A kinetic analysis methodology to elucidate the roles of metal, support and solvent for the hydrogenation of 4-phenyl-2-butanone over Pt/TiO2

The rate and, more importantly, selectivity (ketone vs aromatic ring) of the hydrogenation of 4-phenyl-2-butanone over a Pt/TiO2 catalyst have been shown to vary with solvent. In this study, a fundamental kinetic model for this multi-phase reaction has been developed incorporating statistical analysis methods to strengthen the foundations of mechanistically sound kinetic models. A 2-site model was determined to be most appropriate, describing aromatic hydrogenation (postulated to be over a platinum site) and ketone hydrogenation (postulated to be at the platinum–titania interface). Solvent choice has little impact on the ketone hydrogenation rate constant but strongly impacts aromatic hydrogenation due to solvent-catalyst interaction. Reaction selectivity is also correlated to a fitted product adsorption constant parameter. The kinetic analysis method shown has demonstrated the role of solvents in influencing reactant adsorption and reaction selectivity.

Rapid, simple method for determining the porosity of mesoporous TiO2 films using a quartz crystal microbalance (QCM)

Two different mesoporous films of TiO2 were coated onto a QCM disc and fired at 450o C for 30 min. The first film was derived from a sol-gel paste that was popular in the early days of dye-sensitised solar cell, i.e. dssc, research, a TiO2(sg) film. The other was a commercial colloidal paste used to make examples of the current dssc cell; a TiO2(ds) film. A QCM was used to determine the mass of the TiO2 film deposited on each disc and the increase in the mass of the film when immersed in water/glycerol solutions with wt% values spanning the range 0-70%. The results of this work reveal that with both TiO2 mesoporous films the solution fills the film's pores and acts as a rigid mass, thereby allowing the porosity of each film to be calculated as: 59.1% and 71.6% for the TiO2(sg) and TiO2(ds) films, respectively. These results, coupled with surface area data, allowed the pore radii of the two films to be calculated as: 9.6 and 17.8 nm, respectively. This method is then simplified further, to just a few frequency measurements in water and only air to reveal the same porosity values. The value of the latter ‘one point’ method for making porosity measurements is discussed briefly.

Facile Synthesis of Anatase TiO2 Quantum-Dot/Graphene-Nanosheet Composites with Enhanced Electrochemical Performance for Lithium-Ion Batteries

A facile method to synthesize well-dispersed TiO₂ quantum dots on graphene nanosheets (TiO₂-QDs/GNs) in a water-in-oil (W/O) emulsion system is reported. The TiO₂/graphene composites display high performance as an anode material for lithium-ion batteries (LIBs), such as having high reversible lithium storage capacity, high Coulombic efficiency, excellent cycling stability, and high rate capability. The excellent electrochemical performance and special structure of the composites thus offer a way to prepare novel graphene-based electrode materials for high-energy-density and high-power LIBs. 

In-Situ, Simultaneous Irradiation and Monitoring of a Photocatalysed Organic Oxidation Reaction in a TiO2-coated NMR Tube

The semiconductor photocatalysed (SPC) oxidation of toluene is performed inside an NMR spectrometer and the reaction monitored simultaneously in-situ, using a fibre optic probe/diffuser to provide the UV light to activate the titania photocatalyst coating on the inside of the NMR tube. Such a system has great potential for the simple rapid screening of a wide range of SPC mediated organic reactions.

Enhanced Dispersion of TiO2 Nanoparticles in a TiO2/PEDOT:PSS Hybrid Nanocomposite via Plasma-Liquid Interactions

A facile method to synthesize a TiO2/PEDOT:PSS hybrid nanocomposite material in aqueous solution through direct current (DC) plasma processing at atmospheric pressure and room temperature has been demonstrated. The dispersion of the TiO2 nanoparticles is enhanced and TiO2/polymer hybrid nanoparticles with a distinct core shell structure have been obtained. Increased electrical conductivity was observed for the plasma treated TiO2/PEDOT:PSS nanocomposite. The improvement in nanocomposite properties is due to the enhanced dispersion and stability in liquid polymer of microplasma treated TiO2 nanoparticles. Both plasma induced surface charge and nanoparticle surface termination with specific plasma chemical species are proposed to provide an enhanced barrier to nanoparticle agglomeration and promote nanoparticle-polymer binding.

Nanoporous carbons from sisal residues and their application in hybrid TiO2/carbon photocatalysts for the removal and degradation of phenol in solution

Tese de doutoramento, Química (Química Tecnológica), Universidade de Lisboa, Faculdade de Ciências, 2016

Structural modification of TiO2 nanorod films with an influence on the photovoltaic efficiency of a dye-sensitized solar cell (DSSC).

TiO2 nanorod films have been deposited on ITO substrates by dc reactive magnetron sputtering technique. The structures of these nanorod films were modified by the variation of the oxygen pressure during the sputtering process. Although all these TiO2 nanorod films deposited at different oxygen pressures show an anatase structure, the orientation of the nanorod films varies with the oxygen pressure. Only a very weak (101) diffraction peak can be observed for the TiO2 nanorod film prepared at low oxygen pressure. However, as the oxygen pressure is increased, the (220) diffraction peak appears and the intensity of this diffraction peak is increased with the oxygen pressure. The results of the SEM show that these TiO2 nanorods are perpendicular to the ITO substrate. At low oxygen pressure, these sputtered TiO2 nanorods stick together and have a dense structure. As the oxygen pressure is increased, these sputtered TiO2 nanorods get separated gradually and have a porous structure. The optical transmittance of these TiO2 nanorod films has been measured and then fitted by OJL model. The porosities of the TiO2 nanorod films have been calculated. The TiO2 nanorod film prepared at high oxygen pressure shows a high porosity. The dye-sensitized solar cells (DSSCs) have been assembled using these TiO2 nanorod films prepared at different oxygen pressures as photoelectrode. The optimum performance was achieved for the DSSC using the TiO2 nanorod film with the highest (220) diffraction peak and the highest porosity.