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In the present era, electrochemical water splitting has been showcased as a reliable solution for alternative and sustainable energy development. The development of a cheap, albeit active, catalyst to split water at a substantial overpotential with long durability is a perdurable challenge. Moreover, understanding the nature of surface-active species under electrochemical conditions remains fundamentally important. A facile hydrothermal approach is herein adapted to prepare covellite (hexagonal) phase CuS nanoplates. In the covellite CuS lattice, copper is present in a mixed-valent state, supported by two different binding energy values (932.10 eV for Cu and 933.65 eV for Cu) found in X-ray photoelectron spectroscopy analysis, and adopted two different geometries, that is, trigonal planar preferably for Cu and tetrahedral preferably for Cu. The as-synthesized covellite CuS behaves as an efficient electro(pre)catalyst for alkaline water oxidation while deposited on a glassy carbon and nickel foam (NF) electrodes. Under cyclic voltammetry cycles, covellite CuS electrochemically and irreversibly oxidized to CuO, indicated by a redox feature at 1.2 V (vs the reversible hydrogen electrode) and an Raman study. Electrochemically activated covellite CuS to the CuO phase (termed as CuS) behaves as a pure copper-based catalyst showing an overpotential (η) of only 349 (±5) mV at a current density of 20 mA cm, and the TOF value obtained at η (at 349 mV) is 1.1 × 10 s. A low of 5.90 Ω and a moderate Tafel slope of 82 mV dec confirm the fair activity of the CuS catalyst compared to the CuS precatalyst, reference CuO, and other reported copper catalysts. Notably, the CuS/NF anode can deliver a constant current of ca. 15 mA cm over a period of 10 h and even a high current density of 100 mA cm for 1 h. Post-oxygen evolution reaction (OER)-chronoamperometric characterization of the anode via several spectroscopic and microscopic tools firmly establishes the formation of crystalline CuO as the active material along with some amorphous Cu(OH) via bulk reconstruction of the covellite CuS under electrochemical conditions. Given the promising OER activity, the CuS/NF anode can be fabricated as a water electrolyzer, Pt(-)//(+)CuS/NF, that delivers a of 10 mA cm at a cell potential of 1.58 V. The same electrolyzer can further be used for electrochemical transformation of organic feedstocks like ethanol, furfural, and 5-hydroxymethylfurfural to their respective acids. The present study showcases that a highly active CuO/Cu(OH) heterostructure can be constructed on NF from the covellite CuS nanoplate, which is not only a superior pure copper-based electrocatalyst active for OER and overall water splitting but also for the electro-oxidation of industrial feedstocks.
