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At least 109 records · Page 6

Morphology control of open-framework zinc phosphate Zn{sub 4}(H{sub 3}O)(NH{sub 4}){sub 3}(PO{sub 4}){sub 4} via microwave-assisted technique

Open-framework zinc phosphates were synthesized by microwave-assisted technique, and it was shown that the morphology of as-prepared materials could be easily tailored by changing synthesis temperature, reaction time and pH value. During the synthesis, when the reaction temperature increases from 130 °C to 220 °C, the products transformed from hexagonal prisms to polyhedron along with the disappearance of the hexagonal prisms vertical plane. Simultaneously, both the reaction time and pH value could promote the nucleation and growth of crystal particles. More interestingly, the target products with different morphologies could be obtained by varying the usage of NaOH or NH{sub 3}·H{sub 2}O at 130 °C during the microwave synthesis process. - Graphical abstract: Zinc phosphates with variable morphologies can be obtained by simply tuning the microwave-heating temperatures. Display Omitted - Highlights: • Synthesis of open-framework Zn{sub 4} (H{sub 3}O) (NH{sub 4}){sub 3}(PO{sub 4}){sub 4} compounds employing microwave technique. • Dependence of morphology on the reaction conditions. • Morphology transformation from hexagonal prisms to polyhedron was observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and characterization of polymorphs of photoluminescent Eu(III)-(2,5-furandicarboxylic acid, oxalic acid) MOFs

A novel metal organic framework (MOF) formulated as [Eu(H{sub 2}O){sub 2}(fdc)(ox){sub 0.5}·(H{sub 2}O)]{sub n} (1, fdc{sup 2−}=2,5-furandicarboxylate, ox{sup 2−}=oxalate), was hydrothermally synthesized via in situ ox{sup 2−} generation from the partial decomposition of the fdc{sup 2−} ligand. This material crystallizes in the monoclinic space group C2/c, unit cell parameters of 1: a=16.7570(10), b=10.5708(7), c=13.5348(14) Å, β=116.917(2)° (Z=8), and exhibits a three-dimensional (3D)-porous framework, with guest water molecules residing in the channel linking all other ligands (H{sub 2}O, ox{sup 2−}and fdc{sup 2−}) via hydrogen bonding interactions. Compound 2 is a polymorph of 1 crystallizing in monoclinic P21/c space group. The photoluminescence properties of 1 and 2 were studied at room temperature. The spectra show the typical Eu{sup 3+} red emission and the differences observed reflects the slightly different structures of these polymorphs. - Graphical abstract: Exploring metal organic framework polymorphism in the system Eu(H{sub 2}O){sub 2}(fdc)(ox){sub 0.5}·(H{sub 2}O)]{sub n} (fdc{sup 2−}=2,5-furandicarboxylate, ox{sup 2−}=oxalate) for tuning light emission. Display Omitted - Highlights: • Synthesis of Eu(III)-(2,5-furandicarboxylic acid, oxalic acid) MOF polymorphs. • Detailed single-crystal study of polymorphs including hydrogen-bonding networks. • Photoluminescence spectroscopy show subtle differences light emission properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal structure, magnetism and transport properties of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10}

Single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10} were obtained from a process in which a polycrystalline sample of CeRu{sub 2}Al{sub 2}B was annealed in an excess of a Ni–In flux. The initial phase, CeRu{sub 2}Al{sub 2}B, does not recrystallize, instead, crystals of a new phase, Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10}, could be isolated once the flux was removed. The title compound crystallizes in the tetragonal space group P4/nmm (No. 129) with a=1139.02(8), c=801.68(6) pm (c/a=0.70) in the Nd{sub 3}Ni{sub 29}Si{sub 4}B{sub 10} structure type. Electrical resistivity measurements reveal metallic behavior with a minimum of 700 µΩ cm and a small residual resistivity ratio of RRR=1.4 indicating a large amount of disorder scattering. The cerium atoms are either in the 4+ or an intermediate valence state with a valence fluctuation temperature far above room temperature. - Graphical abstract: Single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}A{sub l4.1}B{sub 10} were obtained using a process in which a polycrystalline sample of CeRu{sub 2}Al{sub 2}B was annealed in an excess of a Ni–In flux. Electrical resistivity measurements reveal metallic behavior with a minimum of 700 μΩ cm and a small residual resistivity ratio of RRR=1.4 indicating a large amount of disorder scattering. The cerium atoms are either in the 4+ or an intermediate valence state with a valence fluctuation temperature far above room temperature. Display Omitted - Highlights: • Flux synthesis of high quality single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10} is presented along with the crystal structure, magnetic and transport properties. • The compound is isostructural to Nd{sub 3}Ni{sub 29}Si{sub 4}B{sub 10} but is first of this structure type showing mixed occupancies of d-elements. • This is an intermetallic phase with Ce in either the 4+ or an intermediate valence state. • The fact that this structure with mixed occupied transition metal sites exists suggests that more compounds of this type should be accessible and the physical properties tuned.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lifting the geometric frustration through a monoclinic distortion in “114” YBaFe{sub 4}O{sub 7.0}: Magnetism and transport

