Eosin photodegradation over TiO2 modified by γ-ray irradiation

TiO₂ thin films are elaborated by sol gel on glass substrates and irradiated with ⁶⁰Co γ-rays. The X-ray diffraction, UV-Visible spectroscopy and transport properties are investigated. The films are nominally non stochiometric and the conductivity occurs by thermally activated hopping of lattice polaron. The oxygen vacancies induced by γ-ray irradiation at lower dose (<10 kGy) generate mixed valences Ti⁴⁺/³⁺, thus altering the transport properties. The photo-electrochemical characterisation is undertaken to evaluate the photo catalytic performance. The Mott-Schottky plots are characteristic of n type conduction from which a flat band potential of ?0.62 V _SCE and a donor density of 5 × 10¹⁷ cm^?3 are determined for the most active film. The Nyquist plot exhibits a semi-circular arc whose center lies below the real axis, due to the constant phase element (CPE). The energy band diagram shows the potentiality of the films for the eosin photodegradation. 68% of initial concentration (10 mg L^?1) disappears after 2 h of exposure to the solar light. TiO₂ irradiated with gamma dose of 10 kGy shows the best efficiency, due to the resistance decrees and high electron mobility (25 cm² V^?1 s^?1). The eosin oxidation follows a first order kinetic with a rate constant of 6 × 10^?2 min^?1.     

Effect of reducing gas on the hydrogen production by thermo-oxidation of water over 1%Rh/Ce0.6Zr0.4O2

We have studied the effect of the reducing gas (H₂, CO and CH₄) on the hydrogen production by thermo-oxidation of water over the 1%Rh/Ce_0.6Zr_0.4O₂ catalyst prepared by impregnation. The catalyst is characterized by hydrogen chemisorption (Hc), before and after catalytic decomposition of water, temperature-programmed desorption, temperature-programmed reduction, X-ray diffraction and scanning electron microscopy. The catalyst is reduced in situ at 500 °C (4 h) under H₂, CO or CH₄ flows and flushed with Ar gas. Then, pulses of water (1 μL/pulse) are injected at 500 °C under Ar flow (30 mL/min). The results show clearly that the reducing gas has a strong effect on the H₂ production which follows the order: H₂?>?CH₄?>?>?CO. H₂ chemisorption measurements at room temperature highlight a strong metal–support interaction over fresh reduced catalysts which decreases after water decomposition (reduced centers?+?H₂O?→?oxidized centers?+?H₂).

     

DFT Study of Donor-Acceptor-Donor [1,2,5]Thiadiazolo[3,4-c]pyridine Conjugated Polymer for Solar Cell Application

Theoretical and Experimental Chemistry - Using the density functional theory (DFT) method, the electronic and optical properties of the most stable conformers of the di(selenophen-2-yl)...     

Electrochemical intercalation of O2− in CuAlO2 single crystal and photoelectrochemical properties

The delafossite CuAlO₂ single crystal, prepared by the flux method, is a low mobility p-type semiconductor with a hole mobility of 1.2 × 10⁻⁵ cm⁻² V⁻¹ s⁻¹. The chronoamperometry showed an electrochemical O²⁻ insertion with a diffusion coefficient D _303K of 3.3 × 10⁻¹⁸ cm² s⁻¹. The thermal variation of D in the range 293–353 K gave an enthalpy of diffusion (ΔH) of 44.7 kJ mol⁻¹. CuAlO₂ is photoactive, and the Mott–Schottky plot indicates a flat band potential of +0.42 V vs saturated calomel electrode and a holes density (N _A) of 10¹⁶ cm⁻³. The photocurrent spectra have been analyzed by using the Gartner model from which the absorption coefficients and diffusion lengths were determined. An optical transition at 1.66 eV, indirectly allowed, has been obtained. The spectral photoresponse provides a high absorption at 480 nm. The low quantum yield (η) is attributed to a small depletion length (440 nm) and a hole diffusion width (271 nm) compared to a very large penetration depth (12 μm).     

