The
development of highly efficient Ni-sulfide-based catalysts
is desirable but limited due to slow kinetics in alkaline hydrogen
evolution reactions (HER) and water electrolysis. Herein, we report
the design of a high-valent doping strategy combined with selective
surface etching to generate an OH-enriched porous heterostructure
NiS/Ni3S2 nanosphere with an optimal electronic
structure. The E-NiS/Ni3S2–Zr(6 mM) electrocatalyst requires only 50 mV to achieve 10 mA cm–2 for the HER. Oxygen evolution reaction (OER) requires 205 and 282
mV to reach 10 and 100 mA cm–2, respectively. In
addition, for total water splitting in alkaline medium, the assembled
cell with E-NiS/Ni3S2–Zr(6 mM) as both the positive and negative electrodes requires ultralow voltages
of 1.41 and 1.51 V at 10 mA and 20 mA cm–2 current
densities, respectively. Notably, E-NiS/Ni3S2–Zr(6 mM) showed excellent stability for 30
h in HER, OER, and water electrolysis. Delving into the underlying
electrochemical processes and electron transfer kinetics, a diverse
array of techniques such as linear sweep voltammogram, electrochemical
impedance spectroscopy, electrochemical active surface area, C
dl, cyclic voltammetry, chronoamperometric,
and turn over frequency were employed. Comprehensive characterization
encompassing X-ray diffraction, X-ray photoelectron spectroscopy,
Fourier transform infrared, Raman, scanning electron microscopy, energy
dispersive X-ray spectroscopy, and transmission electron microscopy
was conducted to explore the electronic and morphological attributes
of the synthesized materials. The approach formulated in this study
paves the way for achieving optimal electrocatalyst performance, positioning
them as compelling alternatives to noble metal-based electrocatalysts.