The possibility to lift the geometric frustration in the “114” stoichiomeric tetragonal oxide YBaFe{sub 4}O{sub 7.0} by decreasing the temperature has been investigated using neutron and synchrotron powder diffraction techniques. Besides the structural transition from tetragonal to monoclinic symmetry that appears at T{sub S}=180 K, a magnetic transition is observed below T{sub N}=95 K. The latter corresponds to a lifting of the 3D geometric frustration toward an antiferromagnetic long range ordering, never observed to date in a cubic based “114’” oxide. The magnetic structure, characterized by the propagation vector k{sub 1}=(0,0,½), shows that one iron Fe2 exhibits a larger magnetic moment than the three others, suggesting a possible charge ordering according to the formula YBaFe{sup 3+}Fe{sub 3}{sup 2+}O{sub 7.0}. The magnetic M(T) and χ′(T) curves, in agreement with neutron data, confirm the structural and magnetic transitions and evidence the coexistence of residual magnetic frustration. Moreover, the transport measurements show a resistive transition from a thermally activated conduction mechanism to a variable range hopping mechanism at T{sub S}=180 K, with a significant increase of the dependence of the resistivity vs. temperature. Mössbauer spectroscopy clearly evidences a change in the electronic configuration of the iron framework at the structural transition as well as coexistence of several oxidation states. The role of barium underbonding in these transitions is discussed. - Graphical abstract: Atomic displacements at the tetragonal-monoclinic transition in YBaFe{sub 4}O{sub 7}. Display Omitted - Highlights: • The structural and magnetic phase transitions of YBaFe{sub 4}O{sub 7} were studied below room temperature. • The tetragonal to monoclinic transition, characterized by NPD and SXRD, was studied using mode crystallography approach. • Monoclinic distortion allows the lifting of the geometrical frustration on the iron sublattice, leading to AF order at T=95 K.

36 MATERIALS SCIENCE↗

Lithium transition metal fluorophosphates (Li{sub 2}CoPO{sub 4}F and Li{sub 2}NiPO{sub 4}F) as cathode materials for lithium ion battery from atomistic simulation

Lithium transition metal fluorophosphates (Li{sub 2}MPO{sub 4}F, M: Co and Ni) have been investigated from atomistic simulation. In order to predict the characteristics of these materials as cathode materials for lithium ion batteries, structural property, defect chemistry, and Li{sup +} ion transportation property are characterized. The core–shell model with empirical force fields is employed to reproduce the unit-cell parameters of crystal structure, which are in good agreement with the experimental data. In addition, the formation energies of intrinsic defects (Frenkel and antisite) are determined by energetics calculation. From migration energy calculations, it is found that these flurophosphates have a 3D Li{sup +} ion diffusion network forecasting good Li{sup +} ion conducting performances. Accordingly, we expect that this study provides an atomic scale insight as cathode materials for lithium ion batteries. - Graphical abstract: Lithium transition metal fluorophosphates (Li{sub 2}CoPO{sub 4}F and Li{sub 2}NiPO{sub 4}F). Display Omitted - Highlights: • Lithium transition metal fluorophosphates (Li{sub 2}MPO{sub 4}F, M: Co and Ni) are investigated from classical atomistic simulation. • The unit-cell parameters from experimental studies are reproduced by the core–shell model. • Li{sup +} ion conducting Li{sub 2}MPO{sub 4}F has a 3D Li{sup +} ion diffusion network. • It is predicted that Li/Co or Li/Ni antisite defects are well-formed at a substantial concentration level.

