Antimicrobial properties of silver nanoparticles synthesized by bioaffinity adsorption coupled with TiO2 photocatalysis

BACKGROUND: On the basis of effective bioaffinity adsorption of Ag⁺, silver nanoparticles (Ag NPs) were synthesized on the surface of chitosan‐TiO₂ adsorbent (CTA) by TiO₂ photocatalysis for crystal growth. RESULTS: Among the microstructure characterizations of the resulting silver nanoparticles‐ loaded chitosan‐TiO₂ adsorbent (Ag‐CTA), X‐ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with energy dispersive X‐ray (EDX) revealed the formation of metallic Ag on the CTA, which was further confirmed by the surface plasmon resonance of Ag NPs in the UV‐visible absorption spectrum. The underlying mechanism behind the formation of Ag NPs on the CTA by TiO₂ photoreduction was studied by Fourier transform infrared (FTIR) spectroscopy. The distinctive feature of Ag‐CTA after adsorption was the highly efficient antimicrobial activity in inactivating different test strains. In the case of Escherichia coli, 1.50 mg 1.67 wt% Ag‐CTA could totally inhibit 1.0–1.2 × 10⁷ colony forming units (CFU) in 100 mL nutrient medium, which was superior to that previously reported. CONCLUSIONS: CTA effectively adsorbed the precious metal ion Ag⁺ onto active imprinting sites on the adsorbent and then exerted efficient antimicrobial effects against diverse microbes. This research will be useful for designing a novel CTA‐based wastewater treatment for multi‐functional performance. Copyright © 2010 Society of Chemical Industry     

Enhanced adsorption of two azo dyes produced by carbon modification of TiO2

The process of removal of two azo dyes (Reactive Red 198 and Direct Green 99) from water was investigated. The adsorption of azo dyes onto surfaces of pristine TiO₂, P25 and carbon-modified TiO₂ (at 120 °C for 24 h) was presented. The Freundlich model of adsorption isotherm was found for pristine TiO₂ and TiO₂-P25. Modification of TiO₂ by carbon lead to the change from the Freundlich model to the Langmuir model of adsorption isotherm. For the TiO₂-C photocatalyst the adsorption capacity was determined, which was almost two times higher for Direct Green 99 than Reactive Red 198 dyes. As a result we observed the increase of photocatalytic activity of carbon-modified TiO₂ photocatalyst.     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Phorate degradation by TiO2 photocatalysis: Parameter and reaction pathway investigations

The photocatalytic degradation of phorate in aqueous suspensions was examined with the use of titanium dioxide (TiO₂) as a photocatalyst. About 99% of phorate was degraded after UV irradiation for 60 min. The photodegradation of phorate followed pseudo-first-order kinetics and parameters such as pH of the system, TiO₂ dosage, and presence of anions were found to influence the reaction rate. To obtain a better understanding of the mechanistic details of this TiO₂-assisted photodegradation of phorate with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) techniques. The probable photodegradation pathways were proposed and discussed. To the best of our knowledge, this is the first study that reports the degradation pathways of phorate. The electrical energy consumption per order of magnitude for photocatalytic degradation of phorate was also calculated and showed that a moderated efficiency (E_EO = 96 kWh/(m³ order)) was obtained in TiO₂/UV process.     

Photocatalytic degradation of methylene blue with TiO2 nanoparticles prepared by a thermal decomposition process

The generation of TiO₂ nanoparticles by the thermal decomposition of titanium tetraisopropoxide (TTIP) was carried out experimentally using a tubular electric furnace at various synthesis temperatures (700-1300 °C) and TTIP heating temperatures (80-110 °C). The photocatalytic activity of the resulting TiO₂ nanoparticles was examined by measuring the rate of methylene blue decomposition. The TiO₂ nanoparticles were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) measurements and transmission electron microscopy (TEM). The crystallite size and crystallinity increased with increasing synthesis temperature and TTIP heating temperature. A TTIP heating temperature and synthesis temperature of 95 °C and 900 °C, respectively, were found to be the optimal synthesis conditions. The primary particle diameter obtained under optimum synthesis conditions was considerably smaller than the commercial photocatalyst (Degussa, P25). The specific surface areas were more than 134.4 m² g^− 1. Under the optimal conditions, the photocatalytic activity for methylene blue was higher than that of the commercial photocatalyst.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Combined TiO2/SiO2 mesoporous photocatalysts with location and phase controllable TiO2 nanoparticles

