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ABSTRACT: Visible-light-induced antibacterial activity of carbon-doped anatase-brookite titania nano-heterojunction photocatalysts are reported for the first time. These heterostructures were prepared using a novel low temperature (100 °C) non-hydrothermal low power microwave (300 W) assisted method. Formation of interband C 2p states was found to be responsible for the band gap narrowing of the carbon doped heterojunctions. The most active photocatalyst obtained after 60 minutes of microwave irradiation exhibits a 2-fold higher visible-light induced photocatalytic activity in contrast to the standard commercial photocatalyst Evonik-Degussa P-25. Staphylococcus aureus inactivation rate constant for carbon-doped nano-heterojunctions and the standard photocatalyst was 0.0023 and -0.0081 min-1 respectively. It is proposed that the photo-excited electrons (from the C 2p level) are effectively transferred from the conduction band of brookite to that of anatase causing efficient electron-hole separation, which is found to be responsible for the superior visible-light induced photocatalytic and antibacterial activities of carbon-doped anatase-brookite nano-heterojunctions.
ACS Applied Materials & Interfaces 02/2013; · 4.53 Impact Factor
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ABSTRACT: A novel ambient pressure microwave assisted technique is developed in which silver and indium-modified ZnS is synthesized. The as-prepared ZnS is characterized by x-ray diffraction, UV-vis spectroscopy, x-ray photoelectron spectroscopy and luminescence spectroscopy. This procedure produced crystalline materials with particle sizes below 10 nm. The synthesis technique leads to defects in the crystal which induce mid-energy levels in the band gap and lead to indoor light photocatalytic activity. Increasing the amount of silver causes a phase transition from cubic blende to hexagonal phase ZnS. In a comparative study, when the ZnS cubic blende is heated in a conventional chamber furnace, it is completely converted to ZnO at 600 °C. Both cubic blende and hexagonal ZnS show excellent photocatalytic activity under irradiation from a 60 W light bulb. These ZnS samples also show significantly higher photocatalytic activity than the commercially available TiO(2) (Evonik-Degussa P-25).
Nanotechnology 01/2013; 24(4):045704. · 3.98 Impact Factor
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ABSTRACT: a b s t r a c t Nanocrystalline photocatalysts, prepared under ambient conditions using a microwave assisted syn-thesis, show indoor light photocatalytic activity for the degradation of Staphylococcus aureus and Escherichia coli. The zinc sulphide (ZnS) nanomaterials, prepared by a microwave assisted synthesis, are shown to be cubic blende structure with an average crystallite size of 4–6 nm. The anti-bacterial activ-ity of these nanomaterials is investigated under irradiation from a 60 W light bulb and photocatalytic activity is revealed to be due to the defects present in the crystal structure. The ZnS shows anti-bacterial action as both a bacteriostatic and bacteriocidal (88% reduction in the amount of bacteria in 5 h) material and the methods of bacterial degradation on the ZnS is discussed. The anti-bacterial actions of these materials were also compared with commercial ZnS and Evonik-Degussa P-25. A detailed mechanism for the light absorption in the visible light region of the microwave prepared ZnS is proposed based on the luminescence spectroscopy.
Applied Catalysis B: Environmental 01/2013; 130(131):106-111. · 5.63 Impact Factor
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ABSTRACT: Highly visible-light-active S,N-codoped anatase-rutile heterojunctions are reported for the first time. The formation of heterojunctions at a relatively low temperature and visible-light activity are achieved through thiourea modification of the peroxo-titania complex. FT-IR spectroscopic studies indicated the formation of a Ti(4+)-thiourea complex upon reaction between peroxo-titania complex and thiourea. Decomposition of the Ti(4+)-thiourea complex and formation of visible-light-active S,N-codoped TiO(2) heterojunctions are confirmed using X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and UV/vis spectroscopic studies. Existence of sulfur as sulfate ions (S(6+)) and nitrogen as lattice (N-Ti-N) and interstitial (Ti-N-O) species in heterojunctions are identified using X-ray photoelectron spectroscopy (XPS) and FT-IR spectroscopic techniques. UV-vis and valence band XPS studies of these S,N-codoped heterojunctions proved the fact that the formation of isolated S 3p, N 2p, and Π* N-O states between the valence and conduction bands are responsible for the visible-light absorption. Titanium dioxide obtained from the peroxo-titania complex exists as pure anatase up to a calcination temperature as high as 900 °C. Whereas, thiourea-modified samples are converted to S,N-codoped anatase-rutile heterojunctions at a temperature as low as 500 °C. The most active S,N-codoped heterojunction 0.2 TU-TiO(2) calcined at 600 °C exhibits a 2-fold and 8-fold increase in visible-light photocatalytic activities in contrast to the control sample and the commercial photocatalyst Degussa P-25, respectively. It is proposed that the efficient electron-hole separation due to anatase to rutile electron transfer is responsible for the superior visible-light-induced photocatalytic activities of S,N-codoped heterojunctions.
