Solvothermal synthesis of soluble, surface modified anatase and transition metal doped anatase hybrid nanocrystals.

Titanium dioxide, or titania, is perhaps the most well-known and widely studied photocatalytic material, with myriad applications, due to a high degree of tunability achievable through the incorporation of dopants and control of phase composition and particle size. Many of the applications of titanium dioxide require particular forms, such as gels, coatings, or thin films, making the development of hybrid solution processable nanoparticles increasingly attractive. Here we report a simple solvothermal route to highly dispersible anatase phase titanium dioxide hybrid nanoparticles from amorphous titania. Solvothermal treatment of the amorphous titania in trifluoroacetic acid leads to the formation of anatase phase nanoparticles with a high degree of size control and near complete surface functionalisation. This renders the particles highly dispersible in simple organic solvents such as acetone. Dopant ions may be readily incorporated into the amorphous precursor by co-precipitation, with no adverse effect on subsequent crystallisation and surface modification.

Air and moisture stable covalently-bonded tin(ii) coordination polymers.

Four covalently-bonded tin(ii) coordination polymers, (1)-(4), were hydrothermally prepared in aqueous alkaline media by the reactions of SnSO4 with 1,2,4,5-benzenetetracarboxylic acid (1), 1,3,5-benzenetricarboxylic acid (2), 4-hydroxypyridine-2,6-dicarboxylic acid (3), and 1,3,5-cyclohexanetricarboxylic acid (4). All products were structurally authenticated by single-crystal X-ray diffraction, and the number of different tin centres and their oxidation states were confirmed by 119Sn Mössbauer spectroscopy. In addition, the comparison between experimental and simulated X-ray powder diffraction patterns confirmed the authenticity of the samples. Our crystallographic results for (1)-(4) show that the Sn(ii) centres are tetracoordinated and exhibit distorted disphenoidal geometries, corroborating the presence of one stereochemically active lone electron pair at each metal site. Products (1) and (2) display bi-dimensional polymeric structures, (3) exhibits a one-dimensional architecture, whereas (4) shows a remarkable three-dimensional coordination network. Hirshfeld surface and supramolecular analyses for the repeating units of (1)-(4) were also performed in order to identify structurally important non-covalent interactions.

The effect of Mg doping on the structural and physical properties of LuFe(2)O(4) and Lu(2)Fe(3)O(7).

The structural and physical properties of the recently discovered electronic ferroelectric materials LuFe(2)O(4) and Lu(2)Fe(3)O(7) have been investigated for Mg substitution of Fe. X-ray diffraction data demonstrate that the lattice parameters in both systems change progressively with increasing Mg content, with a smaller unit cell volume on replacing Fe(2+) by Mg(2+). X-ray absorption near-edge spectroscopy experiments at the Fe K-edge show that the average Fe oxidation state is slightly increased along with Mg doping in Lu(2)Fe(3)O(7) materials, consistent with isomorphous replacement of Fe(2+) by Mg(2+). Measurements of dielectric properties demonstrate that Mg doping could have an effect on the electron hopping energy between Fe(2+) and Fe(3+) ions. Transmission electron microscopy and magnetization analysis reveal that Mg doping in LuFe(2)O(4) has a much greater influence than in Lu(2)Fe(3)O(7) on both the charge ordering and the low-temperature magnetic properties.

Real time observation of the hydrothermal crystallization of barium titanate using in situ neutron powder diffraction.

The hydrothermal crystallization of barium titanate, BaTiO3, has been studied in situ by time-resolved powder neutron diffraction methods using the recently developed Oxford/ISIS hydrothermal cell. This technique has allowed the formation of the ferroelectric ceramic to be followed in a noninvasive manner in real time and under genuine reaction conditions. In a first set of experiments, Ba(OD)2-8D2O was reacted with two different titanium sources, either crystalline TiO2 (anatase) or amorphous TiO2-H2O in D2O, at 100-140 degrees C and the reaction studied using the POLARIS time-of-flight neutron powder diffractometer, at the ISIS Facility. In a second series of experiments, the reaction between barium chloride and crystalline TiO2 (anatase) in NaOD/D2O was studied at temperatures between 100 and 200 degrees C and at different deuterioxide concentrations using the constant-wavelength D20 neutron powder diffractometer at the Institut Laue Langevin. Quantitative growth and decay curves were determined from analysis of the integrated intensities of Bragg reflections of starting materials and product phases. In both sets of experiments the rapid dissolution of the barium source was observed, followed by dissolution of the titanium source before the onset of crystallization of barium titanate. Using a nucleation-growth model we are able to simulate the growth curve of barium titanate at three temperatures. Our results indicate the predominance of a homogeneous dissolution-precipitation mechanism for the hydrothermal formation of barium titanate, rather than other possible mechanisms that have been discussed in the literature. Analysis of the line widths of the Bragg reflections in the neutron diffraction data indicates that the particle size of the BaTiO3 product phase prepared from the amorphous TiO2-H2O is smaller than that prepared from crystalline TiO2 (anatase).

Direct in situ observation of increasing structural dimensionality during the hydrothermal formation of open-framework zinc phosphates.

The first time-resolved in situ X-ray diffraction studies of the hydrothermal crystallisation of open-framework zinc phosphates reveal a pathway of sequential crystallisation involving formation of a metastable low dimensional chain phase before the growth of three-dimensional zeolitic architectures.

Hydrothermal synthesis of (C6N2H14)2(UVI2UIVO4F12), a mixed-valent one-dimensional uranium oxyfluoride.

A new hybrid organic-inorganic mixed-valent uranium oxyfluoride, (C6N2H14)2(U3O4F12), UFO-17, has been synthesized under hydrothermal conditions using uranium dioxide as the uranium source, hydrofluoric acid as mineralizer, and 1,4-diazabicyclo[2.2.2]octane as template. The single-crystal X-ray structure was determined. Crystals of UFO-17 belonged to the orthorhombic space group Cmcm (no. 63), with a = 14.2660(15) A, b = 24.5130(10) A, c = 7.201(2) A, and Z = 4. The structure reveals parallel uranium-containing chains of two types: one type is composed of edge-sharing UO2F5 units; the other has a backbone of edge-sharing UF8 units, each sharing an edge with a pendant UO2F5 unit. Bond-valence calculations suggest the UF8 groups contain UIV, while the UO2F5 groups contain UVI. EXAFS data give results consistent with the single-crystal X-ray structure determination, while comparison of the uranium LIII-edge XANES of UFO-17 with that of related UIV and UVI compounds supports the oxidation-state assignment. Variable-temperature magnetic susceptibility measurements on UFO-17 and a range of related hybrid organic-inorganic uranium(IV) and uranium(VI) fluorides and oxyfluorides further support the formulation of UFO-17 as a mixed-valent UIV/UVI compound.