Combined TiO₂/SiO₂ mesoporous materials were prepared by deposition of TiO₂ nanoparticles synthesised via the acid-catalysed sol–gel method. In the first synthesis step a titania solution is prepared, by dissolving titaniumtetraisopropoxide in nitric acid. The influences of the initial titaniumtetraisopropoxide concentration and the temperature of dissolving on the final structural properties were investigated. In the second step of the synthesis, the titania nanoparticles were deposited on a silica support. Here, the influence of the temperature during deposition was studied. The depositions were carried out on two different mesoporous silica supports, SBA-15 and MCF, leading to substantial differences in the catalytic and structural properties. The samples were analysed with N₂-sorption, X-ray diffraction (XRD), electron probe microanalysis (EPMA) and transmission electron microscopy (TEM) to obtain structural information, determining the amount of titania, the crystal phase and the location of the titania particles on the mesoporous material (inside or outside the mesoporous channels). The structural differences of the support strongly determine the location of the nanoparticles and the subsequent photocatalytic activity towards the degradation of rhodamine 6G in aqueous solution under UV irradiation.     

Effect of TiO2 particle size on the photocatalytic reduction of CO2

Pure TiO₂ anatase particles with a crystallite diameters ranging from 4.5 to 29 nm were prepared by precipitation and sol–gel method, characterized by X-ray diffraction (XRD), BET surface area measurement, UV–vis and scanning electron microscopy (SEM) and tested in CO₂ photocatalytic reduction. Methane and methanol were the main reduction products. The optimum particle size corresponding to the highest yields of both products was 14 nm. The observed optimum particle size is a result of competing effects of specific surface area, charge–carrier dynamics and light absorption efficiency.     

Photoinduced activation of CO2 on TiO2 surfaces: Quantum chemical modeling of CO2 adsorption on oxygen vacancies

Chemical processes that utilize CO₂ emissions from coal-fired power plants will be required as the world progresses towards reducing CO₂ emissions. The conversion of CO₂ using light energy (CO₂ photoreduction) has the potential to produce useful fuels or valuable chemicals while decreasing CO₂ emissions from the use of fossil fuels such as coal. Computational studies on the initial steps of photoinduced CO₂ activation on TiO₂ surfaces, necessary to develop a mechanistic understanding of CO₂ photoreduction are a focus of this article.The results from previous quantum mechanical modeling studies conducted by the authors indicated that stoichiometric TiO₂ surfaces likely do not promote electron transfer to CO₂. Therefore, the role of oxygen vacancies in promoting the light-induced conversion of CO₂ (CO₂ photoreduction) on TiO₂ surfaces was examined in this study. Two different side-on bonded bent-CO₂ (bridging Ti-CO₂^δ•−-Ti species) were formed on the reduced rutile (110) and anatase (010), (001) surfaces, indicating charge transfer from the reduced surface to CO₂. Further steps in the photoexcitation of these bent-CO₂ species were investigated with density functional theory calculations. Consistent with CO₂ adsorption and photodesorption on other n-type metal oxides such as ZrO₂, the results suggest that the bent-CO₂ species do not gain further charge from the TiO₂ surface under illumination and are likely photodesorbed as neutral species. Additionally, although the formation of species such as CO and HCHO is thermodynamically possible, the energy needed to regenerate the oxygen vacancy on TiO₂ surfaces (~ 7 eV) is greater than that available through band-gap illumination (3.2 eV). Therefore, CO₂ reactions with water on irradiated anatase TiO₂ surfaces are likely to be stoichiometric.     

TiO2 nanotubes and CNT–TiO2 hybrid materials for the photocatalytic oxidation of propene at low concentration

In this work, we investigated titanium dioxide (TiO₂) nanotubes and CNT–TiO₂ hybrid materials for the photocatalytic oxidation (PCO) of propene at low concentration (100 ppmv) in gaseous phase. The materials were prepared via sol–gel method using sacrificial multi-walled carbon nanotubes (CNT) as templates and subsequent heat treatments to obtain the desired crystalline phase (anatase, rutile or a mixture of both) and eventually to remove the carbon template. We also studied rutile nanotubes for the first time and demonstrate that the activity strongly depends on the crystalline composition, following rutile < anatase < anatase/rutile mixture. The enhanced activity of the anatase–rutile mixture is attributed to the decrease in the electron–hole pair recombination due to the multiphasic nature of the particles. The key result of this work is the exceptional performance of the CNT–TiO₂ hybrid, which yielded the highest observed photocatalytic activity. The improved performance is attributed to synergistic effects due to the hybrid nature of the material, resulting in small anatase crystalline sizes (CNT act as heat sinks) and a reduced electron–hole pair recombination rate (CNTs act as electron traps). These results demonstrate the great potential of hybrid materials and stimulate further research on CNT-inorganic hybrid materials in photocatalysis and related areas.     

