Photocatalytic nano-optical trapping using TiO2 nanosphere pairs mediated with Mie-scattered near field

The localized enhanced near field on nanostructures has been attracting much attention for a template for size-selective optical trapping (tweezers) beyond the diffraction limit. The near-field optical trapping has mainly been studied using metallic substrates such as Au nanodot pairs, periodic Al nanoslits, nanoapertures on an Au film, etc. In this paper, we newly propose a Mie-scattered-near-field optical trapping scheme for size-selective photocatalytic application using pairs of poly-rutile TiO₂ nanospheres. The optical intensity distribution in a 3D-nanogap space between the nanospheres was simulated by a 3D FDTD method. The simulation system consists of the two TiO₂ nanospheres placed on a silica substrate in water. The 400-nm excitation laser is used for both the near-field trapping and the photocatalyst excitation. The optical trapping forces were calculated based on the near-field optical intensity distribution. The trapping stiffness for 20-nm polystyrene sphere at a gap distance of 20 nm was 6.4 pN/nm/W. The optical force vector shows that the object like virus can be trapped with sufficient forces into the nanogap space and then is driven into the direct surface of the TiO₂ sphere. This result suggests that this system works as a photocatalytic trapping for killing virus, protein, etc.     

Synthesis,characterization, and photocatalytic properties of core/shell mesoporous silica nanospheres supporting nanocrystalline titania

The facile bulk synthesis of silica nanospheres makes them an attractive support for the transport of chemical compounds such as nanocrystalline titanium dioxide. In this contribution we present a promising route for the synthesis of mesoporous silica nanospheres (m-SiO₂) with diameter in range 200 nm, which are ideal supports for nanocrystalline titanium dioxide (TiO₂). The detailed microscopic and spectroscopic characterizations of core/shell structure (m-SiO₂/TiO₂) were conducted. Moreover, the photocatalytic potential of the nanostructures was investigated via phenol decomposition and hydrogen generation. A clear enhancement of photoactivity in both reactions as compared to commercial TiO₂-Degussa P25 catalyst is detected.     

Photoelectrocatalytic degradation of organic contaminants at Bi2O3/TiO2 nanotube array electrode

In the current work, TiO₂ nanotube array was prepared via electrochemical anode method. Then the Bi₂O₃ nanoparticles were deposited onto the TiO₂ nanotube array via dip-coating method from an amorphous complex precursor. The crystal structures were characterized via X-ray diffraction analysis. Their surface textures were observed via electron-scanning microscope. The prepared composite array electrode exhibited high photoelectrocatalytic activities towards degrading organic contaminants under visible light irradiation. High photoelectrocatalytic activities were also exhibited under UV light irradiation. The catalytic mechanism was discussed based on the analysis of electrochemical and degradation kinetics results. It is suggested a P (Bi₂O₃)-N (TiO₂) junction was formed to increase the catalytic activates. The stability of the electrode materials was confirmed finally.     

The interactive effect of agitation condition and titania particle size in hydrothermal synthesis of titanate nanostructures

The nucleation and growth mechanisms of hydrothermal synthesized nanotitanates are proposed based on the interaction effect between agitation condition and pristine titania particle size. TEM examination and N₂ adsorption measurements revealed distinct morphology and textural properties depending on TiO₂ particle size in constant agitation condition. Regarding to the supersaturation degree, heterogeneous nucleation dominates for nanotubes formation from large particle size of raw material. On the other hand, homogeneous nucleation determines nanospheres formation from small particle size of raw material. The nanotubes have an outer diameter ranging from 8 to 10 nm and inner diameter of 2 to 3 nm. The nanospheres have diameters ranging from 50 to 100 nm.     

Gold nanoparticle shape effects on human serum albumin corona interface: a molecular dynamic study

Three-dimensional (3D) hierarchical rutile TiO₂ microspheres composed of nanorods with diameter of several-tens of nanometers, with different morphologies and with average size ranging from 1.3 to 1.8 μm, were successfully synthesized through a surfactant-free solvothermal route. The effects of the solvents n-hexane, chloroform, and cyclohexane on the microstructures of 3D hierarchical TiO₂ nanostructures were investigated. Results of scanning electron microscopy showed that 3D sea-urchin like hierarchical TiO₂ composed of nanorods with a diameter of ~10 nm can only be prepared in the cyclohexane-water system. The growth mechanism of 3D sea-urchin like hierarchical TiO₂ composed of numerous nanorods was further examined and found to differ from the well-known “growth → assembly” mode. The effects of surface tension and polarity of solvents on the morphology and crystal strength of 3D hierarchical TiO₂ nanostructure were also investigated. In addition, the prepared 3D sea-urchin like hierarchical TiO₂ showed highest photocatalytic activity compared with other 3D hierarchical TiO₂ nanostructures in this study and Degussa P25 for the degradation of Rhodamine B solution under UV light irradiation, which could be attributed to its special hierarchical superstructure, the increase of surface catalytic sites and its special composition units.     