Inorganic Chemistry 06/2012; 51(13):7164-73. · 4.60 Impact Factor
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ABSTRACT: In order to study the visible light photocatalytic activity of nitrogen doped titanium dioxide, the interaction between nitrogen dopant sources and titania precursors during sol-gel synthesis is investigated. N-TiO(2) was synthesised using the sol-gel method using 1,3-diaminopropane as a nitrogen source. Samples were annealed several temperatures and the percentage of rutile present determined by X-ray diffraction to be 0% (500°C), 46% (600°C), and 94% (700°C). The reducing amounts of anatase at higher temperatures are studied using FTIR, which suggests the absence of any polymeric chains formed by the chelating agents, which would normally extend anatase-to-rutile transformation temperatures. Differential scanning calorimetry shows that crystalliation occurs before 500°C, providing the crystalline form determined by XRD at 500°C. Increased temperature also resulted in diminished visible light absorption capability, with only the 500°C sample showing significant absorption in the visible region. XPS studies revealed that nitrogen remained within the TiO(2) lattice at higher temperatures. Consequent with the reduced visible light absorption capacity, photocatalytic activity also reduced with increased annealing temperature. Degradation kinetics of methylene blue, irradiated with a 60 W house-bulb, resulted in first order degradation rates constants of 0.40 × 10(-2), 0.19 × 10(-2), and 0.22 × 10(-2)min(-1) for 500, 600, and 700°C respectively. Degradation of Degussa P25 was minimal under the same conditions, and that of undoped TiO(2) was 0.02 × 10(-2)min(-1). Similarly, using 4-chlorophenol under solar irradiation conditions, the N-doped sample at 500°C substantially out-performed the undoped sample. These results are discussed in the context of the effect of increasing temperature on the nature of the band gap.
Journal of hazardous materials 09/2011; 211-212:88-94. · 4.14 Impact Factor
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Advanced Functional Materials 08/2011; 21(19):3744 - 3752. · 10.18 Impact Factor
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ABSTRACT: In the absence of a dopant or precursor modification, anatase to rutile transformation in synthetic TiO2 usually occurs at a temperature of 600−700 °C. Conventionally, metal oxide dopants (e.g., Al2O3 and SiO2) are used to tune the anatase to rutile transformation. A simple methodology is reported here to extend the anatase rutile transformation by employing various concentrations of urea. XRD and Raman spectroscopy were used to characterize various phases formed during thermal treatment. A significantly higher anatase phase (97%) has been obtained at 800 °C with use of a 1:1 Ti(OPr)4:urea composition and 11% anatase composition is retained even after calcining the powder at 900 °C. By comparison a sample that has been prepared without urea showed that rutile phases started to form at a temperature as low as 600 °C. The effect of smaller amounts of urea such as 1:0.25 and 1:0.5 Ti(OPr)4:urea has also been studied and compared. The investigation concluded that the stoichiometric modification by urea 1:1 Ti(OPr)4:urea composition is most effective in extending the anatase to rutile phase transformation by 200 °C compared to the unmodified sample. In addition, BET analysis carried out on samples calcined at 500 °C showed that the addition of urea up to 1:1 (Ti(OPr)4:urea) increased the total pore volume (from 0.108 to 0.224 cm3/g) and average pore diameter (11 to 30 nm) compared to the standard sample. Samples prepared with 1:1 Ti(OPr)4:urea composition calcined at 900 °C show significantly higher photocatalytic activity compared to the standard sample prepared under similar conditions. Kinetic analysis shows a marked increase in the photocatalytic degradation of rhodamine 6G on going from the standard sample (0.027 min-1, decoloration in 120 min) to the urea-modified sample (0.073 min-1, decoloration in 50 min).
