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 R
ct 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.