36 MATERIALS SCIENCE↗

Influence of surface and finite size effects on the structural and magnetic properties of nanocrystalline lanthanum strontium perovskite manganites

Syntheses of nanocrystalline perovskite phases of the general formula La{sub 1−x}Sr{sub x}MnO{sub 3+δ} were carried out employing sol–gel technique followed by thermal treatment at 700–900 °C under oxygen flow. The prepared samples exhibit a rhombohedral structure with space group R3{sup ¯}c in the whole investigated range of composition 0.20≤x≤0.45. The studies were aimed at the chemical composition including oxygen stoichiometry and extrinsic properties, i.e. size of the particles, both influencing the resulting structural and magnetic properties. The oxygen stoichiometry was determined by chemical analysis revealing oxygen excess in most of the studied phases. The excess was particularly high for the samples with the smallest crystallites (12–28 nm) while comparative bulk materials showed moderate non-stoichiometry. These differences are tentatively attributed to the surface effects in view of the volume fraction occupied by the upper layer whose atomic composition does not comply with the ideal bulk stoichiometry. - Graphical abstract: Evolution of the particle size with annealing temperature in the nanocrystalline La{sub 0.70}Sr{sub 0.30}MnO{sub 3+δ} phase. Display Omitted - Highlights: • The magnetic behaviour of nanocrystalline La{sub 1−x}Sr{sub x}MnO{sub 3+δ} phases was analyzed on the basis of their crystal structure, chemical composition and size of the particles. • Their Curie temperature and magnetization are markedly affected by finite size and surface effects. • The oxygen excess observed in the La{sub 1−x}Sr{sub x}MnO{sub 3+δ} nanoparticles might be generated by the surface layer with deviated oxygen stoichiometry.

36 MATERIALS SCIENCE↗

Two unusual 12-connected metal–organic coordination polymers with fcu net

Two new three-dimensional 12-connected metal–organic coordination polymers, [Zn{sub 2}(bptc)(H{sub 2}O)]·C{sub 2}H{sub 5}OH·H{sub 2}O (1) and [Cd{sub 4}(bptc){sub 2}(bbi)(H{sub 2}O)]·H{sub 2}O (2) (H4bptc=biphenyl-2,5,2′,5′-tetracarboxylic acid, bbi=1,1′-(1,4-butanediyl)bis(imidazole)), have been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction analyses. All compounds are also characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray powder diffraction (XRD). Topological analysis indicates that both 1 and 2 are 12-connected frameworks with fcu topology, which are based on cuboid cage and rob-like (Cd3) subunit as 12-connected nodes, respectively. Furthermore, the luminescence properties of the two compounds were discussed in detail. - Graphical abstract: Two new compounds with unusual 12-connected fcu topology display intriguing structural feature, as well as luminescence property. Display Omitted - Highlights: • Two new 3D metal–organic coordination polymers based on biphenyl-2,5,2′,5′-tetracarboxylic acid ligand have been synthesized. • Two compounds exhibit rare 12-connected fcu topology. • Photoluminescent property at room temperature has been investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uniform Cu{sub 2}Cl(OH){sub 3} hierarchical microspheres: A novel adsorbent for methylene blue adsorptive removal from aqueous solution

Using the solution phase method without any surfactants or templates, the hierarchical of Cu{sub 2}Cl(OH){sub 3} microspheres were synthesized by freeze drying. The size and surface area of the microspheres are ca. 1–2 µm and 76.61 m{sup 2} g{sup −1}, respectively. A possible formation mechanism is presented based on the experimental results. Methylene blue was chosen to investigate the adsorption capacity of the as-prepared adsorbent. The effects of various experimental parameters, such as pH, initial dye concentration, and contact time were investigated. The results showed that the dye removal increased with the increasing in the initial concentration of the dye and also increased in the amount of microspheres used and initial pH. Adsorption data fitted well with the Freundlich adsorption isotherm. The thermodynamic analysis presented the exothermic, spontaneous and more ordered arrangement process. The microspheres could be employed effective for removal of dyes from aqueous solution. - Graphical abstract: The single-crystalline hierarchical Cu{sub 2}Cl(OH){sub 3} spheres can be prepared for the first time by using a template-free process through freeze-drying. Meanwhile, the hierarchical spheres exhibited high adsorption capacity to methylene blue. Display Omitted - Highlights: • Cu{sub 2}Cl(OH){sub 3} microspheres were successfully synthesized through a freeze drying process. • A possible formation mechanism of hierarchical microspheres was presented. • The Cu{sub 2}Cl(OH){sub 3} microspheres have high methylene blue adsorption capacity. • Methylene blue adsorption is a spontaneous and exothermic process. • The adsorption mechanism of microspheres onto dye was proposed in detail.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and reversible hydration behavior of the thiosulfate intercalated layered double hydroxide of Zn and Al