Synthesis of silver/SiO2/Eu:Lu2O3 core-shell nanoparticles and their polymer nanocomposites

We report a core-shell approach that combines silver nanoparticles as the metal core component with Eu:Lu₂O₃ as the phosphor shell component. The core-shell design contains an optically transparent SiO₂ intermediate layer that separates the metallic nanoparticle core and the phosphor shell. The thickness of the SiO₂ layer is in the nanometer range and can be tuned, so as to provide for different interactions between the core and shell. To demonstrate the versatility of the design, spherical silver nanoparticles or wavelength-tunable plasmonic silver nanoplates are used as the core component. In addition, a nanocomposite phosphor was fabricated by embedding the core-shell nanoparticles into a transparent polymeric matrix. The core-shell metal-phosphor design presented here serves as framework for the fabrication of inexpensive nanocomposite scintillator.     

Disinfection of spring water and secondary treated municipal wastewater by TiO2 photocatalysis

The photocatalytic disinfection of spring water and secondary treated municipal wastewater by means of UV-A irradiation over TiO₂ suspensions was investigated. Water samples were taken from a spring supplying water to the city of Chania, Western Crete, Greece, while wastewater samples were collected from the outlet of the secondary treatment of Chania municipal wastewater treatment plant. The effect of various operating parameters such as photocatalyst type (rutile, anatase, mixture of anatase and rutile) and concentration (0.5-1 g/L), contact time (up to 60 min) and sample pH (6-8) on the disinfection as assessed in terms of faecal indicator microorganisms (total coliforms and enterococci) inactivation was examined. A commercially available Degussa P25 TiO₂ powder, consisting of 75% anatase and 25% rutile, was found substantially more active than pure anatase or rutile for both groups of bacteria inactivation which increased with increasing contact time and catalyst concentration, whereas small pH changes had little effect on destruction. For both groups of bacteria tested, inactivation followed a first order kinetic expression with the gram positive Enterococcus sp. being considerably more resistant to photocatalytic disinfection than total coliforms.     

Synthesis and electrochemiluminescence of the CeO2/TiO2 composite

CeO₂/TiO₂ composite with kernel–shell structure was synthesized by a sol–gel process. The characterization results show that the composite is made up of anatase phase TiO₂ and cubic system CeO₂. The electrochemiluminescence (ECL) behavior of the CeO₂/TiO₂ composite was studied by a cyclic voltammetry in the presence of persulfate, and the effect factors on ECL emission were discussed. Based on a series of experiments, it is proposed that the strong dual ECL emission produced by the CeO₂/TiO₂ composite resulted from the benefit ECL effect of interface heterojunction in composite.     

Synthesis, microstructure, and photocatalysis of In2O3 hollow particles

Indium oxide (In₂O₃) microspheres with hollow interiors have been prepared by a facile implantation route which enables indium ions released from indium-chloride precursors to implant into nonporous polymeric templates in C₂Cl₄ solvent. The templates are then removed upon calcination at 500 °C in air atmosphere, forming hollow In₂O₃ particles. Specific surface area (0.5-260 m² g⁻¹) and differential pore volume (7 × 10⁻⁹ to 3.8 × 10⁻⁴ m³ g⁻¹ Å⁻¹) of the hollow particles can be tailored by adjusting the precursor concentration. For the hollow In₂O₃ particles with high surface area (260 m² g⁻¹), an enhanced photocatalytic efficiency (up to ∼one-fold increase) against methylene blue (MB) dye is obtained under UV exposure for the aqueous In₂O₃ colloids with a dilute solids concentration of 0.02 wt.%.     

Preparation of UO2/TiO2 composite ceramic fuel by sol gel-press forming method

This paper studies the preparation of UO₂/TiO₂ composite ceramic fuel through sol gel-press forming. The research shows that at 1200–1300 °C, UO₂/TiO₂ composite ceramic grains are small, uniform and compact. Among them, UO₂–0.5 wt%TiO₂ has the highest density and good mechanical strength at 1250 °C.     

Influence of TiO2 and CeO2 on the hydrogenation activity of bulk Ni2P

TiO₂- and CeO₂-promoted bulk Ni₂P catalysts were prepared by impregnation and in-situ H₂ temperature-programmed reduction method. The prepared catalysts were characterized by XRD and XPS. The hydrogenation activities of the catalysts were studied using 1.5 wt.% 1-heptene in toluene and 1.0 wt.% phenylacetylene in ethanol as the model feeds. The results indicate that bulk Ni₂P possesses low hydrogenation activity but is tunable by simply controlling the content of the additives (TiO₂ or CeO₂), suggesting that TiO₂ and CeO₂ are effective promoters to enhance the hydrogenation activity of Ni₂P.