Binding affinities of amino acid analogues at the charged aqueous titania interface : implications for titania-binding peptides

Despite the extensive utilization of biomolecule-titania interfaces, biomolecular recognition and interactions at the aqueous titania interface remain far from being fully understood. Here, atomistic molecular dynamics simulations, in partnership with metadynamics, are used to calculate the free energy of adsorption of different amino acid side chain analogues at the negatively-charged aqueous rutile TiO2 (110) interface, under conditions corresponding with neutral pH. Our calculations predict that charged amino acid analogues have a relatively high affinity to the titania surface, with the arginine analogue predicted to be the strongest binder. Interactions between uncharged amino acid analogues and titania are found to be repulsive or weak at best. All of the residues that bound to the negatively-charged interface show a relatively stronger adsorption compared with the charge-neutral interface, including the negatively-charged analogue. Of the analogues that are found to bind to the titania surface, the rank ordering of the binding affinities is predicted to be "arginine" > "lysine" ≈ aspartic acid > "serine". This is the same ordering as was found previously for the charge-neutral aqueous titania interface. Our results show very good agreement with available experimental data and can provide a baseline for the interpretation of peptide-TiO2 adsorption data.

Photocatalytic degradation of dyes in wastewater using TiO2/UV in a flat-plate reactor

The photocatalyst TiO₂ with UV irradiation was used to degrade dyes in textile effluent in a flat-plate photoreactor. A test system was built with the reactor area of 1 x 0.3m2, UV light of six 36W-blacklight. TiO₂ powder P25 with BET surface area 50±15m2/g, average primary particle size 21 nm, purity> 99.5% and content of 83.9% anatase and 16.1 % rutile was used as the photocatalyst. A number of dyes commonly present in dyeing wastewater were tested in this study. The different operating parameters, such as dosage of photocatalyst, the structure of the reactor, flow rates through the flat-plate reactor, UV radiation intensity and tilted angle of the reactor, were investigated. The results showed that the photocatalytic process could efficiently remove most of the colour contained in the dyeing wastewater. It was experimentally observed that first-order kinetics was adequate for characterising the process. The flow rate and the tilted angle had some influence on the film thickness of the fluid in the reactor and the empirical correlation between the film thickness of the fluid and these two parameters was developed. The photoreaction rate was mainly determined by the film thickness of the fluid on the reactor surface and the dosage of the photocatalyst. Optimum operating parameters of the system were found to be at the film thickness of about 1.4mm and a TiO₂ dosage of 1 gIL. The higher the UV intensity, the faster the reaction rate was. The results of these experiments showed that this method has the great potential for colour removal from wastewater at commercial scale.

To overcome the common difficulty of separating the used TiO₂ suspension after treatment precipitation followed with filtration was used in this study to determine the separation efficiencies. On the other hand, TiO₂ in a small pillar shape was also studied for photocatalytic degradation of textile dye effluent. The pillar pellet was made in Oegussa Company, Germany ranging from 2.5 to 5.3mm long and with a diameter of 3.7mm. It was almost pure TiO₂ (83.2% anatase and 16.8% rutile), with a S-content of <20 ppm and a CI content of the order of 0.1 wt. %. No further elements are present in contents above 0.05 wt.%. The TiO₂ pillars were placed on the flat-plate reactor that was divided by the rectangular slots and irradiated under UV light when the treated solution went through the reactor. Four dyes and their mixtures were tested. The results showed that the photocatalytic process under this configuration efficiently remove the colour from textile dyeing effluent, and pillar shape TiO₂ photocatalyst was not dissolved in water and very easy to be separated from solution, enabling it to be reused many times. The first-order kinetics was adequate for characterising the photocatalytic degradation process and the photocatalytic performance was comparable to TiO₂ powder. It is believed that the TiO₂ pellet would be a preferable form of photocatalyst in applications for textile effluent treatment process, and other wastewater treatment processes.

One-dimensional growth of TiO2 nanorods from ilmenite sands

Growth mechanisms of TiO₂ nanorods synthesized from mineral ilmenite using ball milling and annealing method have been systematically investigated. Two annealing processes are needed to grow the nanorods. The heating rate and gaseous environment in the first annealing step are critical to the formation of intermediate phases; these and the annealing atmosphere in the second heating play very important roles in nanorod growth. One-dimensional growth of the nanorods induced by low-temperature annealing in nitrogen plus hydrogen is possibly driven by atom vacancy diffusion in addition to surface diffusion.

Phase-structure effects of electrospun TiO2 nanofiber membranes on As(III) adsorption

TiO2 nanofibers (NFs) with different phases such as amorphous, anatase, mixed anatase?rutile, and rutile have been prepared by combining the electrospinning technique with the subsequent process of heat treatment or acidic-dissolution method. The obtained NFs are characterized by a Fourier transform infrared spectrometer (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption?desorption isotherm measurements. Phase structure effects of electrospun TiO2 NFs on As(III) adsorption behaviors have been investigated. The results showed a significant effect of the phase structures of TiO2 NFs on As(III) adsorption rates and capacities. Amorphous TiO2 NFs have the highest As(III) adsorption rate and capacity in the investigated samples, which can be attributed to its higher surface area and porous volume. This research provides a simple and low-cost method for phasecontrolled fabrication of TiO2 NFs and application for effective removal of arsenic from aqueous solution.