The thiosulfate-intercalated layered double hydroxide of Zn and Al undergoes reversible hydration with a variation in the relative humidity of the ambient. The hydrated and dehydrated phases, which represent the end members of the hydration cycle, both adopt the structure of the 3R{sub 1} polytype. In the intermediate range of relative humidity values (40–60%), the hydrated and dehydrated phases coexist. The end members of the hydration cycle adopt the structure of the same polytype, and vary only in their basal spacings. This points to the possibility that all the intermediate phases have a kinetic origin. - Graphical abstract: Basal spacing evolution of the thiosulfate ion intercalated [Zn–Al] LDH during one complete hydration–dehydration cycle as a function of relative humidity. Display Omitted - Highlights: • Thiosulfate intercalated [Zn–Al] LDHs were synthesized by co-precipitation. • The LDH exhibits reversible hydration with variation in humidity. • Both the end members of the hydration cycle adopt the same polytype structure. • The interstratified intermediates observed are kinetic in origin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bismuth(III) dialkyldithiophosphates: Facile single source precursors for the preparation of bismuth sulfide nanorods and bismuth phosphate thin films

Two different phase pure materials (Bi{sub 2}S{sub 3} and Bi{sub 2}P{sub 4}O{sub 13}) have been prepared under different conditions using the same single source precursors. Solvothermal decomposition of the complexes, Bi(S{sub 2}P(OR){sub 2}){sub 3} [where, R=Methyl (Me) (1), Ethyl (Et) (2), n-Propyl (Pr{sup n}) (3) and iso-Propyl (Pr{sup i}) (4)] in ethylene glycol gave orthorhombic bismuth sulfide nanorods, whereas aerosol assisted chemical vapor deposition (AACVD) of the same precursors deposited monoclinic bismuth tetraphosphate (Bi{sub 2}P{sub 4}O{sub 13}) thin films on glass substrates. Surface study of the thin films using SEM illustrated the formation of variety of nanoscale morphologies (spherical-, wire-, pendent-, doughnut- and flower-like) at different temperatures. AFM studies were carried out to evaluate quality of the films in terms of uniformity and roughness. Thin films of average roughness as low as 1.4 nm were deposited using these precursors. Photoluminescence studies of Bi{sub 2}P{sub 4}O{sub 13} thin films were also carried out. - Graphical abstract: Solvothermal decomposition of bismuth(III) dialkyldithiophosphates in ethylene glycol gave Bi{sub 2}S{sub 3} nanoparticles, whereas aerosol assisted chemical vapor deposition of these single source precursors deposited Bi{sub 2}P{sub 4}O{sub 13} thin films. Display Omitted - Highlights: • Preparation of phase pure orthorhombic Bi{sub 2}S{sub 3} nanorods and monoclinic Bi{sub 2}P{sub 4}O{sub 13} thin films. • Use of single source precursors for deposition of bismuth phosphate thin films. • Use of solvothermal decomposition and AACVD methods. • Morphology controlled synthesis of Bi{sub 2}P{sub 4}O{sub 13} thin films. • Bi{sub 2}S{sub 3} nanorods and Bi{sub 2}P{sub 4}O{sub 13} thin films using same single source precursors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, single-crystal structure, and optical absorption of Rb{sub 2}Th{sub 7}Se{sub 15}

The compound Rb{sub 2}Th{sub 7}Se{sub 15} has been synthesized by the solid-state reaction at 1273 K of Th, Rb{sub 2}Se{sub 3}, Se, and Ge, and its structure has been determined by single-crystal X-ray diffraction methods. Red crystals of Rb{sub 2}Th{sub 7}Se{sub 15} crystallize at 100(2) K with four formula units in a new structure type in the monoclinic space group C{sub 2h}{sup 5}−P2{sub 1}/c. The structure is three-dimensional and comprises Rb and Th atoms coordinated by Se atoms to form nine-, eight-, and seven-coordinate polyhedra. Infinite channels that contain Rb atoms are present. Crystals of Rb{sub 2}Th{sub 7}Se{sub 15} are red in color; an indirect band gap of 1.83 eV was derived from single-crystal optical measurements. - Graphical abstract: Structure of Rb{sub 2}Th{sub 7}Se{sub 15} viewed down the b-axis. Display Omitted - Highlights: • The new compound Rb{sub 2}Th{sub 7}Se{sub 15} was synthesized at 1273 K from the elements in the presence of Ge. • The structures of the two known Rb/Th/Se compounds, RbTh{sub 2}Se{sub 6} and Rb{sub 2}Th{sub 7}Se{sub 15}, differ markedly. • Optical measurements establish the band gap of Rb{sub 2}Th{sub 7}Se{sub 15} to be indirect with a value of 1.83 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Study of Mg{sub x}Cd{sub 1−x}O applying density functional theory: Stability, structural phase transition and electronic properties

