The delafossite CuCrO2 elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstrncture is fairly homogenous wi...The delafossite CuCrO2 elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstrncture is fairly homogenous with a mean crystallite size of ca. 2 Ixm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of-0.26 VscE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO2/ZnO (1/1). CuCrO2 is photoactivated by visible light and the electrons in the conduction band (-1.34 VscE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25~C, 5x 10-4 mol/L) because of the HCrO4- dark adsorption onto ZnO (4HCrO4- + 3C7H603 + 1802 + 16H~ 4Cr3+ + 21CO2 + 19H20, AGO = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 Ixmol/(hr.g).展开更多
基金Financial support of this investigation by the faculty of chemistry
文摘The delafossite CuCrO2 elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstrncture is fairly homogenous with a mean crystallite size of ca. 2 Ixm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of-0.26 VscE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO2/ZnO (1/1). CuCrO2 is photoactivated by visible light and the electrons in the conduction band (-1.34 VscE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25~C, 5x 10-4 mol/L) because of the HCrO4- dark adsorption onto ZnO (4HCrO4- + 3C7H603 + 1802 + 16H~ 4Cr3+ + 21CO2 + 19H20, AGO = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 Ixmol/(hr.g).