Catalytic dehydration of glycerol over Cu-Fe-Al-based oxides: understanding changes in active sites throughout the reaction.

The glycerol conversion into acetol using Fe, Al and Cu-based oxides was investigated. XRD results indicate the formation of nanosized particles with high phase dispersion, however, Raman, Mössbauer, 27Al NMR and XPS spectroscopies suggest the presence of iron(iii) oxide, Al2O3 and CuO phases. The FTIR with pyridine adsorption revealed high Lewis acidity. The TPR profile showed the reduction temperature range for the Fe3+ and Cu2+ sites, indicating the suitable condition for pretreatment. The N2 adsorption-desorption isotherms indicated the presence of micro-mesopores with interesting textural properties and specific area varying between 71 and 220 m2 g-1, while the porous morphology was observed by SEM and TEM images. The optimized catalytic tests showed glycerol conversion of 60% and acetol selectivity of 92% with 17% of coke according to TG profile. The recycling tests confirmed the efficiency of the solid, reaching 28% conversion and 91% acetol selectivity after four reuses and, after reactivation in an oxidizing atmosphere, the catalytic performance obtained results close to the second reuse. The interaction between the different Lewis acid sites involved in the mechanisms for the acetol and coke formation on the catalyst surface is discussed. The charge distribution represented by colors which indicates the acid-base surface was evaluated by a simple theoretical-computational study based on the DFT approach. The synergy between the active sites indicates that the presence of Cu0/Cu+ drastically increases the acetol selectivity which is a more important characteristic than the high Lewis acidity of Fen+ and Al3+.

Can We Form Mesoporous Zeolites by Steam Assisted Crystallization of MCM-41?

The possibility of crystallizing silicalite-1 (MFI) from the pore walls of as-synthesized MCM-41 via steam-assisted crystallization (SAC) was thoroughly investigated. A kinetic study was conducted through the impregnation of as-synthesized MCM-41 with the structure-directing agent tetrapropyl-ammonium hydroxide (TPAOH). Materials obtained after different SAC treatment times (1−288 h) were characterized by XRD, nitrogen physisorption at 77 K, TGA/DTA, and SEM. The achieved results allowed us to conclude that during SAC treatment, rapid destruction of the hexagonal mesophase occurs with the enlargement of mesopores, probably by their coalescence, until achieving non-porous amorphous silica. Only thereafter is the crystallization of the MFI phase evidenced through the development of micron-sized (>10 µm) MFI structured crystals. This study suggests the probable practical impossibility of even partial crystallization of the pore walls of mesoporous materials by SAC.

Organic-Free Synthesis of Finned Mordenite Zeolite.

Mordenite is a well-known zeolite widely used for industrial processes. However, its pore architecture can be inconvenient due to diffusional issues. A study of the synthesis parameters from an organic-free dense gel was carried out to control the crystal morphology, which resulted in finned mordenite zeolite particles. The obtained materials were characterized by XRD, FTIR, 29Si and 27Al MAS-NMR, elemental analysis, nitrogen physisorption, SEM, and TEM. We found that careful manipulation of the hydrothermal parameters directly affected the sizes and morphologies of the crystallites and particles, as well as the textural properties of the final products. Additionally, it was found that mordenite could exhibit a fin morphology with additional mesoporosity, which is a promising means to reduce the diffusional problems of one-dimensional-channel zeolites.

Hydrothermal Synthesis of Silicoaluminophosphate with AEL Structure Using a Residue of Fluorescent Lamps as Starting Material.

Silicoaluminophosphate molecular sieves of SAPO-11 type (AEL structure) were synthesized by the hydrothermal method, from the residue of a fluorescent lamp as a source or Si, Al, and P in the presence of water and di-propyamine (DPA) as an organic template. To adjust the P2O5/SiO2 and Si/Al and ratios, specific amounts of silica, alumina, or alumina hydroxide and orthophosphoric acid were added to obtain a gel with molar chemical composition 1.0 Al2O3:1.0 P2O5:1.2 DPA:0.3 SiO2:120 H2O. The syntheses were carried out at a temperature of 473 K at crystallization times of 24, 48, and 72 h. The fluorescent lamp residue and the obtained samples were characterized by X-ray fluorescence, X-ray diffraction, scanning electron microscopy, and BET surface area analysis using nitrogen adsorption isotherms. The presence of fluorapatite was detected as the main crystalline phase in the residue, jointly with considered amounts of silica, alumina, and phosphorus in oxide forms. The SAPO-11 prepared using aluminum hydroxide as Al source, P2O5/SiO2 molar ratio of 3.6 and Si/Al ratio of 0.14, at crystallization time of 72 h, achieves a yield of 75% with a surface area of 113 m2/g, showing that the residue from a fluorescent lamp is an alternative source for development of new materials based on Si, Al, and P.

