In situ surface modification of molybdenum-doped organic-inorganic hybrid TiO2 nanoparticles under hydrothermal conditions and treatment of pharmaceutical effluent

Molybdenum-doped TiO2 organic-inorganic hybrid nanoparticles were synthesized under mild hydrothermal conditions by in situ surface modification using n-butylamine. This was carried out at 150 degrees C at autogeneous pressure over 18 h. n-Butylamine was selected as a surfactant since it produced nanoparticles of the desired size and shape. The products were characterized using powder X-ray diffraction, Fourier transform infrared spectrometry, dynamic light-scattering spectroscopy, UV-Vis spectroscopy and transmission electron microscopy. Chemical oxygen demand was estimated in order to determine the photodegradation efficiency of the molybdenum-doped TiO2 hybrid nanoparticles in the treatment of pharmaceutical effluents. It was found that molybdenum-doped TiO2 hybrid nanoparticles showed higher photocatalytic efficiency than untreated TiO2 nanoparticles.

Photocatalytic treatment of municipal wastewater using modified neodymium doped TiO2 hybrid nanoparticles

Photocatalytic degradation of municipal wastewater was investigated using reagent grade TiO2 and modified neodymium doped TiO2 hybrid nanoparticles. For the first time, surface modification of Nd3+ doped TiO2 hybrid nanoparticles were carried out with n-butylamine as surface modifier under mild hydrothermal conditions. The modified nanoparticles obtained were characterized by Powder XRD, FTIR, DLS, TEM, BET surface area, zeta potential and UV-Vis Spectroscopy. The characterization results indicated better morphology, particle size distribution and low agglomeration of the nanoparticles synthesized. It was found that photodegradation of wastewater using surface modified neodymium doped TiO2 nanoparticles was more compared to pure TiO2, which can be attributed to the doping and modification with n-butylamine.

Electrochemical sensing and photocatalysis using Ag-TiO2 microwires

Anatase Ag-TiO2 microwires with high sensitivity and photocatalytic activity were synthesized via polyol synthesis route followed by a simple surface modification and chemical reduction approach for attachment of silver. The superior performance of the Ag-TiO2 composite microwires is attributed to improved surface reactivity, mass transport and catalytic property as a result of wiring the TiO2 surface with Ag nanoparticles. Compared to the TiO2 microwires, Ag-TiO2 microwires exhibited three times higher sensitivity in the detection of cationic dye such as methylene blue. Photocatalytic degradation efficiency was also found to be significantly enhanced at constant illumination protocols and observation times. The improved performance is attributed to the formation of a Schottky barrier between TiO2 and Ag nanoparticles leading to a fast transport of photogenerated electrons to the Ag nanoparticles.

Catalytic performance of highly dispersed Ni/TiO2 for dry and steam reforming of methane

The present study reports a sonochemical-assisted synthesis of a highly active and coke resistant Ni/TiO2 catalyst for dry and steam reforming of methane. The catalyst was characterized using XRD, TEM, XPS, BET analyzer and TGA/DTA techniques. The TEM analysis showed that Ni nanoparticles were uniformly dispersed on TiO2 surface with a narrow size distribution. The catalyst prepared via this approach exhibited excellent activity and stability for both the reactions compared to the reference catalyst prepared from the conventional wet impregnation method. For dry reforming, 86% CH4 conversion and 84% CO2 conversion was obtained at 700 degrees C. Nearly 92% CH4 conversion and 77% CO selectivity was observed under a H2O/CH4 ratio of 1.2 at 700 degrees C for the steam reforming reaction. In particular, the present catalyst is extremely active and resistant to coke formation for steam reforming at low steam/carbon ratios. There is no significant modification of Ni particles size and no coke deposition, even after a long term reaction, demonstrating its potential applicability as an industrial reformate for hydrogen production. The detailed kinetic studies have been presented for steam reforming and the mechanism involving Langmuir-Hinshelwood kinetics with adsorptive dissociation of CH4 as a rate determining step has been used to correlate the experimental data.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively.

