Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Effects of solar wind magnetosphere coupling recorded at different geomagnetic latitudes: Separation of directly-driven and storage/release systems

The effect on geomagnetic activity of solar wind speed, compared with that of the strength of the interplanetary magnetic field, differs with geomagnetic latitude. In this study we construct a new index based on monthly standard deviations in the H-component of the geomagnetic field for all geomagnetic latitudes. We demonstrate that for this index the response at auroral regions correlates best with interplanetary coupling functions which include the solar wind speed while mid- and low-latitude regions respond to variations in the interplanetary magnetic field strength. These results are used to isolate the responsible geomagnetic current systems.

A comparative study of the physical properties of conventional and Grander-modified adhesive systems

Purpose: The objective of this study was to evaluate the influence of the Grander technology in reducing the surface tension and contact angle of a self-etch adhesive system. Methods: Distilled water and Xeno III self-etch adhesive system (Dentsply) were modified by physical contact with the Flexible unit Grander system to revitalize water, for 48 hours, resulting in four groups: Group 1 - Xeno III under normal conditions; Group 2 - Xeno III modified by Grander; Group 3 - distilled water under normal conditions; Group 4 - distilled water system modified by the Grander system;. Surface tension and contact angle (dentin substrate and titanium plate) of the adhesive system and water in normal and Grander-modified conditions was measured with a goniometer. Data were analyzed by ANOVA and Tukey test (5%). Results: Grander technology reduced the surface tension of water but not of the adhesive system Xeno III. The contact angle property of the adhesive ystem was not affected. Conclusion: Grander technology did not interfere with the surface tension and contact angle physical properties of the Xeno III self-etch adhesive system. Copyright: © 2011 Gonçalves et al.;.

Polysaccharides as safer release systems for agrochemicals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Modified release of beclometasone dipropionate from chitosan-basedd spray-dried respirable powders

Dry powders for inhalation were prepared by spray drying a 30% v/v aqueous ethanol formulation containing beclometasone dipropionate (BDP), lactose, leucine and chitosan (low, medium or high molecular weight (MW), or combinations thereof). Following physical characterisation of the powders, the aerosolisation and dissolution properties of the powders were investigated using Multi-Stage Liquid Impinger and USP II dissolution apparatus, respectively. The powders were highly dispersible, with emitted doses in excess of 90% of loaded powder aerosolised from a Spinhaler dry powder inhaler. The fine particle fraction (FPF) was observed to decrease, whereas the time for 100% drug release increased, with increasing chitosan MW. For example, the low MW formulation exhibited an FPF of 64% and a 100% dissolution time of 2 h, whereas the high MW formulation demonstrated an FPF of 54% and a dissolution time of 12 h. These powders would be anticipated to deposit predominately in the lower regions of the lung following inhalation, and then undergo delayed rather than instantaneous drug release, offering the potential to reduce dosing frequency and improve patient compliance. (c) 2008 Elsevier B.V. All rights reserved.

Purificação e caracterização da beta-lapachona e estudo de estabilidade dos cristais em diferentes condições de armazenamento

The beta-lapachone is a product obtained from the Ipê Roxo tree [Tabebuia avellandae], which has proved its excellent antineoplasic potential acting through a particular mechanism of apoptosis against various cancer types. This study aims at determining the identity card of beta-lapachone by means of physico-chemical and pharmaco-technical characterization. A purifying process has been performed, as well as the isolation of a contaminant, its isomer alpha-lapachone. A stability study was also performed, determining the ideal storing conditions for beta-lapachone, essential for the ongoing pre-formulation studies for obtaining the different classic pharmaceutical forms and modified release systems.

Desenvolvimento de nanocápsulas de poli-ε-caprolactona contendo o herbicida atrazina

In this study, polymeric nanocapsules of PCL containing the herbicide atrazine were prepared. In order to optimize the preparation conditions, a 2³ factorial design was performed using different formulations of nanocapsules, which investigated the influence of three variables at two levels. The factors varied were the quantities of PCL, Span 60 and Myritol. The results were evaluated considering the size, polydispersity, zeta potential and association rate and the measures of these parameters were taken immediately after preparation and after 30 days of preparation. The formulations with minimum level of polymer in the preparation showed better stability results.

Processo antissolvente supercrítico para obtenção de dispersões sólidas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Desenvolvimento de nanocápsulas de poli-ε-caprolactona contendo o herbicida atrazina

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Development and In Vitro Evaluation of Surfactant Systems for Controlled Release of Zidovudine

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Poly(hydroxybutyrate-co-hydroxyvalerate) microspheres loaded with atrazine herbicide: screening of conditions for preparation, physico-chemical characterization, and in vitro release studies

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Poly(epsilon-caprolactone) nanocapsules carrying the herbicide atrazine: effect of chitosan-coating agent on physico-chemical stability and herbicide release profile

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Analysis of the nano-surface of a modified glassy carbon electrode by pseudo phase plane method

This paper presents the Pseudo phase plane (PPP) method for detecting the existence of a nanofilm on the nitroazobenzene-modified glassy carbon electrode (NAB-GC) system. This modified electrode systems and nitroazobenze-nanofilm were prepared by the electrochemical reduction of diazonium salt of NAB at the glassy carbon electrodes (GCE) in nonaqueous media. The IR spectra of the bare glassy carbon electrodes (GCE), the NAB-GC electrode system and the organic NAB film were recorded. The IR data of the bare GC, NAB-GC and NAB film were categorized into five series consisting of FILM1, GC-NAB1, GC1; FILM2, GC-NAB2, GC2; FILM3, GC-NAB3, GC3 and FILM4, GC-NAB4, GC4 respectively. The PPP approach was applied to each group of the data of unmodified and modified electrode systems with nanofilm. The results provided by PPP method show the existence of the NAB film on the modified GC electrode.