Hydrothermal synthesis and volatile organic compounds sensing properties of La–TiO2 nanobelts

We report the microstructure and gas-sensing properties of La–TiO₂ nanobelts prepared by the hydrothermal method. In particular, we make a comparison of the volatile organic compounds (VOCs) sensing properties between La–TiO₂ nanobelts and La–TiO₂ nanospheres. The results show that La–TiO₂ nanobelts exhibit higher gas response as well as lower working temperature as compared to that of La–TiO₂ nanospheres, suggesting that the gas sensing properties of nanocrystals can be significantly improved by tailoring the shape and the surface structure of nanocrystals.     

Preparation and photocatalytic activity of nitrogen-doped TiO2 hollow nanospheres

TiO₂ hollow nanospheres were prepared using silicon oxide as a template. N-doped titanium oxide hollow spheres, TiO_2−xN_x were synthesized by reacting TiO₂ hollow spheres with thiourea at 500 °C. XRD and XPS data showed that oxygen was successfully substituted by nitrogen through the nitrogen-doping reaction, and finally N-doped TiO₂ hollow spheres were formed. The N-doped TiO₂ hollow spheres showed new absorption shoulder in visible light region so that they were expected to exhibit photocatalytic activity in the visible light. The photocatalytic activity of N-doped TiO₂ hollow spheres under visible light was similar to that of normal spherical TiO_2−xN_x in spite of the structural difference.     

Evaluation of nanoparticle emission for TiO<Subscript>2</Subscript> nanopowder coating materials

In this study, nanoparticle emission of TiO₂ nanopowder coated on different substrates including wood, polymer, and tile, was evaluated in a simulation box and measured with a Scanning Mobility Particle Sizer (SMPS) for the first time. The coating process for the substrate followed the instructions given by the supply company. In the simulation box, UV light, a fan, and a rubber knife were used to simulate the sun light, wind, and human contacting conditions. Among the three selected substrates, tile coated with TiO₂ nanopowder was found to have the highest particle emission (22 #/cm³ at 55 nm) due to nanopowder separation during the simulation process. The UV light was shown to increase the release of particle below 200 nm from TiO₂ nanopowder coating materials. The results show that, under the conditions of UV lamps, a fan and scraping motion, particle number concentration or average emission rate decreases significantly after 60 and 90 min for TiO₂/polymer and TiO₂/wood, respectively. However, the emission rate continued to increase after 2 h of testing for TiO₂/tile. It is suggested that nanoparticle emission evaluation is necessary for products with nanopowder coating.     

TiO2 Nanotube Array/Monolayer Graphene Film Schottky Junction Ultraviolet Light Photodetectors

Schottky junctions made from a titanium dioxide nanotube (TiO₂NT) array in contact with a monolayer graphene (MLG) film are fabricated and utilized for UV light detection. The TiO₂NT array is synthesized by the anodization and the MLG through a simple chemical vapor deposition process. Photoconductive analysis shows that the fabricated Schottky junction photodetector (PD) is sensitive to UV light illumination with good stability and reproducibility. The corresponding responsivity (R), photoconductive gain (G), and detectivity (D*) are calculated to be 15 A W^?1, 51, and 1.5 × 10¹² cm Hz^1/2 W^?1, respectively. It is observed that the fabricated PD exhibits spectral sensitivity and a simple power‐law dependence on light intensity. Moreover, the height of the Schottky junction diode is derived to be 0.59 V by using a low temperature I–V measurement. Finally, the working mechanism of the TiO₂NT array/MLG film Schottky junction PD is elucidated.     

