Miguel A. Vicente

Recent Advances in the Synthesis and Catalytic Applications of Pillared Clays

New methods have been developed in recent years that are now being successfully applied in the preparation of pillared interlayered clays (PILCs). Variations in the procedures concern different parameters involved in the synthesis, such as the starting clay, the intercalating solution, the intercalation process, and the drying and calcination steps of the pillared solids, among others. In the present article, the latest results obtained when introducing modifications in the chemical aspects of PILC synthesis are reviewed. These include (1) pillaring with mixed solutions containing two or more cations, (2) using coordination or organometallic compounds, (3) using polymers and surfactants, (4) pillaring of acid-activated clays, and (5) enhancement of PILC acidity. A separate section is devoted to the specific features of preparing these solids in amounts large enough to make their manufacture on an industrial scale economically feasible. Recent developments in the catalytic applications of PILCs are also reviewed, with emphasis on the progressively more extended use of these materials as catalytic supports.

Recent Advances in the Control and Characterization of the Porous Structure of Pillared Clay Catalysts

Several methods have been developed and applied in recent years in the characterization of the structure of microporous materials, in general, and of pillared clays, in particular. In the present article, the latest results obtained in the control of the microstructure developed in alumina‐pillared clays and various approaches used to the evaluation of the porosity of these materials are reviewed. These include the control of the microstructure developed in pillared clays by adjusting the several parameters involved in the synthesis process, and the evaluation of the porosity of pillared clays. Emphasis is given to the methods to evaluate the pore size and pore size distribution (PSD) of these materials. Two separate sections are devoted to review mathematical modeling studies and 129Xe NMR spectroscopy of physisorbed Xe to investigate the microporous structural properties of these materials.

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.

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.

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.

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.

Influence of the Ti precursor on the properties of Ti-pillared smectites

Abstract The pillaring of smectites (two saponites and a montmorillonite) with various Ti precursors was studied. The minerals were intercalated with ‘classical’ Ti precursors, such as titanium tetrachloride and titanium tetraethoxide, and also with new precursors, such as solutions of titanium tetraisopropoxide in acetic acid, or titanium (bis (ethylacetoacetato) diisopropoxide) in acetone. A complete characterization of the intercalated solids was carried out and a comparison of the properties of the solids as a function of the precursors used in the intercalation established. The influence of the severe conditions in which the intercalation with Ti oligomers is usually carried out (low pH and/or high temperature) on the properties of the intercalated solids was analysed. Intercalation with TiCl4 and Ti(EtO)4 strongly affected the structure of the clays, not by acid attack on the octahedral sheet, but mainly by disaggregation of particles. Ti(isop)4 was found to be less aggressive for the clays, while Ti(etacet)2(isop)2 did not form pillared solids but organo-clays, and therefore was of no use as a pillaring agent. The solids were thermally stable up to 300°C, showing a high specific surface area.

Fenton degradation of sulfanilamide in the presence of Al,Fe-pillared clay: Catalytic behavior and identification of the intermediates

Liquid phase catalytic degradation of sulfanilamide with H2O2 was carried out in the presence of Fe,Al/M-pillared clay (Fe,Al/M-MM, M=Na(+), Ca(2+) and Ba(2+)) as heterogeneous Fenton type catalyst. Fe,Al/M-MMs were prepared by swelling of layered aluminosilicate (90-95 wt.% montmorillonite) from a bed located in Mukhortala (Buryatia, Russia) in Na(+), Ca(2+) and Ba(2+) forms by means of the exchange of these cations with bulky Fe,Al-polyoxocations prepared at Al/Fe=10/1 and OH/(Al+Fe)=2.0, and then calcinated at 500°C. XRD method and chemical analysis demonstrated that the rate of crystalline swelling was dependent on the interlayer cations and decreased in the order: Fe,Al-/Na-MM>Fe,Al/Ca-MM>Fe,Al/Ba-MM. It was found that the catalytic properties of Fe,Al/M-MMs depended on the type of exchangeable cations. The effect of the H2O2/sulfanilamide molar ratio, the catalyst content, the reaction temperature and the reaction pH on the removal rate of sulfanilamide has been studied in the presence of Fe,Al/Na-MM. The catalyst can be applied for degradation of sulfanilamide with H2O2 for at least three successive cycles without loss of activity. HPLC analyses pointed out that the main degradation intermediate products were sulfanilic acid, benzenesulfonic acid, p-benzoquinone and aliphatic carboxylic acids.

Study of the Porous Solids Obtained by Acid Treatment of a High Surface Area Saponite

A new deposit of saponite, Vicálvaro (Madrid, Spain), has recently been described in the Madrid Basin (provinces of Madrid and Toledo, Central Spain). The acid treatment of such material and the characterization of the solids obtained are reported in the present paper. The surface area of the natural saponite is rather high, 197 m2/g, related to the very small size of the clay particles due to the sedimentary origin of the deposit. The treatment of the saponitic material at room temperature with 0.62 wt% HCl for times of between 2 and 48 h or with 1.25 wt% HCl solutions for times of up to 6 h produces a partial dissolution of the saponite structure, resulting in the formation of mixtures of unattacked saponite and free silica, with a high development of the textural properties of the solids. The treatment with 1.25 wt% HCl solutions for times of over 6 h results in an almost total dissolution of the structure of the clay, the obtained solids being mainly formed by some delaminated saponite sheets, free silica and insoluble impurities. Solids with a maximum surface area of 462 m2/g and a maximum number of acid centres of 0.98 mmol H+/g are obtained.

Catalytic Degradation of Organic Pollutants in Aqueous Streams by Mixed Al/M-Pillared Clays (M = Fe, Cu, Mn)

The low cost, natural origin, high stability, and great versatility for applications in adsorption and catalysis have made pillared interlayered clays (PILCs) one of the families of functional materials most intensively studied in the past three decades. PILCs involving several transition metals like Fe, Cu, or Mn are emerging nanomaterials exhibiting exceptional physicochemical properties. Besides, they also display excellent performance in the heterogeneous catalytic depletion of organic pollutants in aqueous systems. The recent literature involving these materials is reviewed, emphasizing on the works describing their role as active solids in the catalytic wet (hydrogen) peroxide oxidation (CWPO - CWHPO) of harmful organic compounds in contaminated aqueous streams.