Long-chain alkylbenzenes are industrially synthesized precursors to commercial surfactants such as laundry detergent. The currently used catalysts in the processes of their synthesis are corrosive and harmful to the environment. These problems can be avoided utilizing heterogeneous highly acidic catalysts. Solid catalysts do not corrode equipment and are relatively simple to remove from the post-reaction mixture. Phosphotungstic acid (PTA) supported on silica gel could be a possible catalyst due to its high acidity with an estimated pKa ≈ -13. The catalyst PTA-SiO2 was prepared via the sol-gel method to covalently embed it in a silica support. The catalyst was granulated with γ-alumina for use in a fixed bed flow reactor during the alkylation of benzene with long chain alkenes. The isomerization of 1-octene, 1-decene, and 1-octadecene as well as the conversion of 1-decene in the alkylation of benzene were studied under varying conditions. During these reactions, the catalyst demonstrated good catalytic activity at temperatures above 200 °C with an optimal temperature of 250 °C. Of all three alkenes, 1-octadecene showed the highest conversion into respective isomers. The alkylation of benzene with 1-decene experiments showed decreasing of flow rate and increasing the ratio of benzene to 1-decene lead to higher conversions of 1-decene. Characterization of the catalyst after the reaction showed little changes in porosity and particle size. No leaching of PTA was observed. However, carbon deposits were found on the catalyst that requires regeneration before next use in catalysis.

Silica gels containing incorporated heteropolyacids (HPAs) were synthesized in acidic media by co-condensation of tetraethoxysilane (TEOS) with phosphotungstic or phosphomolybdic acids using the sol-gel technique. The effect of the synthesis conditions on their structure and morphology was studied. Yields of modified materials were somewhat lower compared to non-modified silica gels. All materials were mesoporous but contained micropores in their structures. Presence of bands of Keggin's structures in FT-IR spectra along with absence of XRD patterns of crystalline HPAs confirmed their fine incorporation into silica network. Particle sizes of modified materials were 500-1100 nm except for the W-containing sample obtained with trimethylstearylammonium chloride, which was significantly lower. This unusual effect was attributed to stabilization of primary silica nanoparticles by interactions between the surfactant and HPA. High ratio HPA/TEOS resulted in partial loss of porosity. Obtained results might be used for optimization of synthesis of effective catalysts and adsorbents containing HPAs in mesoporous structure.

Mesoporous silica gel containing embedded phosphotungstic acid (PTA) was synthesized by sol-gel co-condensation of tetraethoxysilane with PTA in acidic media. The obtained material had high BET surface area and pore volume. A characteristic band of the Keggin structure of PTA was present in its FT-IR spectrum while its XRD patterns were absent. This proved the embedding of PTA on a sub-molecular level. The material demonstrated high adsorption capacity of Cs. Unexpectedly, porosity of the adsorbent increased after substitution of most protons by cesium cations. Cation exchange also favored agglomeration of the material particles. Kinetic studies showed that the adsorption data correlates strongly with the pseudo-second order model. The adsorbent had two types of adsorption sites: heteropolyacid anions and silanol groups. However, adsorption on silanol groups was very sensitive to the temperature. At the increased temperature, the nature of adsorption fit the Langmuir model extremely well. The obtained results can be used in the development of an effective adsorbent for clean-up of water contaminated by radioactive cesium-137.

