The development of efficient bifunctional catalysts is the key technology to replace oxygen evolution reaction (OER) with hydrazine oxidation reaction (HzOR) with lower theoretical potential to achieve high efficiency and energy-saving hydrogen production. In this work, the Co0·52Cu0·48/Cu@S–C (−1.3 V) composite with flower-like array was prepared by two-step electrodeposition coupled pyrolysis method. The electrochemical measurements showed that the driving voltages of the optimal composite for HzOR and hydrogen evolution reaction (HER) are respectively −118 mV and 47 mV at a current density (j) of 10 mA cm−2. The excellent performance of Co0·52Cu0·48/Cu@S–C (−1.3 V) composite is attributed to the fact that the flower-like structure exposes more active areas and facilitates the diffusion of electrolyte, the strong electron interaction between Co0·52Cu0·48/Cu and S–C substrate, which can be verified by X-ray photoelectron spectroscopy (XPS), enhances the electrical conductivity, the Co0·52Cu0·48/Cu heterogeneous interface reduces the water dissociation barrier and facilitates the dehydrogenation kinetics of N2H4 determined by density functional theory (DFT) calculations. Due to the excellent performance of Co0·52Cu0·48/Cu@S–C (−1.3 V), the overall hydrazine splitting (OHzS) electrolytic cell was constructed with Co0·52Cu0·48/Cu@S–C (−1.3 V) as electrodes. The results showed the voltages required by the cell are 36, 210 and 282 mV at the current density values of 10, 100 and 200 mA cm−2 respectively, showing that Co0·52Cu0·48/Cu@S–C (−1.3 V) can be used for energy-saving hydrogen production by hydrazine assisted water electrolysis.
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