Ag/TiO2 sol prepared by a sol–gel method and its photocatalytic activity

Ag/TiO₂ sol with narrow particle size distribution was synthesized using TiCl₄ as the starting material. TiCl₄ was converted to Ti(OH)₄ gel. The Ag/TiO₂ sol was prepared by a process where H₂O₂ was added and then heated at 90–97 °C. After condensation reaction and crystallization, a transparent sol with suspended Ag/TiO₂ was formed. Ag/TiO₂ was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, contact angle analysis, and X-ray photoelectron spectroscopy. The photocatalytic properties of Ag/TiO₂ film were evaluated by degradation of methylene blue in aqueous solution under UV light irradiation. The suspended Ag/TiO₂ particles were rhombus primary particles with the major axis ca. 40 nm and the minor axis ca. 10 nm. Ag nanoparticles were well dispersed on TiO₂ and the particle size was only 1–2 nm. Ag could restrain the recombination of photo-generated electrons and holes effectively. Transparent thin films could be obtained through dip-coating glass substrate in the sol. The thin film had strong hydrophilicity after being illuminated by UV light. Ag/TiO₂ film showed a significant increase in photocatalytic activity compared to the TiO₂ film. The high amount of surface hydroxyls on Ag/TiO₂ film also played an important role in its photocatalytic activity.     

Natural hybrid organic–inorganic photovoltaic devices

Natural hybrid organic–inorganic photovoltaic devices based on TiO₂ have been realized. Chlorophyll A (from anacystis nidulans algae), chlorophyll B (from spinach), carmic acid (from insect Coccus cacti L.), synthetic trans-β-carotene, natural fresh picked Morus nigra, and their mixtures have been used as an organic photo active layer to fabricate photovoltaic prototypes. In order to reduce the charge’s interfacial recombination, different thicknesses (5–45 nm) of Si layers, subsequently oxidized in air, were inserted between the TiO₂ and chlorophyll B. Scanning electron microscopy of TiO₂ and Si/TiO₂ systems shows the coexistence at least of four classes of nanoparticles of 60, 100, 150 and 250 nm in size. Auger electron spectroscopy of the Si L_2,3V V transition demonstrates the presence of silica and SiO_x suboxides. Photocurrent measurements versus radiation wavelength in the range 300–800 nm exhibit different peaks according to the absorption spectra of the organic molecules.All realized photovoltaic devices are suitable for solar light electric energy conversion. Those made of a blend of all organic molecules achieved higher current and voltage output. The Si/TiO₂-based devices containing chlorophyll B exhibited an enhanced photocurrent response with respect to those with TiO₂ only.     

Study on the photocatalytic activity of TiN/TiO2 nanoparticle formed by ball milling

TiN/TiO₂ nanoparticle photocatalyst was prepared by ball milling of TiO₂ in H₂O solution doped with TiN. The photocatalyst was characterized by UV–Vis diffuse reflection spectroscopy, X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Based on the results of the characterization, the mechanism of the increase in photocatalytic activity was investigated. The results show that when the amount of doped TiN is 0.15 wt%, the photocatalytic activity of the TiN/TiO₂ is at its peak. Compared with TiO₂, the photoabsorption wavelength range of the TiN/TiO₂ photocatalyst red-shifts about 30 nm, and the photoabsorption intensity increases as well. The photocatalytic activities of the photocatalyst are higher than that of TiO₂ under UV and visible light irradiation. The increase of surface Ti³⁺ reactive center and the extension of the photoabsorption wavelength are the main factors for the increase in the photocatalytic activity of the TiN/TiO₂. Doped TiN neither changes the TiO₂ crystal phase nor creates new crystal phase by ball milling.     

Improving the electrical catalytic activity of Pt/TiO<Subscript>2</Subscript> nanocomposites by a combination of electrospinning and microwave irradiation

One of the greatest challenges in preparing TiO₂-based oxygen electrodes for PEM fuel cells is increasing the electrical catalytic activity of Pt nanoparticle/TiO₂ composites by improving the dispersion of Pt. This article describes a new way for improving the dispersion of Pt nanoparticles by depositing them on TiO₂ fibers and using microwave irradiation. The Pt nanoparticles used in this experiment is about 5 nm in diameter and the diameter of TiO₂ fibers could be controlled ranging from 30 to 60 nm and Pt nanoparticles still keep their size when the deposition amount is increased on the surface of TiO₂ fibers. The Pt nanoparticles were highly dispersed without agglomeration even at a weight percentage of composites as high as 40%. The position of Pt nanoparticles located in the fiber and the composition of Pt/TiO₂, which had great influence on the electric conductivity and electrical catalytic activity of the composite, could be easily controlled.     

