C-doped anatase TiO2: Adsorption kinetics and photocatalytic degradation of methylene blue and phenol, and correlations with DFT estimations.

This work shows an easy and eco-friendly methodology to obtain almost pristine anatase phase of TiO2 by using furfural, a biomass-derived molecule, as a bio-template. The photocatalytic activity was studied following the degradation of methylene blue and phenol under artificial solar irradiation. Results were compared against those obtained on a commercial pristine anatase TiO2. The pseudo first-order, the second-order and the intraparticle diffusion kinetic models were verified. The textural and surface chemistry properties of the materials were correlated with the surface density of molecules adsorbed in equilibrium. The reaction-rate showed an almost perfect quadratic regression as a function of the surface density. Theoretical estimations of the density of states by DFT + U were performed showing that the total electron charge in the oxygen bonded to anatase TiO2 increased due to carbon doping in agreement with the prediction of appearance of atomic orbitals 2p from carbon atom in the hybrid material. C-doping is responsible of the red-shift from 3.14 to 2.94 eV observed for a Ti15O32C super-cell than pristine anatase Ti16O32. The increase in the activity of the C-doped TiO2 photocatalyst was due to the decrease in the energy band-gap promoting a higher absorption of photons from the visible light.

Design of Ag/ and Pt/TiO2-SiO2 nanomaterials for the photocatalytic degradation of phenol under solar irradiation.

The design of hybrid mesoporous TiO2-SiO2 (TS1) materials decorated with Ag and Pt nanoparticles was performed. The photocatalytic degradation of phenol under artificial solar irradiation was studied and the activity and selectivity of the intermediate products were verified. TiO2-SiO2 was prepared by sol-gel method while Ag- and Pt-based photocatalysts (TS1-Ag and TS1-Pt) were prepared by photodeposition of the noble metals on TS1. Two series of photocatalysts were prepared varying Ag and Pt contents (0.5 and 1.0 wt%). An increase in the photocatalytic activity up to two and five times higher than TS1 was found on TS1-Ag-1.0 and TS1-Pt-1.0, respectively. Changes in the intermediate products were detected on Ag- and Pt-based photocatalysts with an increase in the catechol formation up to 3.3 and 6.6 times higher than that observed on TS1, respectively. A two-parallel reaction mechanism for the hydroquinone and catechol formation is proposed. A linear correlation between the photocatalytic activity and the surface concentration of noble metals was found indicating that the electron affinity of noble metals is the driven force for both the increase in the photoactivity and for the remarkable changes in the selectivity of products.

Photochemical reactivity of apical oxygen in KSr(2)Nb(5)O(15) materials for environmental remediation under UV irradiation.

The photocatalytic activity of a series of novel KSr2Nb5O15 materials was studied using the photooxidation of methylene blue as model reaction. The influence of the calcination time upon the crystalline structure and photoactivity was verified. Characterization was performed by XRD, SEM, FTIR, UV-Vis/DR, Helium picnometry, and N2 and CO2 adsorption-desorption isotherms. The diffraction line profile and the refinement of the structural parameters of KSr2Nb5O15 were obtained from the XRD patterns by the Rietveld method. Data showed that samples were photoactive under UV irradiation, regardless the synthesis conditions. However, the calcination time had a clear influence upon the photocatalytic activity of the samples, being more efficient towards the degradation of the dye those obtained at a lower calcination time. Indeed, the sample calcined for 4h showed up to 4 times higher photocatalytic activity than commercial TiO2. Additionally, a correlation between the photocatalytic activity and the displacement of the Nb ion from the central position in the [NbO6] octahedron was found. It is suggested that this fact causes an important polarization of the niobate structure. The apical oxygen in these samples is very reactive and can lead to the formation of superoxoradical anions (O2-) showing that KSr2Nb5O15 can be potentially used in photocatalytic reactions under UV irradiation.

Influence of activated carbon upon the photocatalytic degradation of methylene blue under UV-vis irradiation.

Photodegradation of methylene blue (MB) was studied on TiO2 in the presence of activated carbon (AC) prepared from the sawdust of a soft wood by physical activation under CO2 flow, by pyrolysis under N2 flow, and by chemical activation with ZnCl2 and H3PO4 under N2 flow. MB photodegradation was performed under UV and UV-visible irradiation to verify the scaling-up of the present TiO2-AC binary materials. It was verified that oxygenated surface groups on carbon were intrinsically photoactive, and a synergy effect between both solids has been estimated from the first-order apparent rate constants in the photodegradation of MB. This effect enhances the photoactivity of TiO2 up to a factor of about 9 under visible irradiation, and it was associated to the surface properties of AC.