Preparation of Original and Calcined Layered Double Hydroxide as Low-Cost Adsorbents: The Role of the Trivalent Cation on Methylene Blue Adsorption.

Layered double hydroxides with the hydrotalcite-like structure, containing Mg2+, Al3+, and Fe3+ (with different Al/Fe ratios) in the layers, have been synthesized and fully characterized, as have the mixed oxides formed upon their calcination at 500 °C. Both series of solids (original and calcined ones) have been tested for methylene blue adsorption. In the case of the Fe-containing sample, oxidation of methylene blue takes place simultaneously with adsorption. For the calcined samples, their reconstruction to the hydrotalcite-like structure plays an important role in their adsorption ability.

Photocatalytic Degradation of Paracetamol in Aqueous Medium Using TiO2 Prepared by the Sol-Gel Method.

Two titania photocatalysts have been prepared using the sol-gel method using TiCl4 as a precursor, and two different alcohols, namely, ethanol or propanol (Et or Pr). The main aim of this work was to study the effect of the nature of the alcohol on the chemical, structural and photocatalytic properties for paracetamol photodegradation of the final solids. The TiCl4/alcohol molar ratio to obtain the corresponding alkoxides (TiEt and TiPr) was 1/10. These alkoxides were calcined at 400 °C to prepare the oxide catalysts (named as TiEt400 and TiPr400). Powder X-ray diffraction (PXRD) of the original samples showed the presence of anatase diffraction peaks in sample TiPr, while TiEt is a completely amorphous material. Contrary to commercial TiO2-P25, the PXRD diagrams of the calcined samples showed anatase as the exclusive crystalline phase in both solids. The specific surface area (SBET) of sample TiPr400 was larger than that of sample TiEt400, and both larger than that of TiO2-P25. The three solids have been tested in the photodegradation of paracetamol in aqueous solution. It has been established that the alcohol used influences the properties and catalytic activity of the final oxides. The synthesized solids exhibit a higher activity than commercial TiO2-P25, because of their structural characteristics and larger SBET.

Fast and Clean Synthesis of Nylon-6/Synthetic Saponite Nanocomposites.

Nylon/saponite nanocomposites were synthesized and characterized. The nanocomposites were prepared by means of a fast, efficient, low cost, and environmentally friendly method. All of the tested preparations resulted in the pre-designed nanocomposites. To this end, delaminated saponites were directly synthesized to be used as a filler in a polymer matrix formed by nylon-6 by the in situ intercalation polymerisation of an ε-caprolactam monomer without the use of surfactants or other organic reagents to organophilise the clay, thus avoiding the drawbacks of contamination. The efficiency of the preparation method increased, and significant savings were achieved in terms of both energy reaction time, savings of 60% and 70%, respectively, by using microwave radiation as an energy source during the synthesis of the nanocomposites. In addition, given that the method that was followed avoids the use of contaminating organophilic agents, it is important to highlight the savings in reagents and the fact that there was zero environmental contamination.

Preparation of Al/Fe-PILC clay catalysts from concentrated precursors: enhanced hydrolysis of pillaring metals and intercalation.

The modification of bentonite with Al-Fe species from different concentrated precursors at both stages: (i) the preparation of the (Al/Fe)-mixed pillaring solution and (ii) intercalation itself, was studied at lab scale. The final solids were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), Cationic Exchange Capacity (CEC), textural analyses by nitrogen adsorption-desorption at 77 K, and hydrogen-temperature programmed reduction (H2-TPR). Finally, the modified clays were assessed as active materials in the Catalytic Wet Peroxide Oxidation (CWPO) of phenol under very mild conditions through 1.0 h of reaction: T = 25.0 °C ± 0.1 °C, pH = 3.7, ambient pressure (76 kPa), and 0.5 g catalyst per dm3. Metal hydrolysis by the dissolution of elemental aluminium (final Total Metal Concentration TMC = 4.62 mol dm-3) achieved the best results, decreasing the volume of solution per mass unit of clay required to successfully expand the layered starting mineral by a factor of close to 75, in comparison with the widespread conventional preparation using highly diluted Al-based pillaring solutions. Even in the absence of any solvent for the clay dispersion, the intercalating/pillaring method was shown to be favourable, as a novel strategy promoting the process intensification and subsequent preparation of Al/Fe- and other Al-based pillared clays at larger scales. The best catalyst prepared from concentrated precursors exhibited 79.1% phenol conversion, 19.3% TOC mineralization, and pretty low iron leaching (0.037 mg Fe dm-3; ∼0.12% w/w) in such a short catalytic assessment; all these results were quite comparable or even exceeded those exhibited by the catalyst prepared from dilute precursors.

White and Red Brazilian São Simão's Kaolinite-TiO2 Nanocomposites as Catalysts for Toluene Photodegradation from Aqueous Solutions.