Fabrication and characterization of CdS-sensitized TiO<Subscript>2</Subscript> nanotube photoelectrode

CdS quantum dot (Qd)-sensitized TiO₂ nanotube array photoelectrode is synthesised via a two-step method on tin-doped In₂O₃-coated (ITO) glass substrate. TiO₂ nanotube arrays are prepared in the ethylene glycol electrolyte solution by anodizing titanium films which are deposited on ITO glass substrate by radio frequency sputtering. Then, the CdS Qds are deposited on the nanotubes by successive ionic layer adsorption and reaction technique. The resulting nanotube arrays are characterized by scanning electron microscopy, X-ray diffraction (XRD) and UV–visible absorption spectroscopy. The length of the obtained nanotubes reaches 1.60 μm and their inner diameter and wall thickness are around 90 and 20 nm, respectively. The XRD results show that the as-prepared TiO₂ nanotubes array is amorphous, which are converted to anatase TiO₂ after annealed at 450 °C for 2 h. The CdS Qds deposited on the TiO₂ nanotubes shift the absorption edge of TiO₂ from 388 to 494 nm. The results show that the CdS-sensitized TiO₂ nanotubes array film can be used as the photoelectrode for solar cells.     

Controlling SERS intensity by tuning the size and height of a silver nanoparticle array

It is demonstrated that the surface-enhanced Raman scattering (SERS) intensity of R6G molecules adsorbed on a Ag nanoparticle array can be controlled by tuning the size and height of the nanoparticles. A firm Ag nanoparticle array was fabricated on glass substrate by using nanosphere lithography (NSL) combined with reactive ion etching (RIE). Different sizes of Ag nanoparticles were fabricated with seed polystyrene nanospheres ranging from 430 nm to 820 nm in diameter. By depositing different thicknesses of Ag film and lifting off nanospheres from the surface of the substrate, the height of the Ag nanoparticles can be tuned. It is observed that the SERS enhancement factor will increase when the size of the Ag nanoparticles decreases and the deposition thickness of the Ag film increases. An enhancement factor as high as 2×10⁶ can be achieved when the size of the polystyrene nanospheres is 430 nm in diameter and the height of the Ag nanoparticles is 96 nm. By using a confocal Raman mapping technique, we also demonstrate that the intensity of Raman scattering is enhanced due to the local surface plasmon resonance (LSPR) occurring in the Ag nanoparticle array.     

Controlled Formation of TiO2/MoS2 Core–Shell Heterostructures with Enhanced Visible‐Light Photocatalytic Activities

Most recently, much attention has been devoted to photocatalytic materials that may help to solve the global energy crisis and may provide environmental protection. Herein, novel cocatalysts based on few layered MoS₂ and TiO₂ nanomaterials have been designed by growing MoS₂ nanosheets on the surface of TiO₂ nanospheres through a facile hydrothermal method. The method allows the formation of TiO₂/MoS₂ core–shell heterostructures of uniform morphologies and stable structure and provides a good control over shell thickness. The mechanism that forms these heterostructures is discussed in detail. In addition, as cocatalyst, MoS₂ nanosheets can enlarge the light harvesting window to include visible light and improve the photocatalytic ability of TiO₂. Using Rhodamine B as the model, the resultant heterostructure is demonstrated to possess excellent and stable photocatalytic activity in the degradation of organic pollutants under visible light illumination. The TiO₂/MoS₂ heterostructures possess this catalytic activity due to their large surface area and their excellent interface for separating holes and electrons. Therefore, this novel heterostructure nanomaterials possess potential applications in water treatment, degradation of dye pollutants, and environmental cleaning.     

Amplification of Solar Energy Conversion in Quantum‐Confined CdSe‐Sensitized TiO2 Photonic Crystals by Trapping Light

Photonic effects amplifying solar energy conversion are reported in titania inverse opals sensitized with quantum‐confined CdSe films. TiO₂ inverse opals (i‐TiO₂‐o) and unstructured nanocrystalline TiO₂ (nc‐TiO₂) films are sensitized with CdSe deposited via successive ionic layer adsorption and reaction (SILAR) by generating Se^2? in situ under inert atmosphere, and the film absorbance is tuned by the number of SILAR cycles. Photonic effects are investigated while varying the i‐TiO₂‐o stop band position relative to CdSe films’ absorbance. i‐TiO₂‐o films with stop band at 700 and 560 nm are sensitized with CdSe having absorption edges at 600 and 650 nm thus tuning absorbance to the red and the blue of the stop band. Significant amplification in photon‐to‐current conversion efficiency is measured when CdSe films prepared via two cycles are adsorbed on i‐TiO₂‐o with a stop band at 700 nm, with a maximum average enhancement factor equal to 6.7 ± 1.6 at 640 nm, 60 nm to the blue of the stop band center, relative to nc‐TiO₂ sensitized with comparable CdSe amounts. The gain is observed over a wide frequency range to the blue of the stop band and is greatest when film absorbance was low. The photocurrent gain is not a result of differences in the rates of charge separation or charge transport, and occurs in the same frequency range where absorbance amplification is measured to the blue of the 700‐i‐TiO₂‐o stop band, and is thus attributed to slow light effects enhancing absorbance in the photonic crystal environment.     

