La_0.01O nanoparticles decreases from 0.005 to 0.001 emu g⁻¹ as the annealing temperature increases from 500 to 700 °C. The doping of La introduces more oxygen vacancies into ZnO. The decrease of annealing temperature also produces more oxygen vacancies in La-doped ZnO. These results indicate that the origin of the RTFM is related to oxygen vacancies.     

Luminescent properties of Sr2P2O7:Eu,Mn phosphor under near UV excitation

The phosphors in the system Sr_2−x−yP₂O₇:xEu²⁺,yMn²⁺ were synthesized by solid-state reactions and their photoluminescence properties were investigated. These phosphors have strong absorption in the near UV region, which is suitable for excitation of ultraviolet light emitting diodes (UVLEDs). The orange-reddish emission of Mn²⁺ in these phosphors can be used as a red component in the tri-color system and may be enhanced by adjusting the Mn²⁺/Eu²⁺ ratio. The energy transfer from Eu²⁺ to Mn²⁺ is observed with a transfer efficiency of ∼0.45 and a critical distance of ∼10 Å. The results reveal that Sr_2−x−yP₂O₇:xEu²⁺,yMn²⁺ phosphors could be used in white light UVLEDs.     

Anion-exchange properties of nickel–aluminum layered double hydroxide prepared by liquid phase deposition

The optimum coordination structure of Ni–fluoro complexes for the preparation of Ni–Al LDH by LPD process and the diverse anion-exchange properties of as-deposited Ni–Al on α-alumina powder were quantitatively evaluated for the industrial application of new positive material for alkali secondary batteries. The [NiF_6−x−y(NH₃)_x(OH⁻)_y]ⁿ⁺ was more suitable than [NiF₆]⁴⁻ as the precursor of the deposition of Ni–Al LDH in the LPD reaction, and the improved LPD reaction achieved the synthesis of high purity and high crystallinity Ni–Al LDH. All anion-exchanged Ni–Al LDHs for OH⁻–, Cl⁻–, SO₄²⁻–, and CH₃COO⁻–forms kept the high crystallinity and showed the enlargement of interlayer distances. The tilting angle of the intercalated CH₃COO⁻ anions was about 15°. Anion-exchange capacity remained constant at a minimum of 0.8 meq g⁻¹ in pH >10, increased as pH decreased, and reached a maximum of 8 meq g⁻¹ at pH 2. Anion-exchange of OH⁻–form of Ni–Al LDH was accelerated by the neutralization of hydroxide ions in interlayers, in addition, the anion-exchange capacity and the crystallinity of Ni–Al LDH could be controlled by the amount of doped aluminum ions.     

One-step synthesis,characterization and oxidative desulfurization of 12-tungstophosphoric heteropolyanions immobilized on amino functionalized SBA-15

Keggin-type 12-tungstophosphoric [PW₁₂O₄₀]^3? heteropolyanions were successfully immobilized onto mesoporous material surface of SBA-15 functionalized using the (3-aminopropyl)triethoxysilane (APTES) synthesized by one-pot co-condensation method, also called one-step synthesis. The synthesized PW^?-NH₃⁺-SBA-15 catalyst was characterized by XRD, N₂ adsorption–desorption, FT-IR, TGA, SEM, TEM, EDS, XPS methods. The results indicated that ordered hexagonal mesostructure for SBA-15 support was still maintained after being functionalized with amine groups, while the specific surface area of SBA-15 was decreased. The active species of phosphotungstic acid H₃PW₁₂O₄₀ (HPW) retained its Keggin structure of the heteropolyanions on the amine-modified SBA-15. The PW^?–⁺H₃N–SBA–15 catalyst exhibited a high catalytic activity for oxidative desulfurization process of sulfur-containing model fuel. The dibenzothiophene (DBT) conversion of almost 100% was achieved with reaction conditions of 40?mg of catalyst dosage, 2?mL of hydrogen peroxide, 90?°C of reaction temperature, and 120?min of reaction time.     

