Synthesis and characterization of 3-[(thiourea)-propyl]-functionalized silica gel and its application in adsorption and catalysis

The objective of this research was the preparation of a silica gel functionalized successively with 3-chloropropyltrimethoxysilane (SG-PrCl) and thiourea (SG-Pr-THIO), and its application in adsorption and catalysis. The materials were characterized by 13C and 29Si NMR, FTIR, scanning electron micrographs (SEM), analysis of nitrogen and elemental analysis. Aiming at its application in adsorption, the [3-(thiourea)-propyl] silica gel (SG-Pr-THIO) was tested as an adsorbent for transition-metal ions using a batchwise process. The organofunctionalized surface showed the ability to adsorb the metal ions Cd(ii), Cu(ii), Ni(ii), Pb(ii) and Co(ii) from water, ethanol and acetone. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) models. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and pseudo-first order models were the most appropriate to describe the adsorption and kinetic data, respectively. With the purpose of application in catalysis, the SG-Pr-THIO was reacted with a Mo(ii) organometallic complex, forming the new material SG-Pr-THIO-Mo. Only a few works in the literature have reported this type of reaction, and none dealt with thiourea and Mo(ii) complexes. The new Mo-silica gel organometallic material was tested as catalyst in the epoxidation of cyclooctene and styrene. © 2013 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

Estudo da acessibilidade aos sítios ativos e desativação na desidratação do glicerol utilizando catalisadores zeolíticos lamelares

Pós-graduação em Química - IQ

Characterization of corn (Zea mays) leaf powder and Its adsorption properties regarding Cu(II) and Cd(II) from aqueous samples

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

Adsorption of immunoglobulin Y in supermacroporous continuous cryogel with immobilized Cu2+ ions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Biosorption of Cr(III) using in natura and chemically treated tropical peats

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Adsorção de selênio em latossolos

A retenção de Se pelos colóides do solo constitui importante processo para a manutenção da sanidade ambiental. A informação sobre a adsorção de Se em solos altamente intemperizados é restrita e existem poucos padrões quantitativos disponíveis para a definição de estratégias de remediação de áreas contaminadas. Quantidades crescentes de Se (5, 10, 25, 50, 100 e 250 mg L-1), na forma de Na2SeO3, foram adicionadas a amostras de dez Latossolos brasileiros [três Latossolos Vermelho-Amarelos (LVA-1, LVA-2 e LVA-3), dois Latossolos Vermelhos (LV-1 e LV-2), um Latossolo Vermelho eutroférrico (LVef), um Latossolo Vermelho acriférrico (LVwf), dois Latossolos Amarelos (LA-1 e LA-2) e um Latossolo Amarelo acriférrico (LAwf)]. Isotermas de adsorção foram construídas e foi verificado o ajuste dos resultados experimentais aos modelos de Langmuir e de Freundlich. A equação de Langmuir ajustou melhor os resultados de adsorção de Se do que a isoterma de Freundlich. Todas as isotermas apresentaram o formato tipo-L (exponencial), com exceção daquelas obtidas para o LVA-1 e para o LVA-2, que apresentaram comportamento tipo-C (linear). Valores de adsorção máxima (Ads máx), estimada pelo modelo de Langmuir, variaram de 135 (LVA-3) a 2.245 mg kg-1 (LA-1), enquanto os coeficientes de afinidade (K L) estiveram entre 0,002 (LVA-2) e 0,326 (LVA-3). A constante de afinidade estimada pelo modelo de Freundlich (Kf) variou de 13,7 (LVA-2) a 180,1 (LAwf). A adsorção máxima de Se foi mais elevada no LVef e nos Latossolos ácricos (LAwf e LVwf), enquanto os maiores valores de Kf foram encontrados no LV-2, LVef, LVA-3 e LVwf. Não houve correlação entre os atributos dos solos e as constantes de Langmuir. Valores de Kf correlacionaram-se com os teores de argila (r = 0,42*) e com a capacidade de troca de ânions (r = 0,64*).

Adsorção e lixiviação de boro em Latossolo Vermelho-Amarelo

O objetivo deste trabalho foi avaliar a adsorção e a lixiviação do boro em Latossolo Vermelho-Amarelo distrófico, cultivado com soja, em conseqüência das doses de boro e da calagem. Foram analisadas amostras de um solo do Estado do Mato Grosso, cultivado com soja durante três anos, com doses de 0, 1,5, 3, 4,5, 6, 7,5 e 9 Mg ha-1 de calcário, e 0, 1, 3, 5, 7 e 10 kg ha-1 de boro, aplicados no primeiro ano de cultivo. Foram determinadas isotermas de adsorção de boro em função da calagem e do tempo de cultivo, assim como a lixiviação em função da calagem e da adubação boratada. No caso da calagem, mesmo com doses relativamente altas de calcário, a adsorção de boro pelo solo é muito alta apenas no ano de aplicação do corretivo, e diminui significativamente com o tempo. No entanto, a lixiviação de boro guarda estreita relação com o teor do nutriente no solo e com a dose do nutriente que é aplicada, mas é pouco influenciada pela calagem.