Some studies on TiO2 films deposited by sol-gel technique

TiO2 films are extensively used in various applications including optical multi-layers, sensors, photo catalysis, environmental purification, and solar cells etc. These are prepared by both vacuum and non-vacuum methods. In this paper, we present the results on TiO2 thin films prepared by a sol-gel spin coating process in non-aqueous solvent. Titanium isopropoxide is used as TiO2 precursor. The films were annealed at different temperatures up to 3000 C for 5 hours in air. The influence of the various deposition parameters like spinning speed, spinning time and annealing temperature on the thickness of the TiO2 films has been studied. The variation of film thickness with time in ambient atmosphere was also studied. The optical, structural and morphological characteristics were investigated by optical transmittance-reflectance measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM) respectively. The refractive index and extinction coefficient of the films were determined by envelope technique and spectroscopic ellipsometry. TiO2 films exhibited high transparency (92%) in the visible region with a refractive index of 2.04 at 650 nm. The extinction coefficient was found to be negligibly small. The X-ray diffraction analysis showed that the TiO2 film deposited on glass substrate changes from amorphous to crystalline (anatase) phase with annealing temperature above 2500 C. SEM results show that the deposited films are uniform and crack free.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively. (C) 2008 Elsevier B.V. All rights reserved.

Chemical Modification Studies of Gelonin - Involvement of Arginine Residues in Biological-Activity

Gelonin inhibits protein synthesis by inactivating the eukaryotic 60 S ribosomal subunit by an unknown mechanism. The protein was purified in high yield by a new method using Cibacron blue F3GA-Sepharose. Chemical modification studies reveal that arginine residues are essential for biological activity.

Calciothermic reduction of TiO2: A diagrammatic assessment of the thermodynamic limit of deoxidation

Calciothermic reduction of TiO2 provides a potentially low-cost route to titanium production. Presented in this article is a suitably designed diagram, useful for assessing the degree of reduction of TiO2 and residual oxygen contamination in metal as a function of reduction temperature and other process parameters. The oxygen chemical potential diagram à la Ellingham-Richardson-Jeffes is useful for visualization of the thermodynamics of reduction reactions at high temperatures. Although traditionally the diagram depicts oxygen potentials corresponding to the oxidation of different metals to their corresponding oxides or of lower oxides to higher oxides, oxygen potentials associated with solution phases at constant composition can be readily superimposed. The usefulness of the diagram for an insightful analysis of calciothermic reduction, either direct or through an electrochemical process, is discussed. Identified are possible process variations, modeling and optimization strategies.

Electrical, structural and magnetic properties of polyaniline/pTSA-TiO2 nanocomposites

Polyaniline (PANI)/para-toluene sulfonic acid (pTSA) and PANI/pTSA-TiO2 composites were prepared using chemical method and characterized by infrared spectroscopy (IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM). The electrical conductivity and magnetic properties were also measured. In corroboration with XRD, the micrographs of SEM indicated the homogeneous dispersion of TiO nanoparticles in bulk PANI/pTSA matrix. Conductivity of the PANI/pTSA-TiO2 was higher than the PAN[/pTSA, and the maximum conductivity obtained was 9.48 (S/cm) at 5 wt% of TiO2. Using SQUID magnetometer, it was found that PANI/pTSA was either paramagnetic or weakly ferromagnetic from 300 K down to 5 K with H-C approximate to 30 Oe and M-r approximate to 0.015 emu/g. On the other hand,PANI/pTSA-TiO2 was diamagnetic from 300 K down to about 50 K and below which it was weakly ferromagnetic. Furthermore, a nearly temperature-independent magnetization was observed in both the cases down to 50 K and below which the magnetization increased rapidly (a Curie like susceptibility was observed). The Pauli susceptibility (chi(pauli)) was calculated to be about 4.8 X 10(-5) and 1.6 x 10(-5)emug(-1) Oe(-1) K for PANI/pTSA and PANI/pTSA-TiO2, respectively.