Neste trabalho, estudou-se a síntese por sol-gel da ferrita de cobalto (CoFe2O4), variando-se a temperatura de tratamento térmico do xerogel. Nitrato de ferro e nitrato de cobalto foram utilizados como fonte de cátions e ácido cítrico como mineralizador. Os produtos obtidos, tratados a 750, 800 e 850°C, tiveram sua microestrutura e propriedades magnéticas investigadas no intuito de encontrar correlações entre as condições de síntese, as posições ocupadas pelos cátions dentro da estrutura espinélio do composto e as propriedades magnéticas medidas. Estudos de difratometria de raios X exibiram reflexões características da estrutura espinélio, o que sugere que o tratamento térmico não afetou significativamente a estrutura cristalina do material. Uma fração secundária de hematita também foi observada. As ferritas apresentaram área superficial específica (por BET) de aproximadamente 4 m².g-1. Imagens por MEV indicam que o material apresenta-se aglomerado. Quanto às propriedades magnéticas, um máximo de coercividade de 1405.2 Oersted foi encontrado para a amostra tratada a 800°C. Espectros Mößbauer indicaram um baixo grau de inversão nos espinélios formados, o que é incomum para a ferrita de cobalto. Subtraindo do espectro obtido por Mößbauer o excesso de ferro na forma de hematita, há um forte indicativo que a ferrita foi sintetizada de maneira sub-estequiométrica deficiente em ferro. / We herein report a study on the sol-gel synthesis of cobalt ferrite (CoFe2O4) and the effect of treatment temperature on the product outcome. Iron nitrate and cobalt nitrate were used as cation sources and citric acid as mineralizer. Products treated at 750, 800 and 850°C had their microstructure and magnetic properties assessed in order to correlate their synthesis conditions, the positions in which the cations are inserted in the spinel structure and the magnetic behavior displayed by the ferrites. X-ray diffractometry studies exhibit the characteristic reflections of spinel group materials, suggesting that the thermal treatment does not sensibly affect the crystalline structure of the material. A secondary fraction of hematite was also observed. The ferrites exhibit a specific surface area (from BET) of approximately 4 m².g-1. SEM images indicate the material forms agglomerates. As to the magnetic properties, a maximum of 1405.2 Oersted was achieved for the sample treated at 800°C. Mößbauer spectra indicate a fairly low inversion degree in the synthesized materials, which is rather unusual for cobalt ferrite. After deducting the iron fraction present in the form of hematite, there are strong indications that cobalt ferrite was synthesized as a substoichiometric iron-deficient spinel.

Mesoporous silica gel containing embedded phosphotungstic acid (PTA) was synthesized by sol-gel co-condensation of tetraethyl orthosilicate with PTA in acidic media. The obtained material had high Brunauer-Emmett-Teller Theory (BET) surface area and pore volume. A characteristic band of the Keggin structure of PTA was present in its FT-IR spectrum while its X-ray diffraction patterns were absent. This proved the embedding of PTA on a sub-molecular level and not as a second phase. Acidic sites were determined by neutralization with base in aprotic solvent, followed by titration of the remaining base with an acid. The material demonstrated high adsorption capacity of Cs. Kinetic studies showed that the adsorption data correlates strongly with the pseudo-second order model. At higher temperatures, the nature of adsorption fit the Langmuir model extremely well. The obtained results can be used in the development of an effective adsorbent for clean-up of water contaminated by radioactive 137Cs.