Stability of B1 and B2 phases of Mg{sub x}Cd{sub 1−x}O is studied by calculating the formation energy within the framework of density functional theory applying the crystalline-orbital program package. Structural and electronic properties of the two polymorphs are reported for x=0.25, 0.50 and 0.75. The equilibrium lattice constants and bulk moduli are computed. Enthalpy calculations show pressure induced B1→B2 phase transitions at 92 GPa, 138 GPa and 212 GPa, respectively, for Mg{sub 0.25}Cd{sub 0.75}O, Mg{sub 0.50}Cd{sub 0.50}O and Mg{sub 0.75}Cd{sub 0.25}O compositions. Formation energy of ternary oxides in the B1 phase is negative with respect to mixing of B2-MgO with B1-CdO. Mixing B1-MgO with B2-CdO also leads to negative formation energy in Cd rich B1 phase ternary oxides (0≤x≤0.5). Band structure calculations predict direct band gaps in the B1 phase and indirect band gaps in the B2 phase ternary oxides. Mulliken population analysis is performed for the two polymorphs to study the charge transfer. - Graphical abstract: Diagram reveals trends in formation energy while mixing B2-MgO with B1-CdO to form B1-Mg{sub x}Cd{sub 1−x}O. Formation energies obtained from mixing isostructural and nonisostructural components are also shown. Display Omitted - Highlights: • Lattice constants and bulk moduli are computed for Mg{sub 0.25}Cd{sub 0.75}O, Mg{sub 0.50}Cd{sub 0.50}O and Mg{sub 0.75}Cd{sub 0.25}O compositions. • Enthalpy calculations signify pressure induced B1→B2 phase transitions at 92 GPa, 138 GPa and 212 GPa, respectively, in Mg{sub 0.25}Cd{sub 0.75}O, Mg{sub 0.50}Cd{sub 0.50}O and Mg{sub 0.75}Cd{sub 0.25}O. • Band structure calculations predict direct band gaps in the B1 phase ternary oxides. • In the B2 phase ternary oxides band structure calculations show valence band maximum along the Γ–X direction and the conduction band minimum at the Γ point of symmetry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Luminescent nanocrystals in the rare-earth niobate–zirconia system formed via hydrothermal method

Luminescent nanocrystals based on the rare-earth niobates (Ln{sub 3}NbO{sub 7}, Ln=Y, Eu) and zirconia (ZrO{sub 2}) that were composed of 50 mol% Ln{sub 3}NbO{sub 7} and 50 mol% ZrO{sub 2}, were hydrothermally formed as cubic phase under weakly basic conditions at 240 °C. The lattice parameter of the as-prepared nanoparticles corresponding to the composition of Y{sub 3−x}Eu{sub x}NbO{sub 7}–4ZrO{sub 2} that was estimated as a single phase of cubic gradually increased as the content of europium x increased. The existence of small absorbance peaks at 395 and 466 nm corresponding to the Eu{sup 3+7}F{sub 0}→{sup 5}L{sub 6}, and {sup 7}F{sub 0}→{sup 5}D{sub 2} excitation transition, respectively, was clearly observed in the diffuse reflectance spectra of the as-prepared samples containing europium. The optical band gap of the as-prepared samples was in the range from 3.5 to 3.7 eV. The photoluminescence spectra of the as-prepared nanocrystals containing europium showed orange and red luminescences with main peaks at 590 and 610 nm, corresponding to {sup 5}D{sub 0}→{sup 7}F{sub 1} and {sup 5}D{sub 0}→{sup 7}F{sub 2} transitions of Eu{sup 3+}, respectively, under excitation at 395 nm Xe lamp. The emission intensity corresponding to {sup 5}D{sub 0}→{sup 7}F{sub 2} transition increased as heat-treatment temperature rose from 800 to 1200 °C. - Graphical abstract: This graphical abstract shows the excitation and emission spectra and a transmission electron microscopy image of nanocrystals (with composition based on the rare-earth niobates (Ln{sub 3}NbO{sub 7}, Ln=Y, Eu) and zirconia (ZrO{sub 2}) that were composed of 50 mol% Ln{sub 3}NbO{sub 7} and 50 mol% ZrO{sub 2}) formed via hydrothermal route. Display Omitted - Highlights: • Nanocrystals composed of 50 mol% Y{sub 3−x}Eu{sub x}NbO{sub 7} and 50 mol% ZrO{sub 2} was directly formed. • The nanocrystals were hydrothermally formed under weakly basic conditions at 240 °C. • The Y{sub 3}NbO{sub 7} showed an UV-blue and broad-band emission under excitation at 240 nm. • The emission is originated from the niobate octahedral group [NbO{sub 6}]{sup 7−}. • The nanocrystals showed orange and red luminescences ({sup 5}D{sub 0}→{sup 7}F{sub 1} and {sup 5}D{sub 0}→{sup 7}F{sub 2} , Eu{sup 3+})