The presence of volatile organic compounds in groundwater is a major concern when it is used as a drinking water source because many of these compounds can adversely affect human health. This work reports on the preparation and characterization of white and red Brazilian São Simão's kaolinite-TiO2 nanocomposites and their use as catalysts in the photochemical degradation of toluene, a significant volatile organic compound. The nanocomposites were prepared by a sol-gel procedure, using titanium bis(triethanolaminate)diisopropoxide as a precursor. Thermal treatments of the nanocomposites led to different polymorphic titania phases, while the clay changed from kaolinite to metakaolinite. This structural evolution strongly affected the photocatalytic degradation behavior-all the solids efficiently degraded toluene and the solid calcined at 400 °C, formed by kaolinite and anatase, showed the best behavior (90% degradation). On extending the photochemical treatment up to 48 h, high mineralization levels were reached. The advantage of photodegradation using the nanocomposites was confirmed by comparing the results from isolated components (titanium dioxide and kaolinite) to observe that the nanocomposites displayed fundamental importance to the photodegradation pathways of toluene.

Microwave-Assisted Pillaring of a Montmorillonite with Al-Polycations in Concentrated Media.

A montmorillonite has been intercalated with Al3+ polycations, using concentrated solutions and clay mineral dispersions. The reaction has been assisted by microwave radiation, yielding new intercalated solids and leading to Al-pillared solids after their calcination at 500 °C. The solids were characterized by elemental chemical analysis, X-ray diffraction, FTIR spectroscopy, thermal analyses, and nitrogen adsorption. The evolution of the properties of the materials was discussed as a function of the preparation conditions. Microwave treatment for 2.5 min provided correctly pillared solids.

Hydrotalcite catalysis for the synthesis of new chiral building blocks.

The use of hydrotalcites for the synthesis of two chiral building blocks in a simple way is described as a new and green methodology. The synthesis of these compounds implies a regioselective Baeyer-Villiger reaction in a very selective way with ulterior opening and lactonisation. This methodology should be considered green for the use of hydrogen peroxide as the only oxidant and hydrotalcites as the catalyst, and because no residues are produced apart from water. The procedure is very adequate for using in gram scale, in order to increase the value of the obtained compounds. The conditions are excellent and can be applied for nonstable compounds, as they are very mild. The synthesised compounds are magnific starting materials for the synthesis of biologically active or natural compounds. The use of a cheap, commercial and chiral compound as carvone disposable in both enantiomeric forms adds an extra value to this methodology.

Organically Modified Saponites: SAXS Study of Swelling and Application in Caffeine Removal.

This study aimed to assess the capacity of saponite modified with n-hexadecyltrimethylammonium bromide (CTAB) and/or 3-aminopropyltriethoxysilane (APTS) to adsorb and remove caffeine from aqueous solutions. Powder X-ray diffraction (PXRD) revealed increased basal spacing in the modified saponites. Small-angle X-ray scattering (SAXS) confirmed the PXRD results; it also showed how the different clay layers were stacked and provided information on the swelling of natural saponite and of the saponites functionalized with CTAB and/or APTS. Thermal analyses, infrared spectroscopy, scanning electron microscopy, element chemical analysis, and textural analyses confirmed functionalization of the natural saponite. The maximum adsorption capacity at equilibrium was 80.54 mg/g, indicating that the saponite modified with 3-aminopropyltriethoxysilane constitutes an efficient and suitable caffeine adsorbent.

The role of oxidative debris on graphene oxide films.

We study the effect of oxidative impurities on the properties of graphene oxide and on the graphene oxide Langmuir-Blodgett films (LB). The starting material was grupo Antolín nanofibers (GANF) and the oxidation process was a modified Hummers method to obtain highly oxidized graphene oxide. The purification procedure reported in this work eliminated oxidative impurities decreasing the thickness of the nanoplatelets. The purified material thus obtained presents an oxidation degree similar to that achieved by chemical reduction of the graphite oxide. The purified and non-purified graphene oxides were deposited onto silicon by means of a Langmuir-Blodgett (LB) methodology. The morphology of the LB films was analyzed by field emission scanning microscopy (FE-SEM) and micro-Raman spectroscopy. Our results show that the LB films built by transferring Langmuir monolayers at the liquid-expanded state of the purified material are constituted by close-packed and non-overlapped nanoplatelets. The isotherms of the Langmuir monolayer precursor of the LB films were interpreted according to the Volmer's model.

Takovite-aluminosilicate-Cr materials prepared by adsorption of Cr3+ from industrial effluents as catalysts for hydrocarbon oxidation reactions.

The catalytic efficiency of takovite-aluminosilicate-chromium catalysts obtained by adsorption of Cr(3+) ions from aqueous solutions by a takovite-aluminosilicate nanocomposite adsorbent is reported. The adsorbent was synthesized by the coprecipitation method. The catalytic activity of the final Cr-catalysts depended on the amount of adsorbed chromium. (Z)-cyclooctene conversion up to 90% with total selectivity for the epoxide was achieved when the oxidation was carried out with hydrogen peroxide, at room temperature. After five consecutive runs, the catalysts maintained high activity, although after the sixth reuse, the epoxide yields strongly decreased to 35%. The catalysts were also efficient for cyclohexane oxidation, reaching up to 18% conversion, with cyclohexanone/cyclohexanol selectivity close to 1.2. On the whole, their use as catalysts gives a very interesting application for the solids obtained by adsorption of a contaminant cation such as Cr(3+).