Experimental study of the degradation of volatile organic compounds by photocatalytic oxidation using TiO2 pellets

A fixed bed photocatalytic reactor has been designed and built with a UV
radiation source. Ti02 pellets were placed on the three fixed beds within the
reactor. Acetone was used as an indicator of volatile organic compounds (VOCs) during the experiment. Under the flow rate of 12.75 l/min, the oxidation efficiencies were obtained at four different concentrations of acetone laden gas streams ranged from 40ppm to 250ppm. It was found that the lower the acetone concentration of the untreated inlet gas, the higher the oxidation efficiency; the obtained oxidation efficiency was in the range of 40-70% for various concentrations of untreated gases.

Degradation of VOCs by phototcatalytic oxidation reactor using TiO2 pellets

Volatile Organic Compounds (VOCs) are air pollutants that come from burning fossil fuels and industrial emissions. They have potentially adverse health effects being carcinogenic and highly persistent in the environment. The use of photocatalytic oxidation to remove VOCs has the potential to be applied in indoor air quality improvement and industrial emission control. A fixed bed photocatalytic reactor was designed and built. UV black light lamps were installed in the reactor to provide a source of UV radiation. A non-film titania media as pellets were placed on the three fixed beds within the reactor. Toluene and acetone were used as indicators of VOCs during the experiment. With a flow rate of 12.75l/min, the oxidation efficiencies were obtained at four different concentrations of acetone laden gas streams ranging from 40ppm to 250ppm. It was found that the lower the acetone concentration of the untreated inlet gas, the higher the oxidation efficiency. The oxidation efficiency was in the range of 40–70% for various concentrations of untreated gases. Two concentrations of toluene laden gas stream were also tested using the same reactor. The oxidation efficiencies were found as 50% for 120ppm toluene gas and 45% for 300ppm toluene gas. It was found that the times required for toluene to reach oxidization equilibrium have been halved than for acetone gas stream. Other parameters such as flow rate and UV intensity were also altered to see their effects on the oxidation efficiency. A full spectrum scan was carried out using a Bio-rad Infrared spectrometer. It was found that the main components of the treated gas stream from the outlet of the reactor were CO2 and water along with small amount of untreated acetone. The suspected intermediates of aliphatic hydrocarbons and CO were found in very minimal amounts or undetectable. The research experiments supported that the TiO2 pellets can work effectively in a fixed bed photocatalytic reactor and achieve significant oxidation efficiencies for degradation of toluene and acetone as indicators of VOCs.

A comparative study on preparation of TiO2 pellets as photocatalysts based on different precursors

The porous Ti0₂ pellets were prepared based on pigment grade titaina, P25 titania powder and titaniurn(lV) butoxide. The characterization was done with X-Ray diffraction, scanning electron microscopy and BET measurements. The result shows that Ti0₂ pellets by using titaniurn(IV) butoxide with some addictive have the best surface porosity, with specific surface area of 196.9m²/g. For pigment grade titania and P25 titania powder, it is still effective to enhance the surface area after reassembling. The surface area increased from 11.6 to 29.2 m²/g for pigment grade titania and from 50 to 84.4 m²/g for P25 titania powder. Furthermore, it has been investigated on how to optimize and get the highest surface area by controlling the sintering temperature, reaction temperature, pH of solution, and the amount of alcohol and addictive of surfactant during preparation. The experimental photocatalytic degradation of acetone and toluene was performed using titania pellets made from P25 titania powder.

Photocatalytic reduction of carbon dioxide into gaseous hydrocarbon using TiO2 pellets

It has been shown that CO₂ could be transformed into hydrocarbons when it is in contact with water vapour and catalysts under UV irradiation. This paper presents an experimental set-up to study the process employing a new approach of heterogeneous photocatalysis using pellet form of catalyst instead of immobilized catalysts on solid substrates. In the experiment, CO₂ mixed with water vapour in saturation state was discharged into a quartz reactor containing porous TiO₂ pellets and illuminated by various UV lamps of different wavelengths for 48 h continuously. The gaseous products extracted were identified using gas chromatography. The results confirmed that CO₂ could be reformed in the presence of water vapour and TiO₂ pellets into CH₄ under continuous UV irradiation at room conditions. It showed that when UVC (253.7 nm) light was used, total yield of methane was approximately 200 ppm which was a fairly good reduction yield as compared to those obtained from the processes using immobilized catalysts through thin-film technique and anchoring method. CO and H₂ were also detected. Switching from UVC to UVA (365 nm) resulted in significant decrease in the product yields. The pellet form of catalyst has been found to be attractive for use in further research on photocatalytic reduction of CO₂.

Sol-gel derived HA/TiO2 double coatings on Ti scaffolds for orthopaedic applications

Hydroxyapatite/titania (HA/TiO₂) double layers were coated onto Ti scaffolds throughout for orthopaedic applications by sol-gel method. Differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and X-ray diffractometry (XRD) were used for the characterisation of the phase transformations of the dried gels and coated surface structures. Scanning electron microscope (SEM) equipped with energy dispersive spectrometry (EDS) was used for the observation and evaluation of the morphology and phases of the surface layers and for the assessment of the in vitro tests. The in vitro assessments were performed by soaking the HA/TiO₂ double coated samples into the simulated body fluid (SBF) for various periods. The TiO₂ layer was coated by a dipping-coating method at a speed of 12 cm/min, followed by a heat treatment at 600 °C for 20 min. The HA layer was subsequently dipping-coated on the outer surface at the same speed and then heat-treated at difference temperatures. The results indicat that the HA phase begins to crystallize after a heat treatment at 560 °C. The crystallinity increases obviously at 760 °C. SEM observations find no delamination or crack at the interfaces of HA/TiO₂ and TiO₂/Ti. The HA/TiO₂ coated Ti scaffolds displays excellent bone-like apatite forming ability when it is soaked into SBF. Ti scaffolds after HA/TiO₂ double coatings can be anticipated as promising implant materials for orthopaedic applications