36 MATERIALS SCIENCE↗

MWCNT/WO{sub 3} nanocomposite photoanode for visible light induced water splitting

The Multi-walled carbon nanotube (MWCNT)/WO{sub 3} nanocomposite thin films with different MWCNT’s weight percentages were prepared by sol–gel method as visible light induced photoanode in water splitting reaction. Weight percentage of MWCNT in the all nanocomposite thin films was confirmed by TGA/DSC analysis. According to XPS analysis, oxygenated groups at the surface of the MWCNT and stoichiometric formation of WO{sub 3} thin films were determined, while the crystalline structure of the nanocomposite samples was studied by XRD indicating (0 0 2) peak of MWCNT in the monoclinic phase of WO{sub 3}. The influence of different weight percentage (wt%) of MWCNT on WO{sub 3} photoactivity showed that the electron conductivity, charge transfer and electron life time had improved as compared with the pure WO{sub 3}. Based on linear sweep voltammetry and chronoamperometry measurements, the (1 wt%) MWCNT/WO{sub 3} nanocomposite thin films photoanode has a maximum photocurrent density of ∼4.5 A/m{sup 2} and electron life time of about 57 s. - Graphical abstract: Photocurrent density versus time at constant potential (0.7 V) for the WO{sub 3} films containing different MWCNT weight percentages annealed at 400 °C under 1000 Wm{sup −2} visible photo-illumination. Display Omitted - Highlights: • MWCNT/ WO{sub 3} nanocomposite thin films were synthesized using sol–gel derived method. • TGA/DSC confirmed the weight percentage of MWCNT in the all nanocomposite thin films. • XPS analysis revealed that WO{sub 3} was attached on the oxygenated group of MWCNT surface. • The Highest Photoelectrochemical activity is achieved for (1 wt%)MWCNT/WO{sub 3} thin film.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Three Pb{sup II} coordination polymers based on 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid: Syntheses, crystal structures, and fluorescent properties

Three lead coordination polymers, [PbCl(C{sub 10}H{sub 6}N{sub 3}O{sub 4})(H{sub 2}O)·H{sub 2}O]{sub n} (1), [Pb(C{sub 10}H{sub 6}N{sub 3}O{sub 4}){sub 2}(H{sub 2}O)]{sub n} (2) and [Pb{sub 3}(C{sub 10}H{sub 5}N{sub 3}O{sub 4}){sub 3}]{sub n} (3) (C{sub 10}H{sub 7}N{sub 3}O{sub 4}=2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. In 1, Cl anions connected neighboring wave-like 2D layers, which are constructed with left- and right-handed helical chains, into a 3D network structure with a (6{sup 3})(6{sup 5}·8) topology. In 2, Pb cations are linked into a 3D 6{sup 6} network with left- and right-handed helixes by μ{sub 2}-bridging C{sub 10}H{sub 6}N{sub 3}O{sub 4}{sup −} ligands. In 3, C{sub 10}H{sub 5}N{sub 3}O{sub 4}{sup 2−} ligands link Pb{sub 6}O{sub 12} clusters into a 3D (4{sup 12}·6{sup 3}) network. Their fluorescent properties were also investigated. - Graphical abstract: Three 3D lead compounds based on 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid have been hydrothermally synthesized. Four new coordination modes of the organic ligand are first reported. Display Omitted - Highlights: • Three new Pb(II) complexes have been synthesized and characterized. • Left- and right-handed helical chains can be found in the 3D networks of 1 and 2. • Pb{sub 6}O{sub 12} clusters are connected into (4{sup 12}·6{sup 3}) network in 3.

