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).     

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...     

Electrochemical and photoelectrochemical characterization of CuFeO2 single crystal

CuFeO₂ single crystal, synthesized by the flux method, is a narrow band gap semiconductor crystallizing in the delafossite structure with a direct optical transition of 1.63 eV. The oxide exhibits a good chemical stability; the semi-logarithmic plot gave an exchange current density of 0.60 μA cm⁻² in KCl (0.5 M) electrolyte. CuFeO₂ shows p-type conductivity; the origin of acceptors Cu²⁺ results from oxygen insertion in the layered lattice where most of excess holes are trapped in surface-polaron states. The electrochemical study is confined in the (a,b) plane and reversible oxygen intercalation is evidenced from the intensity potential characteristics. The detailed photoelectrochemical studies have been reported for the first time on the single crystal. The photocurrent is ascribed to the transfer Cu⁺:3d→3d. The capacitance measurement (C⁻²–V) shows a linear behavior from which a flat band potential of +0.54 V_SCE and a density N _A of 1.60 × 10¹⁸ cm⁻³ were determined. The valence band, located at 5.33 eV below vacuum, is made up of Cu-3d orbital typical of delafossite oxides. The Nyquist plot shows a semicircle attributed to a capacitive behavior with a low density of surface states within the gap. The centre is localized below the real axis with an angle of 16.2° ascribed to a constant phase element (CPE), a single barrier of the junction CuFeO₂/electrolyte and one relaxation time of the electrical equivalent circuit.

Preparation and physical properties of CuxWO3

We report on the study of WO₃ doped with Cu using sol-gel (Cu_xWO₃^d) and impregnation (Cu_xWO₃ⁱ) methods. All materials are well crystallized and exhibit single phases whose crystallite size ranges from 17 to 100 nm depending on Cu amount and the preparation technique. The conductivity dependence on temperature demonstrates semiconductor behavior and follows the Arrhenius model, with activation energies, E_σ, commonly in the range 0.4-0.6 eV. Moreover, the thermopower study shows that Cu_xWO₃^d is mainly of p-type conductivity, whereas Cu_xWO₃ⁱ is n-type. The mechanism of conduction is attributed to a small polaron hopping. The doping process is found to decrease the interband transition down to 520 nm depending on the preparation conditions. The photoelectrochemical characterization confirms the conductivity type and demonstrates that the photocurrent J_ph increases with Cu-doping. Taking into consideration the activation energy, the flat band potential and the band gap energy, the band positions of each material are proposed according to the preparation method and Cu amount.     

Physical properties of NxTiO2 prepared by sol–gel route

The compounds N_xTiO₂(x=0, 0.05, 0.1, 0.2) with the anatase structure have been synthesized by Sol–Gel method using Tri-ethyl Amine as nitrogen source and their optical, electrical and electrochemical properties are investigated. The electrical conductivity and thermoelectric power are measured in the temperature rang 300–600 K. The samples exhibit p-type behavior in contrast to TiO₂. The doped-samples exhibit two optical transitions (2.35≤E_h−Vis(eV)≤2.55; 1.97≤E_l−Vis (eV)≤2.06) directly allowed in the visible region, while only one transition is observed in UV region (E_UV∼3.00 eV). Pure TiO₂ shows direct band gap transition of 3.17 eV. The results confirm experimentally the calculations of Di. Valentin et al. [42]. The transitions E_h−Vis and E_l−Vis are attributed respectively to the promotion of electrons from the localized N 2p and π^? N–O bond to the conduction band. In all cases, E_UV is associated to the forbidden band energy. Though that the conductivity is generally improved by doping process, only N_0.05TiO₂ and N_0.1TiO₂ shows an enhanced mobility. The mechanism of conduction takes place by small polaron hopping. The band edge positions of N_xTiO₂ (x=0, 0.05, 0.1, 0.2) at room temperature is predicted from the obtained physical properties. This study proves experimentally the principal role of nitrogen in doping process and permits the electronic states localization associated with N-impurities in TiO₂ anatase.