01/2007;
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ABSTRACT: The interactions between luminophore [Ru(bpy)3]2+, and the lacunary Dawson heteropolyanions, [P2W17O61(FeOH2)]7-, [P2W17O61(FeBr)]6- and [P2W17O61]10- were investigated using a combination of photophysics, optical and Raman spectroscopy. Extensive quenching of the excited state of [Ru(bpy)3]2+ was observed in each case. Quenching is attributed to the formation of association complexes between [Ru(bpy)(3)]2+ and the heteropolyanions in which the charge on the heteropolyanions is fully compensated for by the ruthenium polypyridyl species. The interaction appears to be principally electrostatic in nature producing [Ru(bpy)3]3.5[P2W17O61(FeOH2)], [Ru(bpy)3]3[P2W17O61(FeBr)] and [Ru(bpy)3]5[P2W17O61]10-. The association constants for formation of the clusters were obtained from photophysical studies and surprisingly, despite the electrostatic nature of the interaction, there was no correlation between the charge on the polyoxometallate and the association constant. In particular, the unsubstituted lacunary, [P2W17O61]10-, showed considerably weaker association compared to the transition metal substituted lacunaries, in spite of its 10- charge. Difference absorption spectroscopy revealed a new transition at ca. 480 nm for each of the cluster complexes. From resonance Raman spectroscopy the origin of this transition was found to involve the polyoxometallate. Unlike previously reported adducts, the cluster complexes formed were not luminescent. In all cases the cluster complexes exhibit remarkable photostability, with no photodecomposition or photo-induced ligand exchange reactions evident in acetonitrile, under conditions where [Ru(bpy)3]2+ alone exhibits considerable photolability.
Physical Chemistry Chemical Physics 11/2005; 7(19):3426-33. · 3.57 Impact Factor
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ABSTRACT: The interactions between [Ru(bpy)3]2+ and the polyoxotungstate anion [S2W18O62]4- in acetonitrile solution were investigated using a combination of photophysics and optical and Raman spectroscopies. The presence of ion clusters of {[Ru(bpy)3][S2W18O62]}2- (K2 = 7.7 × 105) and [Ru(bpy)3]2[S2W18O62] (K1 = 1.0 × 106 mol-2 dm-6) are inferred. The 2:1 complex is weakly luminescent, with a lifetime at room temperature of 20 ns under aerobic conditions. Difference electronic absorption, excitation, and resonance Raman spectroscopies indicate that the tungstate anion participates in this transition. Under conditions where [Ru(bpy)3]2+ alone is photolabile, the ion clusters are photostable, with no photodecomposition or photoinduced ligand exchange reactions evident in acetonitrile. This characteristic is examined employing temperature-dependent luminescent studies which demonstrate that the observed activation energy and preexponential factor are considerably different from those of free [Ru(bpy)3]2+and are characteristic of a photostable polypyridylruthenium complex.
08/2004;
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ABSTRACT: This paper presents a systematic study on two different preparation methods for titanium dioxide with silver. The silver can be incorporated by irradiating the reaction mixture during preparation to reduce silver ion to silver metal or by direct calcination of the sol–gel material to decompose silver nitrate to silver. Of the two methods, we found the latter produces a more effective photocatalytic material (6–50% improvement in catalytic efficiency), which is attributed to the fact that the silver is homogeneously dispersed throughout the material. The efficiency of the materials were examined using a Q-Sun solar simulator (visible light) and in Dublin summer sunlight (latitude 54°N). In both cases, the addition of increasing amounts of silver, for both batches of samples, significantly increases the rate of degradation of a model dye, rhodamine 6G (R6G), increasing the rate of degradation from 0.06 min−1 for TiO2 to 0.34 min−1 for 5 mol% Ag–TiO2. This is attributed to the increasing visible absorption capacity due to the presence of silver nanoparticles.
Journal of Photochemistry and Photobiology A: Chemistry.
