Phosphorus-Doped Co3O4 Nanowire Array: A Highly Efficient Bifunctional Electrocatalyst for Overall Water Splitting

It is vitally essential to design highly efficient and cost-effective bifunctional electrocatalysts toward water splitting. Herein, we report the development of P-doped Co3O4 nanowire array on nickel foam (P-Co3O4/NF) from Co3O4 nanowire array through low-temperature annealing, using NaH2PO2 as the P source. As a 3D catalyst, such P-Co3O4/NF demonstrates superior performance for oxygen evolution reaction with a low overpotential (260 mV at 20 mA cm–2), a small Tafel slope (60 mV dec–1), and a satisfying durability in 1.0 M KOH. Density functional theory calculations indicate that P-Co3O4 has a reaction free-energy value that is much smaller than that of pristine Co3O4 for the potential determining step of the oxygen evolution reaction. Such P-Co3O4/NF also performs efficiently for hydrogen evolution reaction, and a two-electrode alkaline electrolyzer assembled by P8.6-Co3O4/NF as both anode and cathode needs only 1.63 V to reach a water-splitting current of 10 mA cm–2.