Made available in DSpace on 2014-12-17T15:42:01Z (GMT). No. of bitstreams: 1 EdissonMJ.pdf: 6565731 bytes, checksum: 5d6fdd6db6fc25a30c6100d96fff1edc (MD5) Previous issue date: 2007-08-24 / TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800?C), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7?nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200?C, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400?C. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150?C, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase / Titanatos nanoestruturados, particularmente TiTanatos NanoTubulares (TTNT), foram sintetizados por tratamento hidrot?rmico alcalino de TiO2-anat?sio seguido de repetidas lavagens com diversos graus de troca prot?nica. Amostras de TTNT com diferentes teores de s?dio foram caracterizadas na forma de p? seco e ap?s calcina??o (200-800?C) por difra??o de raios-X, microscopia eletr?nica de varredura e transmiss?o, difra??o de el?trons, an?lise t?rmica, adsor??o de nitrog?nio e t?cnicas espectrosc?picas de infravermelho e de reflet?ncia difusa no UV-Vis?vel. Demonstrou-se que tais materiais de paredes multilamelares s?o trititanatos de f?rmula geral NaxH2−xTi3O7?nH2O, retendo ?gua entre as lamelas. A remo??o de s?dio da estrutura reduz a quantidade de ?gua contraindo o espa?o interlamelar levando, combinado a outros fatores, ao aumento da ?rea e do volume de poros espec?ficos. Os TTNTs s?o materiais mesoporosos com duas contribui??es principais: poros menores que 10 nm devido ao volume interno dos nanotubos e poros entre 5 e 60 nm devido aos espa?os interpart?cula. A composi??o qu?mica e a estrutura cristalina do TTNT n?o dependem do tamanho de cristalito do TiO2-anat?sio precursor, todavia este par?metro afeta significativamente a morfologia e as caracter?sticas texturais do produto nanoestruturado. Tal depend?ncia foi racionalizada atrav?s de um mecanismo de dissolu??o-recristaliza??o que leva em conta a velocidade de dissolu??o do TiO2 de partida e sua influ?ncia sobre a taxa de crescimento de nanofolhas intermedi?rias em rela??o ? taxa de seu curvamento a nanotubos. A estabilidade t?rmica do TTNT ? definida pelo teor de s?dio e em pequena extens?o pelo tipo de anat?sio de partida. Foi demonstrado que o TTNT ap?s perder a ?gua intercalada entre 100 e 200?C se transforma pelo menos parcialmente num hexatitanato NaxH2−xTi6O13 intermedi?rio ainda nanotubular. A transforma??o t?rmica do tri- e hexatitanato nanoestruturados ocorre em maior ou menor temperatura e segue diferentes rotas dependendo do teor de s?dio. No caso de alto s?dio sinterizam e crescem at? grandes cristais de Na2Ti3O7 e Na2Ti6O13 na forma de bast?es e fitas acima de 600?C. No caso da amostra protonizada evoluem para nanotubos de TiO2(B) que facilmente se convertem em nanobast?es de anat?sio acima de 400?C. Al?m de hidroxilas e acidez de Lewis t?picos dos ?xidos de tit?nio, os TTNTs apresentam uma pequena contribui??o de acidez prot?nica capaz de se coordenar com a piridina a 150?C, e que ? perdida ap?s sua calcina??o e transforma??o ? anat?sio. O ponto isoel?trico do TTNT variou dentro da faixa 2,5- 4,0, indicando o comportamento de um ?cido fraco. Apesar de se revelar um semicondutor exibindo banda de absor??o t?pica no espectro de UV-vis?vel com energia de bandgap ligeiramente superior ao do respectivo TiO2-anat?sio precursor, os TTNTs apresentaram baixo desempenho fotocatal?tico na degrada??o de corantes cati?nico e ani?nico. Concluiu-se que a causa fundamental reside em sua estrutura de titanato lamelar que, em rela??o ? forma TiO2, apresentaria maior probabilidade de recombina??o do par el?tron-lacuna (e-/h+), inibindo as rea??es de fotoxida??o. A transforma??o do TTNT prot?nico ? nanobast?es de anat?sio melhorou a atividade fotocatal?tica, por?m ainda sem atingir o mesmo desempenho do TiO2-anat?sio precursor