New highly luminescent hybrid materials: terbium pyridine-picolinate covalently grafted on kaolinite.

Luminescent hybrid materials derived from kaolinite appear as promising materials for optical applications due to their specific properties. The spectroscopic behavior of terbium picolinate complexes covalently grafted on kaolinite and the influence of the secondary ligand and thermal treatment on luminescence are reported. The resulting materials were characterized by thermal analysis, element analysis, X-ray diffraction, infrared absorption spectroscopy, and photoluminescence. The thermogravimetric curves indicated an enhancement in the thermal stability up to 300 °C for the lanthanide complexes covalently grafted on kaolinite, with respect to the isolated complexes. The increase in the basal spacing observed by X-ray diffraction confirmed the insertion of the organic ligands into the basal space of kaolinite, involving the formation of a bond between Al-OH and the carboxylate groups, as evidenced by infrared spectroscopy. The luminescent hybrid material exhibited a stronger characteristic emission of Tb(3+) compared to the isolated complex. The excitation spectra displayed a broad band at 277 nm, assigned to a ligand-to-metal charge transfer, while the emission spectra presented bands related to the electronic transitions characteristic of the Tb(3+) ion from the excited state (5)D(4) to the states (7)F(J) (J=5, 4, and 3), with the 4→5 transition having high intensity with green emission.

New synthesis strategies for effective functionalization of kaolinite and saponite with silylating agents.

Functionalization of Brazilian São Simão kaolinite and Spanish Yunclillos saponite with the alkoxysilanes 3-aminopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane is reported. The resulting hybrids were characterized by X-ray diffraction, thermal analysis, infrared absorption spectroscopy, and scanning electron microscopy, which demonstrated the effectiveness of the interlamellar grafting process. The X-ray diffractograms revealed incorporation of the alkoxide molecules into the interlayer space of the clays. The displacement of the stretching bands of interlayer hydroxyls in the infrared spectra of the modified kaolinites and the increased intensity of the Mg-OH vibrations in the spectra of the modified saponites confirmed the functionalization of the clays. The thermal behavior of the organoclays confirmed the stability of the hybrids, which was dependent on the clay used for preparation of the materials.

Hybrid materials prepared by interlayer functionalization of kaolinite with pyridine-carboxylic acids.

This paper presents the results of the functionalization of Brazilian São Simão kaolinite with pyridine-2-carboxylic and pyridine-2,6-dicarboxylic acids. The functionalization involved refluxing of the pyridine-carboxylic acid in the presence of kaolinite previously intercalated with dimethyl sulfoxide; both acids effectively displaced dimethyl sulfoxide from the clay interlayer. The resulting materials were characterized by X-ray diffraction, thermal analysis, infrared absorption spectroscopy, and C and N elemental analysis. The X-ray diffractograms revealed the incorporation of the acid molecules into the interlayer space of kaolinite. The thermogravimetric curves of the kaolinite samples functionalized with the pyridine-carboxylic acids indicated that the materials were thermally stable up to 300 degrees C. The displacements of the bands due to interlayer hydroxyls in the infrared absorption spectra also confirmed the functionalization of the kaolinite with the pyridine-carboxylic acids.

Porphyrin-kaolinite as efficient catalyst for oxidation reactions.

The preparation, characterization, and application in oxidation reactions of new biomimetic catalysts are reported. Brazilian Sao Simao kaolinite clay has been functionalized with [meso-tetrakis(pentafluorophenyl)porphinato]iron(III), Fe(TPFPP). To obtain the functionalized clay, the natural clay was purified by dispersion-sedimentation, expanded by insertion of dimethyl sulfoxide (DMSO), and functionalized with amino groups by substitution of DMSO with ethanolamine. These previous steps allowed clay functionalization with Fe(TPFPP), leading to a layered material with a basal spacing of 10.73 A. Clay functionalization with the porphyrin was confirmed by formation of the secondary amine, as demonstrated by FTIR bands at 3500-3700 cm(-1). UV-vis spectroscopy revealed a red shift in the Soret band of the iron porphyrin in the functionalized material as compared to the parent iron porphyrin catalyst in solution, indicating Fe(III)P --> Fe(II)P reduction. The catalytic performance of the functionalized clay was evaluated in the epoxidation of cyclooctene, with complete selectivity for the epoxide (100% epoxide yield), and ketonization of cyclohexane, cyclohexanone being the major product. The novel catalyst was also evaluated in the Baeyer-Villiger (BV) oxidation of cyclohexanone, with 85% conversion of cyclohexanone in epsilon-caprolactone, with total selectivity to epsilon-caprolactone.