The
development of a photocatalyst with remarkable activity to
degrade pollutants in aqueous and gas phase requires visible light-responsive
stable materials, easily organized in the form of a thin layer (to
exclude the highly expensive separation step). In this work, we present
a one-step strategy for synthesizing material in the form of a self-organized
TiO2/Ag2O nanotube (NT) array interlaced with
silver nanoparticles (as in a cake with raisins) that exhibited photoactivity
significantly enhanced compared to that of pristine TiO2 NTs under both ultraviolet (UV) and visible (vis) irradiation. An
NT array composed of a mixture of TiO2 and Ag2O and spiked with Ag nanoparticles was formed via the anodization
of a Ti–Ag alloy in a one-step reaction. Silver NPs have been
formed during the in situ generation of Ag ions and
were (i) embedded in the NT walls, (ii) stuck on the external NT walls,
and (iii) placed inside the NTs. The enhancement of photocatalytic
efficiency can be ascribed to the existence of an optimal content
of Ag2O and Ag NPs, which are responsible for decreasing
the number of recombination centers. In contrast to UV–vis
light, performance improvement under vis irradiation occurs with increasing
Ag2O and Ag0 contents in the TiO2/Ag2O/Ag NTs as a result of the utilization of larger
amounts of incident photons. The optimized samples reached phenol
degradation rates of 0.50 and 2.89 μmol dm–3 min–1 under visible and UV light, respectively,
which means degradation activities 3.8- and 2-fold greater than that
of the reference sample, respectively, remained after four photodegradation
cycles under UV light.
Vertically oriented, self-organized TiO2–MnO2 nanotube arrays were successfully obtained by one-step anodic oxidation of Ti–Mn alloys in an ethylene glycol-based electrolyte. The as-prepared samples were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), UV-Vis absorption, photoluminescence spectroscopy, X-ray diffraction (XRD), and micro-Raman spectroscopy. The effect of the applied potential (30–50 V), manganese content in the alloy (5–15 wt. %) and water content in the electrolyte (2–10 vol. %) on the morphology and photocatalytic properties was investigated for the first time. The photoactivity was assessed in the toluene removal reaction under visible light, using low-powered LEDs as an irradiation source (λmax = 465 nm). Morphology analysis showed that samples consisted of auto-aligned nanotubes over the surface of the alloy, their dimensions were: diameter = 76–118 nm, length = 1.0–3.4 μm and wall thickness = 8–11 nm. It was found that the increase in the applied potential led to increase the dimensions while the increase in the content of manganese in the alloy brought to shorter nanotubes. Notably, all samples were photoactive under the influence of visible light and the highest degradation achieved after 60 min of irradiation was 43%. The excitation mechanism of TiO2–MnO2 NTs under visible light was presented, pointing out the importance of MnO2 species for the generation of e− and h+.
TiO2/CuxOy nanotube (NT) arrays were synthesized using the anodization method in the presence of ethylene glycol and different parameters applied. The presence, morphology, and chemical character of the obtained structures was characterized using a variety of methods—SEM (scanning electron microscopy), XPS (X-ray photoelectron spectroscopy), XRD (X-ray crystallography), PL (photoluminescence), and EDX (energy-dispersive X-ray spectroscopy). A p-n mixed oxide heterojunction of Ti-Cu was created with a proved response to the visible light range and the stable form that were in contact with Ti. TiO2/CuxOy NTs presented the appearance of both Cu2O (mainly) and CuO components influencing the dimensions of the NTs (1.1–1.3 µm). Additionally, changes in voltage have been proven to affect the NTs’ length, which reached a value of 3.5 µm for Ti90Cu10_50V. Degradation of phenol in the aqueous phase was observed in 16% of Ti85Cu15_30V after 1 h of visible light irradiation (λ > 420 nm). Scavenger tests for phenol degradation process in presence of NT samples exposed the responsibility of superoxide radicals for degradation of organic compounds in Vis light region. Inactivation of bacteria strains Escherichia coli (E. coli), Bacillus subtilis (B. subtilis), and Clostridium sp. in presence of obtained TiO2/CuxOy NT photocatalysts, and Vis light has been studied showing a great improvement in inactivation efficiency with a response rate of 97% inactivation for E. coli and 98% for Clostridium sp. in 60 min. Evidently, TEM (transmission electron microscopy) images confirmed the bacteria cells’ damage.
V2O5-TiO2 mixed oxide nanotube (NT) layers were successfully prepared via the one-step anodization of Ti-V alloys. The obtained samples were characterized by scanning electron microscopy (SEM), UV-Vis absorption, photoluminescence spectroscopy, energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (DRX), and micro-Raman spectroscopy. The effect of the applied voltage (30–50 V), vanadium content (5–15 wt %) in the alloy, and water content (2–10 vol %) in an ethylene glycol-based electrolyte was studied systematically to determine their influence on the morphology, and for the first-time, on the photocatalytic properties of these nanomaterials. The morphology of the samples varied from sponge-like to highly-organized nanotubular structures. The vanadium content in the alloy was found to have the highest influence on the morphology and the sample with the lowest vanadium content (5 wt %) exhibited the best auto-alignment and self-organization (length = 1 μm, diameter = 86 nm and wall thickness = 11 nm). Additionally, a probable growth mechanism of V2O5-TiO2 nanotubes (NTs) over the Ti-V alloys was presented. Toluene, in the gas phase, was effectively removed through photodegradation under visible light (LEDs, λmax = 465 nm) in the presence of the modified TiO2 nanostructures. The highest degradation value was 35% after 60 min of irradiation. V2O5 species were ascribed as the main structures responsible for the generation of photoactive e− and h+ under Vis light and a possible excitation mechanism was proposed.
Among all kinds of green earth and renewable energy projects underway, semiconductor photocatalysis has received wide interest because it provides an easy way to directly utilize the energy of either natural sunlight or artificial indoor illumination. TiO 2 , the most widely used photocatalyst, due to its wide band gap, can only be activated under UV irradiation, and thus, the development of novel semiconductor photocatalysts makes a significant advancement in photocatalytic functional materials. One of the effective strategies to overcome this shortcoming is photosensitizing these wide band gap semiconductors with narrow band gap semiconductors which have proper energy levels. This method can not only improve the photocatalytic activity, due to increasing visiblelight-harvesting efficiency, but also can decrease the recombination of the charge carriers, because the formation of n-n or n-p heterojunctions between the combined semiconductors can induce internal electric fields between them. In this regard, this review presents some unitary, binary, and ternary non-TiO 2 photocatalysts used for the degradation for organic pollutants and for water splitting.
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