For achieving unified functionalities of rare-earth free
materials,
the development of innovative zinc oxide and β-silicon carbide
(ZnO@β-SiC) composites by a solid-state reaction method is presented.
The evolution of zinc silicate (Zn2SiO4) is
evidenced by X-ray diffraction when annealed in air beyond 700 °C.
Detailed X-ray photoelectron spectroscopy and Fourier transform infrared
spectroscopy analyses reveal the involvement of silicon dioxide in
forming Zn2SiO4. Transmission electron microscopy
and the associated energy-dispersive X-ray spectroscopy elucidate
the evolution of the zinc silicate phase at the ZnO/β-SiC interface,
though it can be averted by vacuum annealing. These results manifest
the importance of air in oxidizing SiC before a chemical reaction
with ZnO from 700 °C. Finally, ZnO@β-SiC composites are
found to be promising for methylene blue dye degradation under ultraviolet
radiation, but the annealing above 700 °C is detrimental due
to the evolution of a potential barrier in the presence of Zn2SiO4 at the ZnO/β-SiC interface.
The work function engineering in metal-oxide nanostructures
by
judicious doping of impurities is not straightforward as it introduces
multiple defects in the system. In this regard, understanding the
nitrogen (N) doping-induced modulation of Fermi levels in TiO2 nanotubes (TNTs) is challenging for visible-range photocatalytic
applications. Here, 50 keV N ions are implanted in TNTs with a fluence
range of 1014–1016 ions/cm2. X-ray diffraction and micro-Raman analyses demonstrate the formation
of anatase-TiO2 in pristine TNTs, while the crystalline
quality is significantly affected by increasing ion fluence. The evolution
of Ti3+ is also established by X-ray photoelectron spectroscopy,
whereas ultraviolet photoelectron spectroscopy reveals the reduction
in work function due to the formation of oxygen vacancies, in good
agreement with X-ray absorption spectroscopy and photoluminescence
results. The electron paramagnetic resonance study further identifies
the evolution of Ti3+/N-substitutional defect centers.
Finally, an enhancement in visible-light-assisted methylene blue and
Rhodamine B dye degradation is recorded up to a fluence of 1 ×
1015 ions/cm2, and it is correlated with the
N-ion implantation-induced formation of electrochemically active states
near the conduction band minimum and the valence band maximum. The
decrease in degradation efficiency beyond a critical fluence of 1015 ions/cm2 is discussed on the ground of ion-beam-mediated
amorphization and the subsequent increase in electron–hole
recombination in the defect states.
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