Photocatalytic degradation of ibuprofen using titanium oxide: insights into the mechanism and preferential attack of radicals.

The present work studied ibuprofen degradation using titanium dioxide as a photocatalyst. Mechanistic aspects were presented and the preferred attack sites by the OH˙ radical on the ibuprofen molecule were detailed, based on experimental and simple theoretical-computational results. Although some previous studies show mechanistic proposals, some aspects still need to be investigated, such as the participation of 4-isobutylacetophenone in the ibuprofen degradation and the preferred regions of attack by OH˙ radicals. The photodegradation was satisfactory using 0.03 g of TiO2 and pH = 5.0, reaching 100% decontamination in 5 min. The zeta potential curve showed the regions of attraction and repulsion between TiO2 and ibuprofen, depending on the pH range and charge of the species, influencing the amount of by-products formed. Different by-products have been identified by GC-MS, such as 4-isobutylacetophenone. Ibuprofen conversion to 4-isobutylacetophenone takes place through decarboxylation reaction followed by oxidation. The proposed mechanism indicates that the degradation of ibuprofen undergoes a series of elementary reactions in solution and on the surface. Three different radicals (OH˙, O2 -˙ and OOH˙) are produced in the reaction sequence and contribute strongly to the oxidation and mineralization of ibuprofen and by-products, but the hydroxyl radical has a greater oxidation capacity. The simple study using the DFT approach demonstrated that the OH˙ radical attacks preferentially in the region of the ibuprofen molecule with high electronic density, which is located close to the aromatic ring (C[double bond, length as m-dash]C bond). The presence of the OH˙ radical was confirmed through a model reaction using salicylic acid as a probe molecule.

Study of Faujasite zeolite as a modified delivery carrier for isoniazid.

The adsorption of isoniazid in the Faujasite zeolite channels has been studied. For that, the influence of the pH from the solution media in the adsorption process was verified to enable higher amount of isoniazid retained. With the information of the best pH and the equilibrium time obtained with the kinetic study, an isotherm was constructed and the hybrid material obtained with the plateau concentration equilibrium was characterized with several techniques. Molecular modeling calculations were also performed for a better understanding of the adsorption process and how the interaction between zeolite and isoniazid occurs. The geometrical disposition of the drug molecules into the zeolite channels, the saturation levels, the different isoniazid protonation states with respect to the pH media and the interaction energy between the zeolite surface and the isoniazid molecule was studied. Finally, a drug release study was made to verify if the Faujasite-Y zeolite could change the isoniazid release in acid and phosphate buffer media. The results show that the Faujasite-Y has the possibility to work as carrier for isoniazid, where the adsorption process is more effective in media at pH 3, result confirmed by the molecular modeling. The isoniazid release essay showed that the hybrid material does not change the drug release profile, provides more stability in acid media, indicating that the zeolite can be used as carrier for isoniazid, and improve the medicine formulations on antituberculosis treatment.

Synthesis of Fe2SiO4-Fe7Co3 Nanocomposite Dispersed in the Mesoporous SBA-15: Application as Magnetically Separable Adsorbent.