Structural aspects of adamantine like multinary chalcogenides

The present state of knowledge of structure, phase relations and metal ordering in 2(ZnX)_x(CuBX₂)_1 − x (B = Ga, In and X = S, Se, Te) and Cu₂Zn_xFe_1 − xSnS₄ multinary compounds is discussed. The chemical disorder process in 2(ZnX)_x(CuBX₂)_1 − x alloys leads to a phase separation, i.e. in a certain composition range (2-phase field) two phases, tetragonal domains and a cubic matrix, coexist. Its width depends on the three-valent cation only and is independent from the size of anion. In the subsolidus region of the 2(ZnX)_x(CuBX₂)_1 − x system the stability range of tetragonal mixed crystals as well as the miscibility gap is decreasing, the stability range of cubic mixed crystals is increasing. The process of structural disorder in 2(ZnX)_x(CuBX₂)_1 − x as well as Cu₂Fe_1 − xZn_xSnS₄ alloys is connected to the cation substructure. In tetragonal 2(ZnX)_x(CuInX₂)_1 − x alloys a non-random Zn distribution on the both cation positions of the chalcopyrite-type structure was revealed, whereas a random distribution of Zn and Cu on two different sites of the kesterite type structure was obtained in Cu₂ZnSnS₄ in contradiction to literature. The crossover from stannite (x = 0) to kesterite (x = 1) in Cu₂Fe_1 − xZn_xSnS₄ is considered as a three-stage process of cation restructure involving Cu⁺, Zn²⁺ and Fe²⁺, whereas Sn⁴⁺ does not take part in this process. In tetragonal 2(ZnX)_x(CuInX₂)_1 − x alloys the anion displacement is decreasing with increasing ZnX content in CuInX₂ indicating a decreasing tetragonal distortion. Here the disorder process in the cation substructure and the displacement process in the anion substructure are coupled.     

Preparation and conductivity of solid high-proton conductor silica gel containing 80 wt.% decatungstodivanadogermanic acid

The silica gel containing decatungstodivanadogermanic heteropoly acid was prepared by means of the sol-gel method. Infrared spectrum and XRD pattern revealed that the Keggin structure characteristic of GeW₁₀V₂O₄₀⁶⁻ anion was present in the silica gel skeleton. The regularity of the change of the characteristic peaks in the infrared spectrum was investigated. The silica gel exhibited considerably high-proton conductivity. The proton conductivity of the gel containing 80 wt.% decatungstodivanadogermanic acid is 5.37 × 10^− 2 S cm^− 1 at room temperature (18 °C).     

Hydrothermal synthesis, crystal structure and spectroscopic and magnetic properties of (C2H10N2)[Mn2.09Co0.91(HPO3)4]

(C₂H₁₀N₂)[Mn_2.09Co_0.91(HPO₃)₄] has been synthesized using mild hydrothermal conditions under autogeneous pressure. The compound crystallizes in the triclinic P-1 space group. The unit-cell parameters are a = 5.4061(8), b = 5.4150(7), c = 14.136(2) Å, α = 80.84(1), β = 85.41(1), γ = 60.00(1) and Z = 1. The compound shows a layered structure constructed from M₃O₁₂ trimer units linked thorough the (HPO₃)²⁻ phosphite oxoanions with the ethylenediammonium cations located between the sheets compensating the anionic charge of the inorganic framework. The IR and Raman spectra confirm the presence of the ethylenediammonium cation and phosphite anion. The diffuse reflectance spectrum is in accordance with the presence of Co(II) and Mn(II) high spin cations in slightly distorted octahedral symmetry. The calculated Dq and Racah parameters for the Co(II) cations are Dq = 710, B = 870 and C = 4100 cm⁻¹. The magnetic measurements indicate the existence of antiferromagnetic interactions as the major interactions. Hysteresis observed at low temperature indicates a weak ferromagnetic component, due to a non-cancellation of spins, with coercitive field of 900 G and magnetization of 700 emu/mol.