Layered niobate nanosheets: building blocks for advanced materials assembly

Layered materials with intracrystalline reactivity undergo intercalation and pillaring reactions to produce materials with useful properties for catalysis, electrodes for Li batteries and adsorbents. New possibilities for the use of layered inorganic solids came out from the layered structures capable of delamination. the exfoliated particles are considered a new class of nanomaterial based on single crystal nanosheets. Due to their unique morphological features and properties, these nanosheets can be used as building blocks for nanomaterials with innovative properties. in this feature article we describe the aspects related to layered niobate exfoliation and the new possibilities that arises from the use of niobate nanosheets in the manufacturing of thin films, layer-by-layer (LbL) assemblies, hybrid structures, sensors and other materials.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Instituto do Milenio de Materiais ComplexosUniv São Paulo, Inst Quim, BR-05508000 São Paulo, BrazilUniversidade Federal de São Paulo, Dept Ciencias Exatas & Terra, BR-09972270 Diadema, SP, BrazilUniversidade Federal de São Paulo, Dept Ciencias Exatas & Terra, BR-09972270 Diadema, SP, BrazilWeb of Scienc

Chemical modification of niobium layered oxide by tetraalkylammonium intercalation

Chemical modification of the layered K4Nb6O17 material was systematically investigated through the reaction of its proton-exchanged form (H2K2Nb6O17) in alkaline solutions containing tetramethylammonium (tma+), tetraethylammonium (tea+) or tetrapropylammonium (tpa+) cations. The intercalated amount reaches 50% (for tma+), 25% (for tea+) and 15% (for tpa+) of the H2K2Nb6O17 negative charge (concerning the exchange at interlayer I) due to the steric hindrance of larger cations. Hexaniobate samples present (020) basal reflections equal to 23.0, 26.3 and 26.5 Å once intercalated respectively with tma+, tea+ and tpa+. When samples are heated above 200-250 ºC, CO2 evolution is observed; Hofmann elimination reaction is also detected for hexaniobate-tpa+ samples. Scanning electron microscopy images show the predominance of plate-like particles; stick-like particles are also observed for samples containing bulky ions. The intercalation reaction is promoted in the order tma+ > tea+ > tpa+, while the formation of a dispersion of colloidal particles is facilitated in the inverse order.A modificação química do material lamelar K4Nb6O17 foi investigada sistematicamente através da reação de sua forma protônica (H2K2Nb6O17) em soluções alcalinas contendo os cátions tetrametilamônio (tma+), tetraetilamônio (tea+) ou tetrapropilamônio (tpa+). A quantidade intercalada corresponde a 50% (para tma+), 25% (para tea+) e 15% (para tpa+) da carga negativa do H2K2Nb6O17 (considerando a troca iônica na região interlamelar I). As amostras de hexaniobato apresentam reflexões basais (020) de 23,0, 26,3 e 26,5 Å quando intercaladas, respectivamente, com tma+, tea+ e tpa+. Aquecendo-se as amostras acima de 200-250 ºC, observa-se a liberação de CO2; a reação de eliminação de Hofmann também é observada para as amostras de hexaniobato-tpa+. As imagens de microscopia eletrônica de varredura mostram a presença predominante de partículas em forma de placas; partículas em forma de bastões também são observadas nas amostras contendo íons volumosos. A reação de intercalação é promovida na ordem tma+ > tea+ > tpa+, enquanto a formação de uma dispersão de partículas coloidais é facilitada na ordem inversa

Evaluation of the influence of sulfur-based functional groups on the embedding of silver nanoparticles into the pores of MCM-41

The incorporation of noble metals in the pores of mesoporous silicas might produce materials with interesting catalytic and sensing capabilities, but the proper control of pore filling and the avoidance of nanoparticles migration to outside the pores are processes not yet completely understood. In this work, we evaluated the role of -SH and -SO3H groups post-grafted into MCM-41 on the production of silver nanoparticles by using 1-butanol as reducing agent. Thiol groups were the most efficient on promoting the formation of nanoparticles within the pores. Conversely, sulfonic groups establish electrostatic interactions with silver cations that preclude the formation of nanoparticle in yields comparable to thiol groups. MCM-41 without functional groups did not have good affinity to silver and the nanoparticles are produced outside the pores. This study showed the importance on selecting an adequate surface functional group in order to obtain silver nanoparticles filling the pores of MCM-41. (C) 2015 Elsevier Inc. All rights reserved.Sao Paulo Research foundation (FAPESP)National Counsel of Technological and Scientific Development (CNPq)Univ Fed Sao Paulo, Inst Ciencias Ambientais Quim & Farmaceut, Lab Mat Hibridos, Diadema, SP, BrazilUniv Fed Sao Paulo, Inst Ciencias Ambientais Quim & Farmaceut, Lab Mat Hibridos, Diadema, SP, BrazilFAPESP: 2011/50318-1CNPq: 483878/2011-1Web of Scienc

