Hyperfine interaction in Zn-Al layered double hydroxides intercalated with conducting polymers

Organic-inorganic hybrid materials based on the assembly between inorganic 2D host structure and polymer have received considerable attention in the last few years. This emerging class of materials presents several applications according to their structural and functional properties. Particularly, among others, layered double hydroxides (LDHs) provide the opportunity of preparing new organically modified 2D nanocomposites. Pyrrole carboxylic acid derivatives, namely 4-(lH-pyrrol-1-yl)benzoate, 3-(pyrrol-i-yl)-propanoate,7-(pyrrol-1-yl)-heptanoate, and aniline carboxylic acid derivative, namely 3-aminobenzoic acid, have been intercalated in LDHs of intralamellar composition Zn2Al(OH)(6). The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by powder X-ray diffraction patterns (PXRD), transmission electron microscopy (TEM) thermogravimetric analysis (TGA), and electron spin resonance (ESR). The basal spacing found by the PXRD technique gives evidence of the formation of bilayers of the intercalated anions. ESR spectra present a typical signal with a superhyperfine structure with 6 + 1 lines (g = 2.005 +/- 0.0004), which is assigned to the interaction between a carboxylate radical from the guest molecules and a nearby aluminium nucleus (I = 5/2) from the host structure. Additionally, the ESR data suggest that the monomers are connected to each other in limited number after thermal treatment. (c) 2007 Elsevier Ltd. All rights reserved.

New layered double hydroxides intercalated with substituted pyrroles. 1. In situ polymerization of 4-(1H-pyrrol-1-yl)benzoate

The two-dimensional hybrid organic-inorganic materials Zn-2-Cr and Zn-2-Al-LDHs (Layered Double Hydroxides) containing 4-(1H-pyrrol-1yl)benzoate anions as the interlayer anions were synthesized by the co-precipitation method at constant pH followed by subsequent hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, ESR, TGA, and TEM. The basal spacing found by the X-ray diffraction technique is coincident with the formation of bilayers of the intercalated anions. Solid-state C-13 NMR and ESR data strongly suggest the partial in situ polymerization of the 4-(1H-pyrrol-1yl)benzoate anions during coprecipitation. (c) 2006 Elsevier Ltd. All rights reserved.

New layered double hydroxides intercalated with substituted pyrroles. 2. 3-(Pyrrol-1-yl)-propanoate and 7-(pyrrol-1-yl)-heptanoate LDHs

We report the synthesis and characterization of organic-inorganic hybrid materials: Zn-2-Al-LDHs (layered double hydroxides) containing 3-(1H-pyrrol-1-yl)-propanoate and 7-(1H-pyrrol-l-yl)-heptanoate as the interlayer anions. The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, TGA, and ESR. The basal spacing found by PXRD technique is coincident with the formation of bilayers of the intercalated anions. The solid state C-13 NMR showed that the interlayered anions remain identical after intercalation. ESR data suggest that the monomers connect each other in a limited number of guests when a thermal treatment is applied. The inorganic LDH sheets delay the temperature of degradation of the monomers. (c) 2006 Elsevier Ltd. All rights reserved.

Synthesis, characterization and electrochemical study of layered double hydroxides intercalated with 2-thiophenecarboxylate anions

The synthesis, characterization, and electrochemical study of the Zn(II)-Al(III) and Zn(II)-Cr(III) Layered Double Hydroxides (LDHs) containing 2-thiopenecarboxylate as the interlayer anions are described. The LDHs were prepared by the constant pH coprecipitation technique followed by hydrothermal treatment for 72 h. The materials were analyzed by PXRD, FT-IR, C-13 CP-MAS, EDX, TEM, and CV. The presence of the organic heterocyclic anions was confirmed by FT-IR and the related solid-state C-13 NMR data strongly suggested that these were dimerised during coprecipitation. Accordingly, the basal spacing found by the X-ray technique was similar to 15.3 Angstrom, a distance coincident with the formation of bilayers of the intercalated anions. The structural organization of all the new materials was greatly enhanced by hydrothermal treatment, as shown by PXRD. The improved organization of the bilayered structures had a strong influence in the electrochemical behaviour of clay-modified electrodes produced with these materials, such as the diminished resistance to the ionic flow through the LDHs films. (C) 2003 Elsevier Ltd. All rights reserved.

Thermal decomposition of crystalline Ni-II-Cr-III layered double hydroxide: A structural study of the segregation process

A structural study of the thermal evolution of Ni0.69Cr0.31(OH)(2)(CO3)(0.155)(.)nH(2)O into NiO and tetragonal NiCr2O4 is reported. The characteristic structural parameters of the two coexisting crystalline phases, as well as their relative abundance, were determined by Rietveld refinement of powder x-ray diffraction (PXRD) patterns. The results of the simulations allowed us to elucidate the mechanism of the demixing process of the oxides. It is demonstrated that nucleation of a metastable nickel chromite within the common oxygen framework of the parent Cr-III-doped bunsenite is the initial step of the cationic redistribution. The role that trivalent cations play in the segregation of crystalline spinels is also discussed.