Hexagonal mesoporous silica modified with 2-mercaptothiazoline for removing mercury from water solution

A method for the attachment of 2-mercaptothiazoline (MTZ) to modified silica gel has been developed. In the first step, a new silylant agent was synthesized, named SiMTZ, by the reaction between MTZ molecule and chloropropyltrimethoxysilane (SiCl). SiMTZ and tetraethylortosilicate were co-condensed in the presence of n-dodecylamine, a neutral surfactant template, to produce a modified ordered hexagonal mesoporous silica named HMTZ. The modified material contained 0.89 +/- 0.03 mmol of 2-mercaptothiazoline per gram of silica. FT-IR, FT-Raman, Si-29- and C-13-NMR spectra were in agreement with the proposed structure of the modified mesoporous silica in the solid state. HMTZ material has been used for divalent mercury adsorption from aqueous solution at 298 I K. The series of adsorption isotherms were adjusted to a modified Langmuir equation. The maximum number of moles of mercury adsorbed gave 2.34 +/- 0.09 mmol/g of material. The same interaction was followed by calorimetric titration on an isoperibol calorimeter. The HMTZ presented a high capacity for the removal of the contaminant mercury from water. The Delta H and Delta G values for the interaction were determined to be -56.34 +/- 1.07 and -2.14 +/- 0.11 kJ mol(-1). This interaction process was accompanied by a decrease of entropy value (- 182 J mol(-1) K-1). Thus, the interaction between mercury and HMTZ resulted in a spontaneous thermodynamic system with a high favorable exothermic enthalpic effect. (c) 2007 Elsevier B.V. All rights reserved.

Nanoparticles of octakis [3-(3-amino-1,2,4-triazole)propyl] octasilsesquioxane as ligands for Cu(II), Ni(II), Cd(II), Zn(II), and Fe(III) in aqueous solution

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) were tested as ligands, for transition-metal ions in aqueous solution with a special attention to sorption isotherms, ligand-metal interaction, and determination of metal ions in natural waters. The adsorption potential of the material ATZ-SSQ was compared with related [3(3-amino-1,2,4-triazole)propyl]silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from aqueous solution. The Langmuir model was used to simulate the sorption isotherms. The results suggest that the sorption of these metals on ATZ-SSQ and ATZ-SG occurs mainly by surface complexation. The equilibrium condition is reached at time lower than 3 min for ATZ-SSQ, while for ATZ-SG is only reached at time of 25 min. The maximum metal ion uptake values for ATZ-SSQ were higher than the corresponding values achieved with the ATZ-SG. In order to obtain more information on the ligand-metal interaction of the complexes on the surface of the ATZ-SSQ nanomaterial, ESR study with various degrees of copper loadings was carried out. The ATZ-SSQ was tested for the determination (in flow using a column technique) of the metal ions present in natural waters. (C) 2007 Elsevier B.V. All rights reserved.

4-amine-2-mercaptopyrimidine modified silica gel applied in Cd(II) and Pb(II) extraction from an aqueous medium

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

Preconcentration and determination of Cu(II) in a fresh water sample using modified silica gel as a solid-phase extraction adsorbent

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

Structure of copper(II) complexes adsorbed on functionalized polyhedral oligomeric silsesquioxane

The 3-amino-1,2,4-triazole-modified silsesquioxane nanoplatforms have been prepared and characterized. The silsesquioxane nanocages readily react with CuX(2) in aqueous solution to form copper complex-substituted silsesquioxanes. Adsorption isotherms of CuX(2) from aqueous solution were studied at 25 degrees C. The electronic and ESR spectral parameters indicated that the copper ion is in a distorted-tetragonal symmetry field. (C) 2007 Elsevier B.V. All rights reserved.

Preconcentration and determination of metal ions in commercial ethanol used as fuel for automotive engines

The present investigation reports the synthesis, characterization, and adsorption properties of a new nanomaterial based on organomodified silsesquioxane nanocages. The adsorption isotherms for CuCl,, CoCl2, ZnCl2, NiCl2, and FeCl3 from ethanol solutions were performed by using the batchwise method. The equilibrium condition is reached very quickly (3 min), indicating that the adsorption sites are well exposed. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of the nanomaterial, using 5 mL of 1.0 mol L-1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the development of a method for preconcentration and determination of metal ions at trace level in commercial ethanol, used as fuel for car engines. The values determined by recommended method for plants 1, 2, and 3 indicated an amount of copper of 51, 60, and 78 mu g L-1, and of iron of 2, 15, and 13 mu g L-1, respectively. These values are very close to those determined by conventional analytical methods. Thus, these similar values demonstrated the accuracy of the determination by recommended method.

Study on soluble heavy metals with preconcentration by using a new modified oligosilsesquioxane sorbent

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

Attachment of 2,2-bipyridine onto a silica gel for application as a sequestering agent for copper, cadmium and lead ions from an aqueous medium

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