Characterization of Cu2O/CuO heterostructure photocathode by tailoring CuO thickness for photoelectrochemical water splitting.

Cu2O/CuO heterostructure is a well-known strategy to improve the performance of Cu2O photocathodes for photoelectrochemical (PEC) water splitting. The CuO thickness in the Cu2O/CuO heterostructure is considered as a critical factor affecting the PEC performance because it is highly related to the light utilization and charge separation/transport. In this study, the Cu2O/CuO photocathode tailoring the CuO thickness was investigated to examine the CuO thickness influence on the PEC performance. Cu2O/CuO photocathodes were prepared by the electrodeposition and subsequent thermal annealing process and the Cu2O/CuO heterostructure was controlled by the annealing temperature and time. It was demonstrated that the increased CuO thickness enhances the light absorption in the long wavelength region and improves the charge separation by the reinforced band bending. However, the thick CuO hinders the efficient charge transport in the Cu2O/CuO heterostructure, resulting in the decreased PEC performance. Therefore, it is necessary to optimize the CuO thickness for the enhanced PEC performance of Cu2O/CuO photocathodes. Consequently, the Cu2O/CuO photocathode consisting of the similar CuO thickness with its minority carrier diffusion length (∼90 nm) was fabricated by annealing at 350 °C for 20 min, and it shows the optimal PEC performance (-1.2 mA cm-2 at 0 V vs. RHE) in pH 6.5 aqueous solution, resulting from the enhanced light utilization and the reinforced band bending.

Electrocatalytic Properties of Pulse-Reverse Electrodeposited Nickel Phosphide for Hydrogen Evolution Reaction.

Nickel phosphide (Ni-P) films as a catalytic cathode for the hydrogen evolution reaction (HER) of a water splitting were fabricated by a pulse-reverse electrodeposition technique. The electrochemical behaviors for the electrodeposition of Ni-P were investigated by the characterization of peaks in a cyclic voltammogram. The composition of the electrodeposited Ni-P alloys was controlled by adjusting duty cycles of the pulse-reverse electrodeposition. The HER electrocatalytic properties of the Ni-P electrodeposits with an amorphous phase as a function of phosphorous contents existing in Ni-P were electrochemically characterized by the analysis of overpotentials, Tafel slopes, and electrochemical impedance spectrometry. Additionally, the elemental Ni-embedded crystalline Ni3P was prepared by an annealing process with the amorphous Ni69P31 electrodeposit with high contents of phosphorus. The crystalline structure with Ni inclusions in the matrix of Ni3P was formed by the precipitation of excess Ni. The electrocatalytic properties of crystalline Ni3P with elemental Ni inclusions were also investigated by electrochemical characterization.