Electrochemically Derived Crystalline CuO from Covellite CuS Nanoplates: A Multifunctional Anode Material.

Abstract

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 CuI and 933.65 eV for CuII) found in X-ray photoelectron spectroscopy analysis, and adopted two different geometries, that is, trigonal planar preferably for CuI and tetrahedral preferably for CuII. 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 ex situ Raman study. Electrochemically activated covellite CuS to the CuO phase (termed as CuSEA) behaves as a pure copper-based catalyst showing an overpotential (η) of only 349 (±5) mV at a current density of 20 mA cm-2, and the TOF value obtained at η349 (at 349 mV) is 1.1 × 10-3 s-1. A low Rct of 5.90 Ω and a moderate Tafel slope of 82 mV dec-1 confirm the fair activity of the CuSEA catalyst compared to the CuS precatalyst, reference CuO, and other reported copper catalysts. Notably, the CuSEA/NF anode can deliver a constant current of ca. 15 mA cm-2 over a period of 10 h and even a high current density of 100 mA cm-2 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)2 via bulk reconstruction of the covellite CuS under electrochemical conditions. Given the promising OER activity, the CuSEA/NF anode can be fabricated as a water electrolyzer, Pt(-)//(+)CuSEA/NF, that delivers a j of 10 mA cm-2 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)2 heterostructure can be constructed in situ 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.