Electrocatalytic performance of cobalt microparticles film-modified platinum disk electrode for amperometric detection of ascorbic acid

Deposited cobalt microparticales (Co-MPs) film onto the platinum disk electrode has been successfully used as a new amperometric sensor for the determination of ascorbic acid (AA). AA is detected by surface catalyzed oxidation involving cobalt(III) oxyhydroxides in alkaline solution. The Co-MPs/Pt electrode exhibits a high electrocatalytic activity toward the AA oxidation. The diffusion coefficient of AA (6.09 × 10⁵ cm²/s) and the catalytic rate constant (k _cat = 6.27 × 10³ M^–1s^–1) have been determined using electrochemical approaches. The amperometric response of the modified electrode is linear against the AA concentration in the range (0.01?0.48 mM). The sensor displays the best activity with a high response signal, a good sensitivity of 74.3 μA/mM, a low detection limit of 2.5 μM (signal/noise = 3) and a fast response time (<3 s). Moreover, the reproducibility, selectivity and applicability of this biosensor are satisfactorily evaluated.     

Photoelectrochemical study of La2NiO4 synthesized using citrate sol gel method—application for hydrogen photo-production

Journal of Solid State Electrochemistry - The semi conducting properties of La2NiO4 synthesized through sol gel method are studied for the first time using photoelectrochemistry. The X-ray...     

Preparation and characterization of the system NiMn2O4/TiO2 by sol–gel: application to the photodegradation of benzamide under visible light

Journal of Sol-Gel Science and Technology - Benzamide is successfully degraded on the novel heterosystem NiMn2O4/TiO2 under visible light. The nanosized spinel is synthesized by the sol–gel...     

Physical and photo-electrochemical properties of oxygen-rich delafossite CuYO2.25

Journal of Solid State Electrochemistry - CuYO2.25, prepared by soft chemistry, crystallizes in a pseudo delafossite structure and exhibits p-type conductivity. The oxygen inserts reversibly in the...     

Visible light photocatalytic reduction of water using SrSnO3 sensitized by CuFeO2

SrSnO_3–δ, prepared in sealed ampoules, crystallizes in the perovskite structure. The band gap is directly allowed at 3.93 eV. The conductivity was found to change markedly and occurs by polaron hopping with activation energy of 0.22 eV. The thermal variation of the thermopower indicates an electron mobility μ_{e 300K} = 3.15∙10^–6 cm²∙V^–1∙s^–1), thermally activated. The capacitance measurement shows a linear behavior from which a flat band potential of –0.20 V_SCE and an electronic density of 5.56∙10¹⁸ cm^–3 were determined. The conduction band edge (–4.32 eV/–0.42 V_SCE) lies below the H₂O/H₂ level. Accordingly, SrSnO_3–δ can be used for water photoreduction when combined with the delafossite CuFeO₂ as sensitizer. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 3, pp. 160-166, May-June, 2009.     

Photocatalytic reduction of cadmium over CuFeO2 synthesized by sol–gel

The Cd²⁺ photo-electrodeposition was successfully carried out in air-equilibrated aqueous CuFeO₂ suspension. The delafossite CuFeO₂ is p-type semiconductor characterized by a low optical gap, properly matched to the sun spectrum, and a long term chemical stability in neutral solution. It has been elaborated by the sol–gel technique where the specific surface area is increased via the surface/bulk ratio. The TG/DSC plots and IR spectra show that the solid phases are formed only at temperatures exceeding 400 and at 700 °C, the system is mixed phases. When fired at 950 °C under nitrogen flow, the delafossite has been identified (CuO + CuFe₂O₄ → CuFeO₂ + ½O₂). All the XRD lines index in a hexagonal unit cell with the lattice constants a = 284.2 and c = 169.4 pm. The photocurrent onset potential (+0.35 V_SCE) is close to the flat band potential (+0.23 V_SCE) determined from the capacitance measurement. CuFeO₂/Cd²⁺ solution is a self photo-driven system, the absorption of light promotes electrons into CuFeO₂–CB with a potential (?0.93 V_SCE) sufficient to reduce Cd²⁺. This occurs because of the dark Cd²⁺ adsorption on the surface powder. The system was optimized with respect to the following physical parameters: pH 6.8, Cd²⁺ (100 ppm) and a mass concentration C_m (1 mg catalyst/ml solution). The hetero-system CuFeO₂/TiO₂ has been also reported for a comparative purpose. Prolonged irradiation (>50 min) was accompanied by a pronounced decrease in the rate of Cd-deposition owing to the competitive water reduction. Indeed, the generated bi-functional CuFeO₂/Cd particles account for the low over-potential of hydrogen and favour its evolution in aqueous solution.