Pažangių medžiagų bei technologijų kūrimas ir taikymas - tai labai svarbus šiandieninės informacinės visuomenės uždavinys. Granato kristalinės struktūros medžiagos, pasižymėdamos ypatingomis fizikinėmis bei cheminėmis savybėmis, yra plačiai naudojamos informacinių technologijų, kietafazių lazerių, optikos įrenginių gamybose, medicinos įrangose, bei daugelyje kitų sričių. Todėl jos dėl savo unikalių savybių ir plačiai tebetyrinėjamos iki šiol. Šiame darbe pirmą kartą buvo susintetinti Ce-Al-O, Pr-Al-O, Nd-Al-O, Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O, Lu-Al-O, Y(Nd)-Al-O ir Y(Sm)-Al-O acetatiniai-nitratiniai-glikoliatiniai geliai zolių-gelių metodu vandeniniuose tirpaluose. Jie buvo panaudoti pradinėmis medžiagomis atitinkamų lantanoidų aliuminio granatų sintezei. Vienfaziai terbio aliuminio granatas (Tb3Al5O12), disprozio aliuminio granatas (Dy3Al5O12), holmio aliuminio granatas (Ho3Al5O12), erbio aliuminio granatas (Er3Al5O12), tulio aliuminio granatas (Tm3Al5O12), iterbio aliuminio granatas (Yb3Al5O12) ir liutecio aliuminio granatas (Lu3Al5O12) buvo gauti, terbio jonų šaltiniu naudojant terbio oksidą, disprozio – disprozio oksidą, holmio – holmio oksidą, erbio – erbio oksidą, tulio – tulio oksidą, iterbio – iterbio oksidą, lutecio – liutecio oksidą, kompleksus sudarančiu reagentu 1,2-etandiolį. Tyrimų rezultatai parodė, kad šių lantanoidų aliuminio granatai gauti santykinai žemoje temperatūroje (1000°C). Zolių-gelių metodu sintetinant cerio aliuminio granatą... [toliau žr. visą tekstą] / The development and application of advanced materials is a very important task of today's information society. Garnet crystal structure compounds because of their specific physical and chemical properties are widely used in information technology, manufacturing of solid-state lasers and optical equipments, medical equipments and many other areas. Therefore, these materials because of their unique properties and characteristics are of high interest so far. For the first time Ce-Al-O, Pr-Al-O, Nd-Al-O, Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O, Lu-Al-O, Y(Nd)-Al-O and Y(Sm)-Al-O acetate-nitrate-glycolate gels have been synthesized using environmentally friendly, economical and simple aqueous sol-gel method. They were used as starting materials for the synthesis of appropriate lanthanide aluminium garnets. The results of X-ray difraction analysis have indicated that single-phase terbium aluminium garnet (Tb3Al5O12), dysprosium aluminium garnet (Dy3Al5O12), holmium aluminium garnet (Ho3Al5O12), erbium aluminium garnet (Er3Al5O12), thulium aluminium garnet (Tm3Al5O12), ytterbium aluminium garnet (Yb3Al5O12) and lutetium aluminium garnet (Lu3Al5O12) have been synthesized by annealing Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O and Lu-Al-O precursor gels for 10 hours at 1000 °C, respectively. For the first time these garnet structure compounds were synthesized using sol-gel method. Moreover, these lanthanide aluminium garnets were synthesized at relatively low... [to full text]

The development and application of advanced materials is a very important task of today's information society. Garnet crystal structure compounds because of their specific physical and chemical properties are widely used in information technology, manufacturing of solid-state lasers and optical equipments, medical equipments and many other areas. Therefore, these materials because of their unique properties and characteristics are of high interest so far. For the first time Ce-Al-O, Pr-Al-O, Nd-Al-O, Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O, Lu-Al-O, Y(Nd)-Al-O and Y(Sm)-Al-O acetate-nitrate-glycolate gels have been synthesized using environmentally friendly, economical and simple aqueous sol-gel method. They were used as starting materials for the synthesis of appropriate lanthanide aluminium garnets. The results of X-ray difraction analysis have indicated that single-phase terbium aluminium garnet (Tb3Al5O12), dysprosium aluminium garnet (Dy3Al5O12), holmium aluminium garnet (Ho3Al5O12), erbium aluminium garnet (Er3Al5O12), thulium aluminium garnet (Tm3Al5O12), ytterbium aluminium garnet (Yb3Al5O12) and lutetium aluminium garnet (Lu3Al5O12) have been synthesized by annealing Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O and Lu-Al-O precursor gels for 10 hours at 1000 °C, respectively. For the first time these garnet structure compounds were synthesized using sol-gel method. Moreover, these lanthanide aluminium garnets were synthesized at relatively low... [to full text] / Pažangių medžiagų bei technologijų kūrimas ir taikymas - tai labai svarbus šiandieninės informacinės visuomenės uždavinys. Granato kristalinės struktūros medžiagos, pasižymėdamos ypatingomis fizikinėmis bei cheminėmis savybėmis, yra plačiai naudojamos informacinių technologijų, kietafazių lazerių, optikos įrenginių gamybose, medicinos įrangose, bei daugelyje kitų sričių. Todėl jos dėl savo unikalių savybių ir plačiai tebetyrinėjamos iki šiol. Šiame darbe pirmą kartą buvo susintetinti Ce-Al-O, Pr-Al-O, Nd-Al-O, Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O, Lu-Al-O, Y(Nd)-Al-O ir Y(Sm)-Al-O acetatiniai-nitratiniai-glikoliatiniai geliai zolių-gelių metodu vandeniniuose tirpaluose. Jie buvo panaudoti pradinėmis medžiagomis atitinkamų lantanoidų aliuminio granatų sintezei. Vienfaziai terbio aliuminio granatas (Tb3Al5O12), disprozio aliuminio granatas (Dy3Al5O12), holmio aliuminio granatas (Ho3Al5O12), erbio aliuminio granatas (Er3Al5O12), tulio aliuminio granatas (Tm3Al5O12), iterbio aliuminio granatas (Yb3Al5O12) ir liutecio aliuminio granatas (Lu3Al5O12) buvo gauti, terbio jonų šaltiniu naudojant terbio oksidą, disprozio – disprozio oksidą, holmio – holmio oksidą, erbio – erbio oksidą, tulio – tulio oksidą, iterbio – iterbio oksidą, lutecio – liutecio oksidą, kompleksus sudarančiu reagentu 1,2-etandiolį. Tyrimų rezultatai parodė, kad šių lantanoidų aliuminio granatai gauti santykinai žemoje temperatūroje (1000°C). Zolių-gelių metodu sintetinant cerio aliuminio granatą... [toliau žr. visą tekstą]

