Band Gap Implications on Nano-TiO2 Surface Modification with Ascorbic Acid for Visible Light-Active Polypropylene Coated Photocatalyst.

The effect of surface modification using ascorbic acid as a surface modifier of nano-TiO2 heterogeneous photocatalyst was studied. The preparation of supported photocatalyst was made by a specific paste containing ascorbic acid modified TiO2 nanoparticles used to cover Polypropylene as a support material. The obtained heterogeneous photocatalyst was thoroughly characterized (scanning electron microscope (SEM), RAMAN, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Diffuse Reflectance Spectra (DRS) and successfully applied in the visible light photodegradation of Alizarin Red S in water solutions. In particular, this new supported TiO2 photocatalyst showed a change in the adsorption mechanism of dye with respect to that of only TiO2 due to the surface properties. In addition, an improvement of photocatalytic performances in the visible light photodegration was obtained, showing a strict correlation between efficiency and energy band gap values, evidencing the favorable surface modification of TiO2 nanoparticles.

Aggregation and metal-complexation behaviour of THPP porphyrin in ethanol/water solutions as function of pH.

The effect of pH change on 5,10,15,20-Tetrakis(4-hydroxyphenyl)-21H,23H-porphine (THPP) with its aggregation as function of water-ethanol mixture was studied with UV-vis, fluorescence, Raman and computational analysis. In neutral pH, THPP was present as free-base and, increasing the water amount, aggregation occurred with the formation of H- and J-aggregates. The aggregation constant and the concentration of dimers were calculated, other information about the dimer aggregation were evaluated by computational study. In acidic pH, by the insertions of two hydrogens in the porphyrin rings, the porphyrin changed its geometry with a ring deformation confirmed by red-shifted spectrum and quenching in fluorescence; at this low pH, increasing the water amount, the acidic form (THPPH2)2+ resulted more stable due to a polar environment with stronger interaction by hydrogen bonding. In basic pH, reached by NH4OH, THPP porphyrin was able to react with alkali metals in order to form sitting-atop complex (M2THPP) confirmed by the typical absorption spectrum of metallo-porphyrin, Raman spectroscopy and by computational analysis.

Spectroscopic studies of porphyrin functionalized multiwalled carbon nanotubes and their interaction with TiO2 nanoparticles surface.

UV-vis and fluorescence investigations about the non-covalent interaction, in ethanolic solutions, of multi-wall carbon nanotube (MWCNT) with Coproporphyrin-I, and its Cu(II) and Zn(II) complexes (MCPIs) have been reported. Evidence of binding between MWCNTs and porphyrins was discovered from spectral adsorption decrease with respect to free porphyrins and by the exhibition of photoluminescence quenching with respect to free porphyrins demonstrating that MWCNT@MCPIs are potential donor-acceptor complexes. Equilibrium and kinetic aspects in the interactions with monolayer transparent TiO2 thin films with the obtained MWCNT@MCPIs are clarified showing their effective adsorption by porphyrin links on the TiO2 monolayer support, with respect to not only MWCNTs, according to the Langmuir model and with pseudo-first-order kinetics. Morphological description of the adsorption of MWCNT@MCPIs on TiO2 with scanning electron microscopy has been reported. The obtained experimental evidences describe therefore MWCNT@MCPIs as potential sensitizers in the DSSC (Dye-Sensitized Solar Cell) applications.