Highly visible-light-active sulfur and carbon co-doped TiO2 (SC-TiO2) heterogeneous photocatalysts prepared by underwater discharge plasma.

To promptly and simply create highly crystalline S/C co-doped TiO2 (SC-TiO2) photocatalysts at room temperature and atmospheric pressure, we suggest a novel plasma-assisted sol-gel synthesis method. This method is a simultaneous synthetic process, in which an underwater plasma undergoes continuous reactions to generate high-energy atomic and molecular species that enable TiO2 to achieve crystallinity, a large surface area, and a heterogeneous structure within a few minutes. In particular, it was demonstrated that the heterogeneously structured TiO2 was formed by doping that sulfur and carbon replace O or Ti atoms in the TiO2 lattice depending on the composition of the synthesis solution during underwater plasma treatment. The resultant SC-TiO2 photocatalysts had narrowed bandgap energies and extended optical absorption scope into the visible range by inducing the intermediate states within bandgap due to generation of oxygen vacancies on the surface of TiO2 through synthesis, crystallization, and doping. Correspondingly, SC-TiO2 showed a significant degradation efficiency ([k] = 6.91 h-1) of tetracycline (TC, antibiotics) under solar light irradiation, up to approximately 4 times higher compared to commercial TiO2 ([k] = 1.68 h-1), resulting in great water purification. Therefore, we anticipate that this underwater discharge plasma system will prove to be an advantageous technique for producing heterostructural TiO2 photocatalysts with superior photocatalytic efficiency for environmental applications.

High removal efficiency of industrial toxic compounds through stable catalytic reactivity in water treatment system.

We identified optimal conditions for the disposal of high concentration of organic contaminants within a short time using a hybrid advanced oxidation process (AOP) combining various oxidizing agents. Plasma-treated water (PTW) containing many active species, that play dominant roles in the degradation of organic substances like hydroxyl radicals, atomic oxygen, ozone, and hydrogen peroxide, was used in this study as a strategy to improve degradation performance without the use of expensive chemical reagents like hydrogen peroxide. In particular, the optimal decomposition conditions using PTW, which were combined with 10 mg/h ozone, 2 g/L iron oxide, and 4 W UV light, demonstrated excellent removal abilities of a high concentration of reactive black 5 (RB5; 100 mg/L, >99%, [k] = 4.15 h-1) and tetracycline (TC; 10 mg/L, >96.5%, [k] = 3.35 h-1) for 25 min, approximately 1.5 times higher than that without PTW (RB5; 100 mg/L, 94%, [k] = 2.80 h-1). These results confirmed that the production of strong reactive hydroxyl radicals from the decomposition process, as well as various reactive species included in PTW efficiently attacked pollutant substances, resulting in a higher removal rate. This suggests that a water treatment system with this optimal condition based on complex AOP systems using PTW could be useful in critical environmental and biomedical applications.

Synthesis of Lead-Free CaTiO3 Oxide Perovskite Film through Solution Combustion Method and Its Thickness-Dependent Hysteresis Behaviors within 100 mV Operation.

Perovskite is attracting considerable interest because of its excellent semiconducting properties and optoelectronic performance. In particular, lead perovskites have been used extensively in photovoltaic, photodetectors, thin-film transistors, and various electronic applications. On the other hand, the elimination of lead is essential because of its strong toxicity. This paper reports the synthesis of lead-free calcium titanate perovskite (CaTiO3) using a solution-processed combustion method. The chemical and morphological properties of CaTiO3 were examined as a function of its thickness by scanning electron microscopy, X-ray diffraction (XRD), atomic force microscopy, X-ray photoelectron spectroscopy, and ultraviolet-visible spectrophotometry. The analysis showed that thicker films formed by a cumulative coating result in larger grains and more oxygen vacancies. Furthermore, thickness-dependent hysteresis behaviors were examined by fabricating a metal-CaTiO3-metal structure. The electrical hysteresis could be controlled over an extremely low voltage operation, as low as 100 mV, by varying the grain size and oxygen vacancies.

Carrier Transport at Metal/Amorphous Hafnium-Indium-Zinc Oxide Interfaces.

