Physical properties of the delafossite CuCoO2 synthesized by co-precipitation /hydrothermal route

Abstract

CuCoO2 crystallizing in the delafossite structure was prepared by co-precipitation/hydrothermal method at low temperature (~ 150 °C). It is stable in air up to ~400 °C beyond which it turns into the spinel. The oxide has a direct optical transition attributed to the crystal field splitting of Cu+, linearly coordinated. It exhibits p-type behavior due to O2− insertion in the layered lattice. Such property is corroborated by a cathodic photocurrent in the intensity-potential (J – E) plot and a negative slope of the capacitance potential (C−2– E) plot. The latter traced in NaOH (0.01 M) electrolyte, exhibits a straight line from which a flat band potential of +0.411 V and a hole density of 6.9 × 1023 m−3 were extracted. An exchange current density of 7.36 μA cm−2and a polarizarion resistance (6.69 kΩ cm2), derived from the semi-logarithmic curve (log(J) – E), indicate a good electrochemical stability with a medium hysteresis loop and a low H2-over potential. The anisotropy of the 2 D dimensional crystal structure allows reversible oxygen insertion in the (0 0 n) planes evidenced from the (J – E) profiles. The Electrochemical Impedance Spectroscopy (EIS) measurements give two well-distinguished depressive semicircles in the dark. The diameter of the semicircle at high frequencies (1.49 kΩ cm2) decreases down to (1.28 kΩ cm2) under irradiation, a behavior typical of a non-degenerate semi conductivity of CuCoO2