36 MATERIALS SCIENCE↗

Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer composite material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

4,4′-Bipyridine-aided synthesis and characterization of Zn(II) and Cd(II) 2-sulfoterephthalate complexes

Six d{sup 10} complexes, [Zn{sub 1.5}(stp)(bpy){sub 0.5}(H{sub 2}O){sub 2}]·0.5H{sub 2}O (1), Cd{sub 1.5}(stp)(bpy){sub 0.5}(H{sub 2}O){sub 2} (2), [Cd{sub 1.5}(stp)(bpy)(H{sub 2}O)]·H{sub 2}O (3), [Zn{sub 0.5}(bpy){sub 0.5}(H{sub 2}O){sub 2}][Zn(stp)(bpy)(H{sub 2}O)]·0.5H{sub 2}O (4), Cd{sub 3}(stp){sub 2}(bpy){sub 3}(H{sub 2}O){sub 3} (5), Hbpy·[Zn{sub 0.5}(bpy)(H{sub 2}O){sub 2}][Zn{sub 0.5}(stp)(H{sub 2}O)]·H{sub 2}O (6) based on 2-sulfoterephthalate (stp{sup 3−}) and 4,4′-bipyridine (bpy) have been synthesized under hydro/solvo-thermal conditions and structurally characterized. Complex 1 exhibits a three-fold interpenetrated 3D porous architecture. Complexes 2 and 3 possess helices with different chirality arranging alternately. 4 and 6 are addition compounds, which compose of complex cation and complex anion. Complex 5 features a 3D layer-pillar framework in which a (4, 4) grid layer is constructed by stp{sup 3−} ligands and Cd(II) ions, and the layers are further connected by bpy pillars. The solid-state luminescent properties of the coordination polymers have also been investigated. - Graphical abstract: Display Omitted - Highlights: • Complexes 1–3 possess helices with different chirality arranging alternately. • The structural diversity can be attributed to various coordination modes of ligands. • The formation of helical structure is related to the adjacent carboxyl and sulfonate groups. • Bpy exhibits three roles: bridge, hydrogen bonding acceptor, and template.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, structural characterization and properties of SrAl{sub 4−x}Ge{sub x}, BaAl{sub 4−x}Ge{sub x}, and EuAl{sub 4−x}Ge{sub x} (x≈0.3–0.4)—Rare examples of electron-rich phases with the BaAl{sub 4} structure type

Three solid solutions with the general formula AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba; 0.32(1)≤x≤0.41(1)) have been synthesized via the aluminum self-flux method, and their crystal structures have been established from powder and single-crystal X-ray diffraction. They are isotypic and crystallize with the well-known BaAl{sub 4} structure type, adopted by the three AEAl{sub 4} end members. In all structures, Ge substitutes Al only at the 4e Wyckoff site. Results from X-rays photoelectron spectroscopy on EuAl{sub 4−x}Ge{sub x} and EuAl{sub 4} indicate that the interactions between the Eu{sup 2+} cations and the polyanionic framework are enhanced in the Ge-doped structure, despite the slightly elevated Fermi level. Magnetic susceptibility measurements confirm the local moment magnetism, expected for the [Xe]4f{sup 7} electronic configuration of Eu{sup 2+} and suggest strong ferromagnetic interactions at cryogenic temperatures. Resistivity data from single-crystalline samples show differences between the title compounds, implying different bonding characteristics despite the close Debye temperatures. A brief discussion on the observed electron count and homogeneity ranges for AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba) is also presented. - Graphical abstract: AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba; 0.32(1)≤x≤0.41(1)), three “electron-rich” phases with BaAl{sub 4} structure type have been synthesized and characterized. Display Omitted - Highlights: • Three BaAl{sub 4}-type ternary aluminum germanides have been synthesized with Eu, Sr and Ba. • Eu, Sr and Ba cations have no apparent influence on the solubility of Ge. • The Ge atoms substitute Al on one of two framework sites, thereby strengthening the interactions between the cations and the polyanionic framework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