We
report on the first fabrication of vertically oriented niobium–zirconium
oxynitride nanotube arrays and their use as an attractive and robust
material for visible-light-driven water oxidation. These nanotube
arrays with an average diameter of ∼120 nm and very short length
∼90 nm were synthesized via one-step anodization of Nb–Zr
alloy sheet in NH4F-containing electrolytes. Ammonolysis
of the nanotubes resulted in narrowing the bandgap energy from 3.23
to ∼2.67 eV. The Nb–Zr oxynitride nanotube arrays showed
approximately an enhancement of about 1900% over that reported for
thin film electrodes made of niobium oxynitride and 3700% greater
than that recorded for nitrogen-doped mesoporous Nb2O5. Mott–Schottky and the valence band XPS analyses revealed
the favorable band positions of the fabricated oxynitride nanotubes
with respect to the water redox potentials with very high charge carriers
density. The photocurrent transient measurements revealed the remarkable
stability of the fabricated oxynitride nanotubes.
Herein,
the ability to convert waste stainless steel (SS) 316L
meshes into highly efficient and durable oxygen evolution reaction
(OER) catalysts is demonstrated. The process involves surface treatment
of previously anodized SS meshes in different gaseous atmospheres.
The activity of the resulted electrocatalysts varies as-anodized SS
annealed in oxygen (ASS-O2) > anodized SS annealed in
hydrogen
(ASS-H2) > anodized SS annealed in air (ASS-Air). The
ASS-O2 showed an impressive low overpotential of 280 mV
at the benchmark
current density of 10 mA/cm2, which is 120 mV less than
that of the as-received SS (SS-AR), and a low Tafel slope of 63 mV
dec–1 in 1 M KOH. These findings have also been
asserted by the estimated electrochemical active surface area, electrochemical
impedance spectroscopy analysis, Mott–Schottky analysis, and
the calculated turnover frequency, affirming the superiority of the
ASS-O2 electrocatalyst over the ASS-H2 and ASS-Air
counterparts. The high activity of the ASS-O2 electrocatalyst
can be ascribed to the surface composition that is rich in Fe3+ and Ni2+ as revealed by the X-ray photoelectron
spectroscopy analysis. The simple method of anodization and thermal
annealing in O2 at moderate conditions (450 °C for
1 h) lead to the formation of a SS mesh-based OER electrocatalyst
with activity exceeding that of the state-of-the-art IrO2/RuO2 and other complex modified SS catalysts. These results
were also confirmed via density functional theory calculations, which
unveiled the OER reaction mechanism and elucidated the d-band center
in different SS samples with different oxygen content. The presence
of oxygen moved the d-band center closer to the Fermi level in the
case of ASS-O2, explaining its superior activity.
Designing efficient and stable water
splitting photocatalysts is
an intriguing challenge for energy conversion systems. We report on
the optimal fabrication of perfectly aligned nanotubes on trimetallic
Ti–Mo–Fe alloy with different compositions prepared
via the combination of metallurgical control and facile electrochemical
anodization in organic media. The X-ray diffraction (XRD) patterns
revealed the presence of composite oxides of anatase TiO2 and magnetite Fe3O4 with better stability
and crystallinity. With the optimal alloy composition Ti–(5.0
atom %) Mo–(5.0 atom %) Fe anodized for 16 h, enhanced conductivity,
improved photocatalytic performance, and remarkable stability were
achieved in comparison with Ti–(3.0 atom %) Mo–(1.0
atom %) Fe samples. Such optimized nanotube films attained an enhanced
photocatalytic activity of ∼0.272 mA/cm2 at 0.9
VSCE, which is approximately 4 times compared to the bare
TiO2 nanotubes fabricated under the same conditions (∼0.041
mA/cm2 at 0.9 VSCE). That was mainly correlated
with the emergence of Mo and Fe impurities within the lattice, providing
excess charge carriers. Meanwhile, the nanotubes showed outstanding
stability with a longer electron lifetime. Moreover, carrier density
variations, lower charge transfer resistance, and charge carriers
dynamics features were demonstrated via the Mott–Schottky and
electrochemical impedance analyses.
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