The mixture containing alloy and oxide with iron-based phases has shown interesting properties compared to the isolated species and the synergy between the phases has shown positive effect on dye adsorption. This paper describes the synthesis of Fe2SiO4-Fe7Co3-based nanocomposite dispersed in Santa Barbara Amorphous (SBA)-15 and its application in dye adsorption followed by magnetic separation. Thus, it was studied the variation of reduction temperature and amount of hydrogen used in synthesis and the effect of these parameters on the physicochemical properties of the iron and cobalt based oxide/alloy mixture, as well as the methylene blue adsorption capacity. The XRD and Mössbauer results, along with the temperature-programmed reduction (TPR) profiles, confirmed the formation of Fe2SiO4-Fe7Co3-based nanocomposites. Low-angle XRD, N2 isotherms, and TEM images show the formation of the SBA-15 based mesoporous support with a high surface area (640 m2/g). Adsorption tests confirmed that the material reduced at 700 °C using 2% of H2 presented the highest adsorption capacity (49 mg/g). The nanocomposites can be easily separated from the dispersion by applying an external magnetic field. The interaction between the dye and the nanocomposite occurs mainly by π-π interactions and the mixture of the Fe2SiO4 and Fe7Co3 leads to a synergistic effect, which favor the adsorption.

Incorporation of Brazilian Diatomite in the Synthesis of An MFI Zeolite.

The need for greener procedures is a fact to reduce residues, to decrease industrial costs, and to accomplish the environmental agreements. In an attempt to address this question, we propose the addition of a natural resource, Brazilian diatomite, to an MFI zeolite traditional synthesis. We have characterized the resulting product with different techniques, such as X-ray diffraction, microscopy, and gas sorption, and, afterwards, we evaluate the greenness of the process by the Green Star method. The results were promising: We obtained the desired topology in the form of small crystallites aggregated and a pore diameter of 0.8 nm. In conclusion, the product has the necessary characteristics for an adsorption or catalytic future tests and escalation to industrial production.

Functional Carboxymethylcellulose/Zein Bionanocomposite Films Based on Neomycin Supported on Sepiolite or Montmorillonite Clays.

The present work introduces new functional bionanocomposite materials based on layered montmorillonite and fibrous sepiolite clays and two biopolymers (carboxymethylcellulose polysaccharide and zein protein) to produce drug-loaded bionanocomposite films for antibiotic topical delivery. Neomycin, an antibiotic indicated for wound infections, was employed as the model drug in this study. The physical properties and the antimicrobial activity of these materials were evaluated as a function of the type of hybrid and the amount of zein protein incorporated in the bionanocomposite films. In addition, the interfacial and physicochemical properties of these new clay-drug hybrids have been studied through a combination of experimental and computational methodologies, where the computational studies confirm the intercalation of neomycin into the montmorillonite layers and the possible penetration of the drug in the tunnels of sepiolite, as pointed out by N2 adsorption and X-ray diffraction techniques. The antimicrobial activity of these bionanocomposite materials show that the films based on montmorillonite-neomycin display a more pronounced inhibitory effect of the bacterial growth than those prepared with the sepiolite-neomycin hybrid. Such effect can be related to the difficult release of neomycin adsorbed on sepiolite due to a strong interaction between both components.

Scale Up Pillaring: A Study of the Parameters That Influence the Process.

Pillared clays (PILCs) are interesting materials mostly due to their high basal spacing and surface area, which make them suitable for adsorption and catalysis applications, for example. However, the production of these materials on industrial scale is dependent on research about what parameters influence the process. Thus, the objective of this work was to evaluate what parameters influence the pillaring procedure. For this, pillared clays were synthesized following three series of experiments. In the first series, the effect of the amount of water in a clay suspension was evaluated. The best results were obtained by using diluted suspensions (1 g of clay to 100 mL of water). In the second series, several pillaring methods were tested. In the third series, the amount of pillared clay was raised to 50 g. Fifty grams of pillared clay can be obtained using the pillaring agent synthesized at 60 °C with further aging for 24 h, and this material exhibited high basal spacing (17.6 Å) and surface area (233 m²/g). These values are comparable with the traditional pillaring method using only 3 g of clay.

Reuse of Pillaring Agent in Sequential Bentonite Pillaring Processes.

This work describes the synthesis and characterization of pillared clays using a new pillaring method: the reuse of the pillaring solution. First, an Al pillared clay (PILC) was synthesized, and after filtration, the pillaring agent was stored and reused for an additional three pillaring procedures (P1, P2, and P3). The filtered pillaring solution was stored for one year and then reused for one additional pillaring procedure (P4). The samples were analyzed using XRD, N2 physisorption measurements and chemical analysis (EDX). All of the samples exhibited basal spacings larger than 17 Å and BET surface areas greater than 160 m²/g. After the P4 pillaring, the pillaring agent was precipitated with a Na2SO4 solution, and the resulting solid was analyzed using XRD and SEM. The results indicated that even after a total of five pillaring procedures, Al13 ions were still present in solution. Therefore, it is possible to reuse the pillaring solution four times and to even store the solution for one year, which is important from an industrial perspective.