The effect of carrier gas flow on structural and optical properties of TiO2 nanowires

Optical properties and photoluminescence of TiO₂ nanowires, synthesized by two-step thermal evaporation process, under different Ar gas flow as carrier have been studied. The gas flow was varied from 50 to 150 sccm in order to find the optimum gas flow to growth TiO₂ nanowires. As evidenced by X-ray diffraction patterns, our synthesized nanowires, were found to be crystalline rutile TiO₂. Our results indicated a convenient gas flow for controlling diameter size of nanowires was about 100 sccm. In this case, diameters and lengths were, respectively, within the ranges of 40–100 and 400–1800 nm. The experimental data of the reflectance of TiO₂ nanowires have been obtained through using spectrometer of wavelength 250–800 nm that has been indicated reflectance decreasing with increasing the gas flow, due to the scattering from the surface of the nanowires and also an increase in voids’ roughness. Under excitation 370 nm, the TiO₂ nanowires can emit light peaked at 435 nm. It is believed that peak 435 may be due to free excitons emission.     

First-principle calculations on optical properties of C-N-doped and C-N-codoped anatase TiO2

The electronic structures, dipole moment and optical properties of C-N-doped and C-N-codoped anatase titanium dioxide (TiO₂) are studied using the plane-wave ultrasoft pseudopotential method of density functional theory (DFT). The results revealed that the absorption coefficients of pure TiO₂ and N-doped TiO₂ are consistent with experimental values in the visible-light region. The bands originating from C/N-2p states lie in the band gap of doped TiO₂. A visible-light absorption edge red-shift can be observed. The atomic charges have changed, resulting in devation of the center of gravity of the negative electric charge from the positive electric charge in the super-cell, and their dipole moment would not be zero. The dipole moment has large influence on the optical responses in the visible region of TiO₂. Because of the small distance (0.531 nm) between C and N atoms, the covalent bond component was easily enhanced between C atom and adjacent O atom, the covalent bonds making it more difficult for the carrier transfer. Moreover, its optical absorption coefficient is going to reduce in the visible-light region. Under the condition of the larger distance (0.691 nm) between C and N atoms, their interaction can be reduced, which is beneficial to electrons transition; as a result, a significant improvement of the photocatalytic activity of TiO₂ has been found under the visible-light irradiation.     

Thickness dependent activity of nanostructured TiO2/α-Fe2O3 photocatalyst thin films

The effect of thickness of TiO₂ coating on synergistic photocatalytic activity of TiO₂ (anatase)/α-Fe₂O₃/glass thin films as photocatalysts for degradation of Escherichia coli bacteria in a low-concentration H₂O₂ solution and under visible light irradiation was investigated. Nanograined α-Fe₂O₃ films with optical band-gap of 2.06 eV were fabricated by post-annealing of thermal evaporated iron oxide thin films at 400 °C in air. Increase in thickness of the Fe₂O₃ thin film (here, up to 200 nm) resulted in a slight reduction of the optical band-gap energy and an increase in the photoinactivation of the bacteria. Sol-gel TiO₂ coatings were deposited on the α-Fe₂O₃ (200 nm)/glass films, and then, they were annealed at 400 °C in air for crystallization of the TiO₂ and formation of TiO₂/Fe₂O₃ heterojunction. For the TiO₂ coatings with thicknesses ≤50 nm, the antibacterial activity of the TiO₂/α-Fe₂O₃ (200 nm) was found to be better than the activity of the bare α-Fe₂O₃ film. The optimum thickness of the TiO₂ coating was found to be 10 nm, resulting in about 70 and 250% improvement in visible light photo-induced antibacterial activity of the TiO₂/α-Fe₂O₃ thin film as compared to the corresponding activity of the bare α-Fe₂O₃ and TiO₂ thin films, respectively. The improvement in the photoinactivation of bacteria on surface of TiO₂/α-Fe₂O₃ was assigned to formation of Ti-O-Fe bond at the interface.