Surface Assistant Charge Separation in PEC Cu₂S-Ni/Cu₂O Cathode

Fabrication of a high efficiency photocathode is a challenging issue in photoelectrocatalysis (PEC). In this work, a Cu₂S-Ni/Cu₂O photocathode was constructed via electrodeposition followed by a two-step overlayer deposition procedure including direct-current magnetron sputtering (DCMS) and ion exchange reaction. We found that the presence of Ni in the inner-layer could not only affect the morphology but also enhance the formation rate of the outer-layer Cu₂S. The XPS results indicate that the Ni exist as NiO instead of Ni⁰. The photocurrent of Cu₂S-Ni/Cu₂O achieved 2 times of it on the pristine Cu₂O. The charge dynamic characterizations, including electrochemical impedance spectroscopy (EIS), Tafel slopes, and photoluminescence (PL) spectra, demonstrated that the Ni can promote the hydrogen evolution reaction follow the Heyrovsky reaction, while Cu₂S shows a crucial role on the surface charge separation. At last, surface photovoltage microscopy (SPVM) technology was used to reveal the function of each overlayer. It gives direct evidence for the charge transportation pathway in the system and explains the function of each component.