In this paper, the carrier transport mechanism at the metal/amorphous hafnium-indium-zinc oxide (a-HIZO) interface was investigated. The contact properties were found to be predominantly affected by the degree of interfacial reaction between the metals and a-HIZO; that is, a higher tendency to form metal oxide phases leads to excellent Ohmic contact via tunneling, which is associated with the generated donor-like oxygen vacancies. In this case, the Schottky-Mott theory is not applicable. Meanwhile, metals that do not form interfacial metal oxide, such as Pd, follow the Schottky-Mott theory, which results in rectifying Schottky behavior. The Schottky characteristics of the Pd contact to a-HIZO can be explained in terms of the barrier inhomogeneity model, which yields a mean barrier height of 1.40 eV and a standard deviation of 0.14 eV. The work function of a-HIZO could therefore be estimated as 3.7 eV, which is in good agreement with the ultraviolet photoelectron spectroscopy (3.68 eV). Our findings will be useful for establishing a strategy to form Ohmic or Schottky contacts to a-HIZO films, which will be essential for fabricating reliable high-performance electronic devices.

Innovative three-dimensional (3D) eco-TiO2 photocatalysts for practical environmental and bio-medical applications.

It is known that water purified by conventional TiO2 photocatalysts may not be safe enough for drinking, due to the toxicity by tiny existence of TiO2 nanoparticles after water treatment. We herein demonstrate a facile design of a three-dimensional (3D) TiO2 photocatalyst structure with which both the efficiency of purification and the safety level of the final purified water can be improved and ensured, respectively. The structure, consisting of 3D sulfur-doped TiO2 microtubes in nanotubes (eco-TiO2), is suitable for both environmental and bio-medical applications. Investigation of its formation mechanism reveals that anodic aluminum oxide (AAO), owing to a spatial constraint, causes a simple, nanoparticles-to-nanotubes structural rearrangement as a template for nanotube growth. It is found that eco-TiO2 can be activated under visible-light irradiation by non-metal (sulfur; S) doping, after which it shows visible-light photocatalytic activities over a range of solar energy. Importantly, an in vitro cytotoxicity test of well-purified water by eco-TiO2 confirms that eco-TiO2 satisfies the key human safety conditions.

Photoluminescent carbon nanotags from harmful cyanobacteria for drug delivery and imaging in cancer cells.

Using a simple method of mass production of green carbon nanotags (G-tags) from harmful cyanobacteria, we developed an advanced and efficient imaging platform for the purpose of anticancer therapy. Approximately 100 grams of G-tags per 100 kilograms of harmful cyanobacteria were prepared using our eco-friendly approach. The G-tags possess high solubility, excellent photostability, and low cytotoxicity (<1.5 mg/mL for 24 h). Moreover, doxorubicin-conjugated G-tags (T-tags; >0.1 mg/mL) induced death in cancer cells (HepG2 and MCF-7) in-vitro at a higher rate than that of only G-tags while in-vivo mice experiment showed enhanced anticancer efficacy by T-tags at 0.01 mg/mL, indicating that the loaded doxorubicin retains its pharmaceutical activity. The cancer cell uptake and intracellular location of the G- and T-tags were observed. The results indicate that these multifunctional T-tags can deliver doxorubicin to the targeted cancer cells and sense the delivery of doxorubicin by activating the fluorescence of G-tags.

Influence of visible-light irradiation on physicochemical and photocatalytic properties of nitrogen-doped three-dimensional (3D) titanium dioxide.

We report highly active visible-light driven nitrogen-doped three-dimensional polycrystalline anatase TiO2 photocatalysts (N-3D TiO2) for environmental and biomedical applications. N-3D TiO2 is synthesized at a low temperature (<90°C) without thermal treatment via a modified hydrothermal process (HP) and ultrasound irradiation (UI). The N-3D TiO2 is additionally irradiated with visible-light to improve the hydroxylation of its surface. Under visible-light irradiation, the photocatalytic activity of visible-light irradiated N-3D TiO2 (*N-3D TiO2; [k]=1.435 h(-1)) is 26.1 times higher than that of 3D TiO2 ([k]=0.055 h(-1)). The *N-3D TiO2 is highly recyclable and retained 91.8% of the initial decolorization rate after fifteen cycles. Interestingly, the *N-3D TiO2 shows very strong antibacterial properties against both Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) after exposure to visible-light for 3h. The antibacterial properties of *N-3D TiO2 are more effective than those of TiO2, 3D TiO2, and N-3D TiO2. More than 91.3% of the E. coli is sterilized after ten cycles. There are a large increase in the photocatalytic and antibacterial activity of *N-3D TiO2 relative to that of N-3D TiO2 owing to the hydroxylation of the N-3D TiO2 surface as a result of the visible-light irradiation. These results indicate that *N-3D TiO2 might have utility in several promising applications such as highly efficient water/air treatment, inactivation of pathogenic microorganisms, and solar-energy conversion.

Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams.

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.