An Introduction to Zeolite Synthesis Using Imidazolium-Based Cations as Organic Structure-Directing Agents.

Zeolite synthesis is a wide area of study with increasing popularity. Several general reviews have already been published, but they did not summarize the study of imidazolium species in zeolite synthesis. Imidazolium derivatives are promising compounds in the search for new zeolites and can be used to help understand the structure-directing role. Nearly 50 different imidazolium cations have already been used, resulting in a variety of zeolitic types, but there are still many derivatives to be studied. In this context, the purpose of this short review is to help researchers starting in this area by summarizing the most important concepts related to imidazolium-based zeolite studies and by presenting a table of recent imidazolium derivatives that have been recently studied to facilitate filling in the knowledge gaps.

Bionanocomposite systems based on montmorillonite and biopolymers for the controlled release of olanzapine.

Olanzapine (OLZ) is a drug that is used in the treatment of schizophrenia and other psychoses, and it belongs to the thienobenzodiazepine class. The OLZ molecule has low solubility decreasing bioavailability, but has high permeability in membrane biological being classified as a Class II drug substance according to the Biopharmaceutics Classification System. It was reported many side effects of administering OLZ orally. So, in order to increase the bioavailability of drug and possibly reducing some of side effects, this paper proposes a new material able to controllably release the drug in the body. To control the dissolution rate, this work proposes a system that incorporates the drug into montmorillonite (MMT) dispersed in a mixture of alginate (ALG) and xanthan gum (XG) biopolymers. The proposed hybrids and bionanocomposites were characterized by several physicochemical techniques, including XRD, IR-ATR, TG DTA, SEM-EDS and HPLC. The characterization data confirmed the intercalation of the OLZ into the MMT by the ion exchange process, as well as the interaction of the MMT-OLZ with the biopolymers. The release test, conducted under various pH conditions, showed that the proposed system exhibited a more controlled drug release than commercial tablets, indicating that the ALG-XG/MMT-OLZ bionanocomposite can act as a controlled release system for OLZ.

Assessment of two immobilized lipases activity and stability to low temperatures in organic solvents under ultrasound-assisted irradiation.

Both stability and catalytic activity of two commercial immobilized lipases were investigated in the presence of different organic solvents in ultrasound-assisted system. In a general way, for Novozym 435, the use of ethanol as solvent led to a loss of activity of 35% after 10 h of contact. The use of iso-octane conducted to a gradual increase in lipase activity in relation to the contact time, reaching a maximum value of relative activity of 126%. For Lipozyme RM IM, after 5 h of exposure, the enzyme presented no residual activity when ethanol was used as solvent. The solvents tert-butanol and iso-octane showed an enhancement of about 20 and 17% in the enzyme activity in 6 h of exposure, respectively. Novozym 435 and Lipozyme IM presented high stability to storage after treatment under ultrasound-assisted system using n-hexane and tert-butanol as solvents.

Magnetic zeolites: a new adsorbent for removal of metallic contaminants from water.

In this work the adsorption features of Na Y zeolite with the magnetic properties of iron oxides have been combined in a composite to produce a magnetic adsorbent. These magnetic composites can be used as an adsorbent for metallic contaminants in water and subsequently removed from the medium by a simple magnetic process. The zeolites:iron oxide magnetic composites, were prepared by using Na Y with weight ratio of 3:1 and were characterized by powder X-ray diffraction (XRD), magnetization measurements, chemical analyses, N(2) adsorption isotherms and Mössbauer spectroscopy. Nitrogen adsorption isotherms showed that the surface area decreased from 505 m(2)g(-1) for the pure Na Y to 353 m(2)g(-1) for the Na Y:Fe oxide 3:1 composite. The adsorption isotherms of metal ions Cr(3+), Cu(2+) and Zn(2+) from aqueous solution onto the composites also showed that the presence of iron oxide does not affect the adsorption capacity.