Redox reactions of uranium hexafluoride. Comparison with phosphorus pentafluoride and preparation of copper(I) hexafluorouranate(V) [1]

Molecular iodine is oxidised by phosphorus pentafluoride in iodine pentafluoride at room temperature giving I₂⁺, PF₆^?, and PF₃. I₂⁺ is formed from uranium hexafluoride under similar conditions, but further oxidation occurs depending on the reaction stoicheiometry used. In all cases uranium pentafluoride is formed. Copper(II) fluoride reacts with UF₅ in acetonitrile at room temperature to give copper(II) hexafluorouranate(V), which is reduced by copper metal to give the copper(I) salt. The latter compound is formed from UF₆ and Cu metal, via the Cu^II salt, only if a fresh Cu surface is used for the reduction step.     

An infrared and inelastic neutron scattering spectroscopic investigation on the interaction of eta-alumina and methanol

The industrially important interaction of methanol with an eta-alumina catalyst has been investigated by a combination of infrared spectroscopy (diffuse reflectance and transmission) and inelastic neutron scattering (INS) spectroscopy. The infrared and INS spectra together show that chemisorbed methoxy is the only surface species present. Confirmation of the assignments was provided by a periodic DFT calculation of methoxy on eta-alumina (110). The thermal conversion of adsorbed methoxy groups to form dimethylether was also followed by INS, with DFT calculations assisting assignments. An intense feature about 2600 cm(-1) was observed in the diffuse reflectance spectrum. This band is poorly described in the extensive literature on the alumina/methanol adsorption system and its observation raised the possibility of a new surface species existing on this particular catalyst surface. INS measurements established that the 2600 cm(-1) feature could be assigned to a combination band of the methyl rock with the methyl deformation modes. This assignment was reinforced by an analysis of the neutron scattering intensity at a particular energy as a function of momentum transfer, which confirmed this particular adsorbed methoxy feature to arise from a second order transition. Similar behaviour was observed in the model compound Al(OCH3)3. The anomalous infrared intensity of the 2600 cm(-1) peak in the diffuse reflectance spectrum is a consequence of the different absorption coefficients of the C-H stretch and the combination mode. The implications for catalyst studies are discussed.     

From complex fluorides to CFC alternatives — an account of fluorine chemistry at Glasgow

Advances in the areas of complex fluorides, high-oxidation state fluorides, perfluorocarbon ligand complexes, solvated cations and radiotracer catalytic studies made in the city of Glasgow are described.     

Application of Bessel beams to 2D microfabrication

Fs laser-based two-photon polymerisation (2PP) has been widely reported as a means of directly writing three-dimensional nanoscale structures. Usually the voxel of a high numerical aperture microscope objective is scanned through the resin to build up the required model. In the case of high aspect ratio two-dimensional structures, such as cell scaffolds, repeated scanning is required to build up the height.The voxel shape can be substantially elongated by the inclusion of an axicon lens in the laser beam line. In this report we describe the use of a Bessel beam produced in the region beyond the focus of an objective lens when the beam has been modified in this way.A Ti:sapphire laser was used to write a range of 2D square cell structures in a Zr-loaded sol-gel system. The process was characterised, in terms of the dimensions of the polymerised Bessel region, for different processing conditions. Examples of the structures are also described.     

Laser polymerization-based novel lift-off technique

The fabrication of microstructures by two-photon polymerization has been widely reported as a means of directly writing three-dimensional nanoscale structures. In the majority of cases a single point serial writing technique is used to form a polymer model. Single layer writing can also be used to fabricate two-dimensional patterns and we report an extension of this capability by using two-photon polymerization to form a template that can be used as a sacrificial layer for a novel lift-off process.A Ti:sapphire laser, with wavelength 795 nm, 80 MHz repetition rate, 100 fs pulse duration and an average power of 700 mW, was used to write 2D grid patterns with pitches of 0.8 and 1.0 μm in a urethane acrylate resin that was spun on to a lift-off base layer. This was overcoated with gold and the grid lifted away to leave an array of gold islands.The optical transmission properties of the gold arrays were measured and found to be in agreement with a rigorous coupled-wave analysis simulation.     

Oxidation of molybdenum and tungsten metals by molybdenum and tungsten hexafluorides in acetonitrile. Preparation of the 1:1 pentafluoride acetonitrile complexes

Molybdenum and tungsten metal powders are oxidized by their respective hexafluorides in the presence of acetonitrile at room temperature to give the 1:1 pentafluoride, acetonitrile complexes, MF₅.NCMe, M = Mo or W. Their i.r. spectra are consistent with C_4v symmetry for the MF₅N moiety. The tungsten pentafluoride complex appears to be stable with respect to disproportionation at room temperature.     

Fabrication of grating structures by simultaneous multi-spot fs laser writing

Two-photon polymerisation is an established technique for the fabrication of three-dimensional microstructures. To date structures have mostly been developed using single beam serial writing. A novel approach to simultaneous multi-spot two-photon polymerisation, that uses a SiO₂ on glass Fraunhofer diffractive optical element to generate an array of beamlets, is described. A Ti:sapphire laser, with wavelength 790 nm, 80 MHz repetition rate, 100 fs pulse duration and an average power of 25 mW, was used to initiate two-photon polymerisation. The DOE, in combination with a high power microscope objective, efficiently transforms the laser beam into a linear array of four spots of equal intensity. The fabrication of a periodic transmission grating, using parallel processing with these four spots, is shown. The grating was written in a Zr-loaded resin prepared on a glass substrate using dip coating deposition of a Zr/PMMA hybrid prepared by the sol-gel method. The operation of the diffractive element and the performance of the diffraction grating are also discussed.