Neste trabalho, estudou-se a síntese por sol-gel da ferrita de cobalto (CoFe2O4), variando-se a temperatura de tratamento térmico do xerogel. Nitrato de ferro e nitrato de cobalto foram utilizados como fonte de cátions e ácido cítrico como mineralizador. Os produtos obtidos, tratados a 750, 800 e 850°C, tiveram sua microestrutura e propriedades magnéticas investigadas no intuito de encontrar correlações entre as condições de síntese, as posições ocupadas pelos cátions dentro da estrutura espinélio do composto e as propriedades magnéticas medidas. Estudos de difratometria de raios X exibiram reflexões características da estrutura espinélio, o que sugere que o tratamento térmico não afetou significativamente a estrutura cristalina do material. Uma fração secundária de hematita também foi observada. As ferritas apresentaram área superficial específica (por BET) de aproximadamente 4 m².g-1. Imagens por MEV indicam que o material apresenta-se aglomerado. Quanto às propriedades magnéticas, um máximo de coercividade de 1405.2 Oersted foi encontrado para a amostra tratada a 800°C. Espectros Mößbauer indicaram um baixo grau de inversão nos espinélios formados, o que é incomum para a ferrita de cobalto. Subtraindo do espectro obtido por Mößbauer o excesso de ferro na forma de hematita, há um forte indicativo que a ferrita foi sintetizada de maneira sub-estequiométrica deficiente em ferro. / We herein report a study on the sol-gel synthesis of cobalt ferrite (CoFe2O4) and the effect of treatment temperature on the product outcome. Iron nitrate and cobalt nitrate were used as cation sources and citric acid as mineralizer. Products treated at 750, 800 and 850°C had their microstructure and magnetic properties assessed in order to correlate their synthesis conditions, the positions in which the cations are inserted in the spinel structure and the magnetic behavior displayed by the ferrites. X-ray diffractometry studies exhibit the characteristic reflections of spinel group materials, suggesting that the thermal treatment does not sensibly affect the crystalline structure of the material. A secondary fraction of hematite was also observed. The ferrites exhibit a specific surface area (from BET) of approximately 4 m².g-1. SEM images indicate the material forms agglomerates. As to the magnetic properties, a maximum of 1405.2 Oersted was achieved for the sample treated at 800°C. Mößbauer spectra indicate a fairly low inversion degree in the synthesized materials, which is rather unusual for cobalt ferrite. After deducting the iron fraction present in the form of hematite, there are strong indications that cobalt ferrite was synthesized as a substoichiometric iron-deficient spinel.