Effect of Structural Modification on the Quantum-Size Effect in II-VI Semiconducting Nanocrystals

The electronic structure of group II-VI semiconductors in the stable wurtzite form is analyzed using state-of-the-art ab initio approaches to extract a simple and chemically transparent tight-binding model. This model can be used to understand the variation in the bandgap with size, for nanoclusters of these compounds. Results complement similar information already available for same systems in the zinc blende structure. A comparison with all available experimental data on quantum size effects in group II-VI semiconductor nanoclusters establishes a remarkable agreement between theory and experiment in both structure types, thereby verifying the predictive ability of our approach. The significant dependence of the quantum size effect on the structure type suggests that the experimental bandgap change at a given size compared to the bulk bandgap, may be used to indicate the structural form of the nanoclusters, particularly in the small size limit, where broadening of diffraction features often make it difficult to unambiguously determine the structure.

Studies on tryptophan residues of Abrus agglutinin Stopped-flow kinetics of modification and fluorescence-quenching studies

The presence of two essential tryptophan residues/molecule was implicated in the binding site of Abrus agglutinin [Patanjali, Swamy, Anantharam, Khan & Surolia (1984) Biochem. J. 217, 773-781]. A detailed study of the stopped-flow kinetics of the oxidation of tryptophan residues revealed three classes of tryptophan residues in the native protein. A discrete reorganization of tryptophan residues into two phases was observed upon ligand binding. The heterogeneity of tryptophan exposure was substantiated by quenching studies with acrylamide, succinimide and Cs+. Our study revealed the microenvironment of tryptophan residues to be hydrophobic, and also the presence of acidic amino acid residues in the vicinity of surface-localized tryptophan residues.

EPR study of trap-centres produced on TiO2 particles during water photolysis

The results of an EPR investigation are presented on the paramagnetic trap-centres produced on hydrothermally prepared TiO2 particles during water photolysis at room temperature under band-gap irradiation. The trapped holes correspond to O− species adjacent to cation vacancies that are formed to compensate the hydroxyl ions in the subsurface layers. The trapped electrons are accounted for as Ti3+ in the conduction band or Ti3+ - adjoining oxygen vacancy to form shallow donor states. Although hole-centres are normally stabler than electron-centres, strongly adsorbed donor molecules reverse the stability. Concentration of hole-centres is increased by the presence of platinum on TiO2 surface and electron-centres are not detected on Pt/TiO2 during water photolysis.

Sacrificial photolysis of water on TiO2 fine powders prepared by the hydrothermal method

The often discussed role of surface hydroxylation of TiO2 particles as an essential characterestics for their photocatalytic activity can be verified by preparing TiO2 powders by hydrothermal method since hydroxylated surface layers will be better retained on these particles formed in superheated water. Thus, fine powders of TiO2 (rutile) with high degree of crystallinity are formed from titanium oxychloride in the mixed solvent of water and 2-propanol at 160–230°C and 20–120 atm. The anatase phase is produced from the same medium when sulfate ion impurity is present, with Image . TiO2 powders are washed free of anions and 2-propanol by ultrafiltration and are Pt mounted by a photochemical method. Aqueous suspensions of both forms of TiO2 neither as such nor after Pt-loading, do not produce H2 on band gap illumination whereas, H2 is generated in presence of hole scavengers such as EDTA, TEOA, sulfite or hypophosphite. The effects of hole scavenger concentration, Pt : TiO2 ratio, particulate suspension density and the nature of hole scavengers on H2 production are presented. Platinised rutile powders are equally active as anatase in sacrificial systems.

Modification of chemical reactivity by cyclodextrins. Observation of moderate effects on Norrish type I and type II photobehavior

The photochemistry and photophysics of organic molecules in organized assemblies are being studied with great interest in order to understand the features controlling the selectivity in the photoreactions brought about by these media.l These studies have paved the way to an intriguing number of possibilities by which photoreactivity can be modified. In this connection, we have investigated the photobehavior of a number of phenyl alkyl ketones and cu,cu-dimethylphenyl alkyl ketones (Scheme I) incorporated in the hydrophobic interior of cyclodextrin cavities.