Intercalation compounds involving inorganic layered structures

Two-dimensional inorganic networks can shown intracrystalline reactivity, i.e., simple ions, large species as Keggin ions, organic species, coordination compounds or organometallics can be incorporated in the interlayer region. The host-guest interaction usually causes changes in their chemical, catalytic, electronic and optical properties. The isolation of materials with interesting properties and making use of soft chemistry routes have given rise the possibility of industrial and technological applications of these compounds. We have been using several synthetic approaches to intercalate porphyrins and phthalocyanines into inorganic materials: smectite clays, layered double hydroxides and layered niobates. The isolated materials have been characterized by elemental and thermal analysis, X-ray diffraction, surface area measurements, scanning electronic microscopy, electronic and resonance Raman spectroscopies and EPR. The degree of layer stacking and the charge density of the matrices as well their acid-base nature were considered in our studies on the interaction between the macrocycles and inorganic hosts

Intercalation Compounds involving Inorganic Layered Structures

ABSTRACT Two-dimensional inorganic networks can shown intracrystalline reactivity, i.e., simple ions, large species as Keggin ions, organic species, coordination compounds or organometallics can be incorporated in the interlayer region. The host-guest interaction usually causes changes in their chemical, catalytic, electronic and optical properties. The isolation of materials with interesting properties and making use of soft chemistry routes have given rise the possibility of industrial and technological applications of these compounds. We have been using several synthetic approaches to intercalate porphyrins and phthalocyanines into inorganic materials: smectite clays, layered double hydroxides and layered niobates. The isolated materials have been characterized by elemental and thermal analysis, X-ray diffraction, surface area measurements, scanning electronic microscopy, electronic and resonance Raman spectroscopies and EPR. The degree of layer stacking and the charge density of the matrices as well their acid-base nature were considered in our studies on the interaction between the macrocycles and inorganic hosts

A new method for producing highly concentrated non-aqueous dispersions of silver nanoparticles and the evaluation of their bactericidal activity

Different preparation methods of silver nanoparticles (AgNP) are well described in the literature, most of them in aqueous medium. Aqueous dispersions of AgNP normally have a limited capacity to tolerate high nanosilver concentrations. However, AgNP production in non-aqueous medium is still scarce although its exploitation for example, as coating for hydrophobic surfaces, would be of a huge importance in many technological applications. in this work, we report the chemical preparation of highly concentrated non-aqueous AgNP dispersions obtained by reduction of silver cation, from two distinct salt sources (AgNO3 and AgBF4), by 1-butanol in the presence of a biocompatible poly(ether-block-amide) copolymer, named PEBA. the highest concentration reached was around 5 mM, when it used AgBF4 as silver source and 4 % (w/w) of a PEBA solution in 1-butanol. This AgNP concentration is notably higher than the values reported in aqueous medium. the AgNP formation was attested by UV-Vis spectroscopic analysis, which showed the characteristic strong plasmon band at 420 nm. the X-ray diffraction patterns confirmed the formation of a crystalline fcc silver metallic phase with particle diameters ranging from 5 to 10 nm accordingly to transmission electron microscopy examination. It was also observed that the AgNP dimensions are dependent on the PEBA and silver salt concentrations. the AgNP dispersions presented a very high antimicrobial activity against E. coli and S. aureus microorganisms, even in low concentration, attested by the Kirby-Bauer method.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Universidade Federal de São Paulo, Lab Mat Hibridos, Inst Ciencias Ambientais Quim & Farmaceut, BR-09913030 São Paulo, BrazilUniversidade Federal de São Paulo, Dept Cirurgia, Lab Transplante Expt Orgaos, BR-09913030 São Paulo, BrazilUniversidade Federal de São Paulo, Lab Mat Hibridos, Inst Ciencias Ambientais Quim & Farmaceut, BR-09913030 São Paulo, BrazilUniversidade Federal de São Paulo, Dept Cirurgia, Lab Transplante Expt Orgaos, BR-09913030 São Paulo, BrazilCNPq: 483878/2011-1Web of Scienc