Neste trabalho, estudou-se a síntese por sol-gel da ferrita de cobalto (CoFe2O4), variando-se a temperatura de tratamento térmico do xerogel. Nitrato de ferro e nitrato de cobalto foram utilizados como fonte de cátions e ácido cítrico como mineralizador. Os produtos obtidos, tratados a 750, 800 e 850°C, tiveram sua microestrutura e propriedades magnéticas investigadas no intuito de encontrar correlações entre as condições de síntese, as posições ocupadas pelos cátions dentro da estrutura espinélio do composto e as propriedades magnéticas medidas. Estudos de difratometria de raios X exibiram reflexões características da estrutura espinélio, o que sugere que o tratamento térmico não afetou significativamente a estrutura cristalina do material. Uma fração secundária de hematita também foi observada. As ferritas apresentaram área superficial específica (por BET) de aproximadamente 4 m².g-1. Imagens por MEV indicam que o material apresenta-se aglomerado. Quanto às propriedades magnéticas, um máximo de coercividade de 1405.2 Oersted foi encontrado para a amostra tratada a 800°C. Espectros Mößbauer indicaram um baixo grau de inversão nos espinélios formados, o que é incomum para a ferrita de cobalto. Subtraindo do espectro obtido por Mößbauer o excesso de ferro na forma de hematita, há um forte indicativo que a ferrita foi sintetizada de maneira sub-estequiométrica deficiente em ferro. / We herein report a study on the sol-gel synthesis of cobalt ferrite (CoFe2O4) and the effect of treatment temperature on the product outcome. Iron nitrate and cobalt nitrate were used as cation sources and citric acid as mineralizer. Products treated at 750, 800 and 850°C had their microstructure and magnetic properties assessed in order to correlate their synthesis conditions, the positions in which the cations are inserted in the spinel structure and the magnetic behavior displayed by the ferrites. X-ray diffractometry studies exhibit the characteristic reflections of spinel group materials, suggesting that the thermal treatment does not sensibly affect the crystalline structure of the material. A secondary fraction of hematite was also observed. The ferrites exhibit a specific surface area (from BET) of approximately 4 m².g-1. SEM images indicate the material forms agglomerates. As to the magnetic properties, a maximum of 1405.2 Oersted was achieved for the sample treated at 800°C. Mößbauer spectra indicate a fairly low inversion degree in the synthesized materials, which is rather unusual for cobalt ferrite. After deducting the iron fraction present in the form of hematite, there are strong indications that cobalt ferrite was synthesized as a substoichiometric iron-deficient spinel.

In the present thesis we propose the development of hybrid polymer titanium dioxide (TiO2) nanoparticles for use in biomedical applications. TiO2 exhibits high biocompatibility in the dark however, upon illumination in aqueous media with near UV light it produces an array of reactive oxygen species (ROS) which have the capability to induce death in neighbouring cells. The process of inducing cell death using a photosensitive material which produces ROS is known as photodynamic therapy (PDT) and is used to treat a wide range of maladies from psoriasis to cancer.We have demonstrated the ability to produce anatase nanoparticles with high control over their resulting size through a novel water mediated sol-gel synthetic method in benzyl alcohol, using either Ti(OnPr)4, Ti(OnBu)4 or Ti(OiPr)4 as the metal precursor. Through dynamic light scattering (DLS) analysis we have shown that the mechanism of nanoparticle growth appears to proceed through the agglomeration of primary nanoparticles formed instantly upon adding the reagents together. After synthesis the nanoparticles could be easily redispersed in aqueous media at pH2 with any further agglomeration being controlled by the parent alkoxide.After synthesis the nanoparticles were coated with PEG, conjugated to either a catechol or phosphate as ligand, in order to stabilise the nanoparticles at neutral pH. Uncoated nanoparticles exhibited good photoactive capability in the photooxidation of methylene blue. However, on coating with catechols the photoactivity of the nanoparticles was abolished. Coating with phosph(on)ates on the other hand preserved or even enhanced the photoactivity which makes this system promising for in vivo applications.At the same time this thesis also reports preliminary investigations on the use of TiO2 embedded into the walls of model drug loaded poly electrolyte multilayer microspheres for UV triggered delivery applications.