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A thorough study is presented concerning the interfacial chemistry of the impregnation step involved in the preparation of molybdenum(VI) supported titania catalysts. This is based on a recently developed picture for the "titania/electrolyte solution" interface. In the frame of this work, we investigated the mode of interfacial deposition of the Mo(VI) oxo-species at the titania/electrolytic solution interface, the Mo(VI) interfacial speciation, and the structure of the deposited Mo(VI) oxo-species. Several methodologies based on potentiometric titrations, microelectrophoretic mobility, and macroscopic adsorption measurements were applied. The deposition model developed describes very well the experimental "proton-ion" linear curves and the "adsorption edges". Moreover, it was verified by laser Raman spectroscopy. At Mo(VI) solution concentration up to 3 × 10 -2 M and in the pH range 9-5, the mounted Mo(VI) is practically deposited as monomer MoO 42species in two configurations: an inner sphere mononuclear monosubstituted complex with the terminal surface oxygen atoms of titania [TiOMoO 3 ] 0.35and a surface species where the MoO 4 2ions are retained above a bridging surface hydroxyl through a hydrogen bond [Ti 2 OH • • • O-MoO 3 ] 1.57-. In both configurations, the Mo atom is situated between the surface plane and plane 1, whereas the solution oriented oxygen atoms are situated at plane 1 of the compact layer of the interface. The concentration of the [Ti 2 OH • • • O-MoO 3 ] 1.57increases with pH, while the concentration of the [TiOMoO 3 ] 0.35decreases. Thus, at pH > 8, the [Ti 2 OH • • • O-MoO 3 ] 1.57predominates, whereas at pH < 5.5 the [TiOMoO 3 ] 0.35is the most important species. In the pH range 5-4 and for the maximum initial Mo(VI) solution concentration, the contribution of the polymer species to the whole deposition process is not negligible. The deposited polymer species, Mo 7 O 24 6and HMo 7 O 24 5-, are adsorbed through electrostatic forces and located in a range extended from plane 1 up to the first layers of the stagnant-diffuse layer being close to plane 2 of the interface. The adsorption sites involve five bridging and five terminal neighboring (hydr)oxo-groups. A preferential deposition of the monomers, MoO 4 2-, with respect to the polymer ones was generally found. The above findings could prove useful for controlling the impregnation-equilibration step involved in the preparation of the molybdenum supported titania catalysts by equilibrium deposition filtration.

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The interfacial chemistry of the impregnation step involved in the synthesis of cobalt catalysts supported on titania was investigated with regard to the mode of interfacial deposition of the aqua complex [Co(H(2)O)(6)](2+) on the "titania/electrolyte solution" interface, the structure of the inner-sphere complexes formed, and their relative interfacial concentrations. Several methodologies based on the application of deposition experiments and electrochemical techniques were used in conjunction with diffuse-reflectance spectroscopy and EPR spectroscopy. These suggested the formation of mononuclear/oligonuclear inner-sphere complexes on deposition of the [Co(H(2)O)(6)](2+) ions at the "titania/electrolyte solution" interface. The joint application of semiempirical quantum-mechanical calculations, stereochemical considerations, and modeling of the deposition data revealed the exact structure of these complexes and allowed their relative concentrations at various Co(II) surface concentrations to be determined. It was found that the interface speciation depends on the Co(II) surface concentration. Mononuclear complexes are formed at the compact layer of the "titania/electrolyte solution" interface for low and medium Co(II) surface concentrations. Formation of mono-hydrolyzed Ti(2)O-TiO and the dihydrolyzed TiO-TiO disubstituted configurations is very probable. In the first configuration one water ligand of the [Co(H(2)O)(6)](2+) ion is substituted by a bridging surface oxygen atom and another by a terminal surface oxygen atom. In the second configuration two water ligands of the [Co(H(2)O)(6)](2+) ion are substituted by two terminal surface oxygen atoms. Binuclear and trinuclear inner-sphere complexes are formed, in addition to the mononuclear ones, at relatively high Co(II) surface concentrations.

The aim of this work was to develop bioprocesses to produce a high-value microbial product, bacterial cellulose (BC), utilizing the industrial side-stream of Corinthian currants finishing (CFS), with/without the addition of N-sources and cheese whey, and at various process conditions (temperature, pH level, and sugar concentration). For the optimization of BC production, the response surface methodology based on the central composite design was applied. Among the possible retrieved combinations, the most ideal conditions for BC in CFS extracts supplemented with N-source were 28 °C, pH 6.42, and 46.24 g/L concentration of sugars. In a similar manner, the best conditions for BC production in CFS/whey mixtures were pH 6.36, 50.4% whey percentage in the mixture, and 1.7% yeast extract. The textural characteristics of the produced BC, at different times of production and using different drying methods, were studied by scanning electron microscopy, X-ray diffractometry, porosimetry, Fourier-transform infrared spectroscopy, and thermogravimetric/differential thermal analysis, revealing increased porosity of BC compared with delignified cellulosic materials of plant origin, and a level of crystallinity that depended on the BC production time. The proposed methodology can be used to produce foods with potential prebiotic properties, using the highly nutritious CFS and the abundant cheese whey effluent as raw materials.