Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 118-126).

Thesis (M.Sc.(Chemistry))--University of Pretoria, 2008. / Includes bibliographical references (leaves 85-104).

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Hidróxidos Duplos Lamelares (HDL) são materiais lamelares constituídos de camadas positivamente carregadas de um hidróxido misto de dois metais (um di e um trivalente), com ânions hidratados no domínio interlamelar. Apesar de serem potenciais adsorventes, o estudo da adsorção de colato de sódio sobre estes sólidos foi pouco explorado até hoje. Este estudo é importante, pois abre caminho para uma potencial aplicação farmacêutica de HDL na remoção de colato produzido em excesso pelo corpo humano, e diminuindo o risco de doenças conseqüentes desse excesso. Este trabalho teve por objetivo estudar a adsorção e a sorção de colato de sódio a partir de soluções aquosas, em hidróxido duplo lamelar de magnésio e alumínio intercalado com carbonato, Mg-Al-CO3-HDL, verificando o efeito de variáveis como temperatura, pH e força iônica do meio. O adsorvente foi preparado pelo método de coprecipitação a pH variável e caracterizado quanto à composição, organização estrutural, textura e morfologia, sendo utilizado na forma original ou após calcinação. A adsorção de colato de sódio no HDL não calcinado indicou que não ocorre a substituição do ânion interlamelar (CO32-), mas sim a adsorção por interação do ânion orgânico com as cargas residuais na superfície do HDL. O processo mostrou uma grande dependência das variáveis estudadas. A análise multivariacional confirmou e quantificou a importância de cada variável. Em todos os casos, o aumento da temperatura resultou em uma diminuição na quantidade máxima adsorvida. O aumento da força iônica do meio, por meio da adição de um sal neutro, resulta em uma melhoria na capacidade de remoção de ânions. Na faixa avaliada, quanto maior o valor do pH das soluções de colato, menor a quantidade máxima adsorvida. Os resultados obtidos para a sorção no HDL calcinado mostraram que inicialmente o HDL é reconstituído com a intercalação de ânions OH-. Em casos onde a concentração do composto orgânico era alta, o colato foi intercalado formando uma nova fase. Neste caso, a sorção de colato apresentou curvas com perfil semelhante às da adsorção: as isotermas atingem um patamar onde a sorção torna-se constante e o aumento da temperatura diminui a quantidade sorvida. Pelos resultados obtidos, foi proposto um modelo de intercalação de colato em bicamada. Os resultados indicam também que a remoção do colato pelo HDL calcinado se mostra mais eficiente do que aquela obtida com o HDL não calcinado. / Layered Double Hydroxides (LDH), are lamellar materials constituted of positively charged layers of two mixed cations hydroxide (a bi and a trivalent one), with hydrated anions in the interlayer domain. In spite of being potential adsorbents, the study of the sodium cholate adsorption on these solids has not been well explored yet. This study is important, because it opens the perspective for the application of LDH in the pharmaceutical field in the removal of cholate produced in excess by the human organism and decreasing the risk of consequent diseases from this excess. The aim of this work was to study the adsorption and the sorption of sodium cholate from aqueous solutions, in Mg-Al-CO3-LDH, verifying the effect of the variables: temperature, pH and ionic strength of the media. The adsorbent was prepared by the coprecipitation at variable pH method and characterized with respect to their composition, structural organization, texture and morphology, being utilized in the pristine form or after calcination. The adsorption of sodium cholate in pristine LDH indicated that the exchange of the interlayer anion (CO32-) doesn\'t occur, but the adsorption process occurs by the interaction of the anion with the residual charges on the LDH surface. The process showed great dependence on the parameters studied. The multivariational analysis confirmed and quantified the influence of each variable. In all the experiments, increasing the temperature resulted in a decrease in the maximum adsorbed quantity. Increasing the ionic strength of the media, by the addition of a neutral salt, results in a better anions removal capacity. In the evaluated interval, the bigger the initial pH value of the cholate solutions, the lower the maximum adsorbed quantity. The results obtained for the sorption in calcined LDH showed that initially the LDH are reconstituted with the OH- anions intercalated. In the experiments at high concentration, the cholate is intercalated forming a new phase. The profile of cholate sorption are similar to that of the adsorption: the isotherms reach a plateau where the sorption becomes constant and the raise in the temperature decreases the sorbed quantity. By the obtained results, it was proposed a cholate intercalation model forming a bilayered structure. The results indicate that the cholate removal by the calcined LDH is more efficient than that presented by the uncalcined one.