XAS/WAXS time-resolved phase speciation of chlorine LDH thermal transformation: Emerging roles of isovalent metal substitution

The XAS/WAXS time-resolved method was applied for unraveling the complex mechanisms arising from the evolution of several metastable intermediates during the degradation of chlorine layered double hydroxide (LDH) upon heating to 450 °C, i.e., Zn2Al(OH)6·nH2O, ZnCuAl(OH)6·nH2O, Zn2Al 0.75Fe0.25(OH)6·nH2O, and ZnCuAl0.5Fe0.5(OH)6·nH2O. After a contraction of the interlamellar distance, attributed to the loss of intracrystalline water molecules, this distance experiences an expansion (T > 175-225 °C) before the breakdown of the lamellar framework around 275-295 °C. Amorphous prenucleus clusters with crystallo-chemical local order of zinc-based oxide and zinc-based spinel phases, and if any of copper-based oxide, are formed at T > 175-225 °C well before the loss of stacking of LDH layers. This distance expansion has been ascribed to the migration of Zn II from octahedral layers to tetrahedral sites in the interlayer space, nucleating the nano-ZnO or nano-ZnM2O4 (M = Al or Fe) amorphous prenuclei. The transformation of these nano-ZnO clusters toward ZnO crystallites proceeds through an agglomeration process occurring before the complete loss of layer stacking for Zn2Al(OH)6· nH2O and Zn2Al0.75Fe0.25(OH) 6·nH2O. For ZnCuAl(OH)6·nH 2O and ZnCuAl0.5Fe0.5(OH)6· nH2O, a cooperative effect between the formation of nano-CuO and nano-ZnAl2O4 amorphous clusters facilitates the topochemical transformation of LDH to spinel due to the contribution of octahedral CuII vacancy to ZnII diffusion. © 2013 American Chemical Society.

Bacterial cellulose as a template for preparation of hydrotalcite-like compounds

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

Materiais derivados de hidróxidos duplos lamelares: síntese, caracterização e aplicação em adsorção e processos avançados de oxidação

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

Produção de biodiesel etílico utilizando óxidos mistos derivados de hidróxidos duplos lamelares como catalisadores

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Dynamical study of ZnO nanocrystal and Zn-HDS layered basic zinc acetate formation from sol-gel route

We have pointed out that zinc based particles obtained from ethanolic solution of a zinc acetate derivative (zinc oxy-acetate, Zn4O(Ac)(6)) are a mixture of nanometer sized ZnO, zinc oxy-acetate, and zinc hydroxide double salt (Zn-HDS). The knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, and the evolution of Zn species in reaction medium was monitored in situ during 14 h by simultaneous measurements of UV-vis absorption and extended X-ray absorption fine structures (EXAFS) spectra. This spectroscopic monitoring was initialized just after the addition of an ethanolic lithium hydroxide solution ([LiOH]/[Zn] = 0. 1) to the reaction medium kept under controlled temperature (40 degrees C). This study points out the first direct evidence of the reaction between ZnO nanoparticles and unreacted zinc oxy-acetate to form a Zn-HDS phase. The dissolution of ZnO and the reprecipitation of Zn-HDS are induced by the gradual release of water mainly produced by ethanol esterification well evidenced by gas chromatography coupled to mass spectroscopy and FT-IR measurements.

Platinum-Group Minerals in Chromitites of the Niquelandia Layered Intrusion (Central Goias, Brazil): Their Magmatic Origin and Low-Temperature Reworking during Serpentinization and Lateritic Weathering

A variety of platinum-group-minerals (PGM) have been found to occur associated with the chromitite and dunite layers in the Niquelandia igneous complex. Two genetically distinct populations of PGM have been identified corresponding to phases crystallized at high temperatures (primary), and others formed or modified during post-magmatic serpentinization and lateritic weathering (secondary). Primary PGM have been found in moderately serpentinized chromitite and dunite, usually included in fresh chromite grains or partially oxidized interstitial sulfides. Due to topographically controlled lateritic weathering, the silicate rocks are totally transformed to a smectite-kaolinite-garnierite-amorphous silica assemblage, while the chromite is changed into a massive aggregate of a spinel phase having low-Mg and a low Fe3+/Fe2+ ratio, intimately associated with Ti-minerals, amorphous Fe-hydroxides, goethite, hematite and magnetite. The PGM in part survive alteration, and in part are corroded as a result of deep chemical weathering. Laurite is altered to Ru-oxides or re-crystallizes together with secondary Mg-ilmenite. Other PGM, especially the Pt-Fe alloys, re-precipitate within the altered chromite together with kaolinite and Fe-hydroxides. Textural evidence suggests that re-deposition of secondary PGM took place during chromite alteration, controlled by variation of the redox conditions on a microscopic scale.

Identification of a bisegmented double-stranded RNA virus (picobirnavirus) in calf faeces

To determine the incidence of rotavirus infection among dairy herds in the State of Sdo Paulo, Brazil, 576 faecal samples obtained from calves aged 1-45 days with and without diarrhoea, reared on 63 dairy cattle farms, were analyzed. Polyacrylamide gel electrophoresis (PAGE) identified 28 samples positive for group A rotavirus, while four samples, two diarrhoeic and two non-diarrhoeic, showed a bisegmented genome with a typical picobirnavirus pattern. Electron microscopy revealed spherical virus particles with a diameter of 37 nm and without a defined surface structure. The present study is the first report of a bisegmented virus identified in cattle in Brazil. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Voltammetric performance and application of a sensor for sodium ions constructed with layered birnessite-type manganese oxide

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effects of probiotic bacteria, isoflavones and simvastatin on lipid profile and atherosclerosis in cholesterol-fed rabbits: a randomized double-blind study

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

Effects of isoflavone-supplemented soy yogurt on lipid parameters and atherosclerosis development in hypercholesterolemic rabbits: a randomized double-blind study

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