The main object of the present investigation has been to establish a titration curve for mohair keratin and to compare it with similar data for wool, to determine whether the differences in physical and chemical properties could be attributed in any way to the acidic and basic character of these fibres. As shown in subsequent discussion such measurements provide extremely useful information regarding the chemical structure of proteins in general, and in the technical fields involving processes such as wool scouring, carbonizing and dyeing. The study has been extended to include certain modified wools, i.e. photochemically damaged, and oxidized keratin. The most successful contribution to the titration data of wool keratin is the work of Steinhardt and Harris and subsequent authors have tended to adopt their procedures without modification. In the present study attempts have been made to obtain a clearer understanding of the fundamental processes. New techniques and analytical methods have been introduced to improve the accuracy of the measurements.

Hydrotalcite-like compounds are synthetic anionic clays that have outstanding adsorption and catalytic properties. Hydrotalcite nanoclays (Mg–Al layered hydroxides) were synthesized by co-precipitation method. Obtained solids were converted into mixed metal oxides by thermal decomposition at temperatures up to 723 K. High adsorption and reconstructive properties of the mixed metal oxides allowed incorporating metal ions in their structure. Thus, these materials can be used as ion traps from aqueous media. Cesium ions were incorporated into hydrotalcite lamellar structure by impregnation method. Effects of different loads of Cs+ and adsorption times on the material properties were studied. The materials were characterized by X-ray diffraction, surface area analysis, scanning electron microscopy, energy dispersive X-ray spectrometry for obtaining a localized chemical analysis, and temperature-programmed desorption of CO2 for measurement of basic sites density. The amounts of metal incorporated in the structure was high enough due to small size of Cs+ ion. Synthetized materials also demonstrated high concentrations of strong surface basic sites formed through a synergistic effect of Cs and Mg ions. Basic properties of Cs-containing hydrotalcites enable their potential use as catalysts of base-catalyzed reactions.

Water polluted by metals and phosphates can be hazardous to both the environment and human health. The aim of this study was used to improve understanding of the adsorption properties of low-cost, green adsorbents for removal of pollutants from aqueous solution. Biochar was used as an adsorbent, which was produced from the gasification of pine wood waste and the fast pyrolysis of Douglas fir. Biochar is a bio-renewable product that can easily be modified, and the cost is lower compared to other adsorbents like activated carbon. The gasifier produced biochar was modified by coating the biochar surface with chitosan. Douglas fir biochar, produced by pyrolysis, was used in Mg/Al-layered double hydroxides (LDHs) and magnetization modifications. The Mg/Al-LDHs were prepared by co-precipitation using solutions of Mg and Al salts and NaOH treatment. The magnetization modification of the biochar was prepared by magnetite (Fe3O4) precipitation onto the biochar’s surface from Fe2+/Fe3+ solution upon NaOH treatment. Chapter I provides an introduction into biochar production, uses, and modification methods. Chapter II is a study of the aqueous adsorption Cu2+ and Cd2+ metals using chitosan coated and uncoated gasifier biochars. Chapter III focused on the removal of phosphate from aqueous solutions. Different ratios of Mg:Al in the LDHs were used to test the ratio’s affect on the adsorption properties of the modified adsorbents. Chapter IV describes the removal of phosphate from water using LDH modified biochars that are magnetized. This study looks at how the order in which the modifications were done influences the biochars adsorption ability. The surface chemistry and composition of each biochar in chapters II-IV were examined by SEM, SEM-EDX, TEM, PZC, XRD, elemental analysis, and surface area measurements. Each biochar’s adsorption ability was studied by pH effects, kinetics, and maximum capacity for the analyte.