Mário César Guerreiro

Cyclohexane oxidation continues to be a challenge

Abstract Many efforts have been made to develop new catalysts to oxidize cyclohexane under mild conditions. Herein, we review the most interesting systems for this process with different oxidants such as hydrogen peroxide, tert -butyl hydroperoxide and molecular oxygen. Using H 2 O 2 , Na-GeX has been shown to be a most stable and active catalyst. Mesoporous TS-1 and Ti-MCM-41 are also stable, but the use of other metals such as Cr, V, Fe and Mo leads to leaching of the metal. Homogeneous systems based on binuclear manganese(IV) complexes have also been shown to be interesting. When t -BuOOH is used, the active systems are those phthalocyanines based on Ru, Co and Cu and polyoxometalates of dinuclear ruthenium and palladium. Microporous metallosilicates containing different transition metals showed leaching of the metal during the reactions. Molecular oxygen can be used directly as an oxidant and decreases the leaching of active species in comparison to hydrogen peroxide and tert -butyl hydroperoxide. Metal aluminophosphates (metal: Mn, Fe, Co, Cu, Cr V) are active and relatively stable under such conditions. Mn-AlPO-36 yields directly adipic acid, but large amounts of carboxylic acids should be avoided, as they cause metal leaching from the catalysts. Rare earth exchanged zeolite Y also shows good selectivity and activity. In the last part of the review, novel alternative strategies for the production of cyclohexanol and cyclohexanone and the direct synthesis of adipic acid are discussed.

Activated carbon/iron oxide composites for the removal of atrazine from aqueous medium

The adsorption features of activated carbon and the oxidation properties of iron oxides were combined in a composite to produce new materials for atrazine removal from aqueous medium. Activated carbon/iron oxide composites were prepared at 1/1 and 5/1 mass ratios and characterized with powder X-ray diffractometry (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and nitrogen adsorption measurements. The adsorption and oxidation processes were evaluated in batch experiments, in order to monitor the atrazine removal capacity of these composites. The main iron oxide actually present in the composites was goethite (alpha-FeOOH). Impregnation with iron oxide reduced the surface area by its deposition in the activated carbon pores. However, a higher iron concentration promoted a higher oxidation rate, indicating that the efficiency of the oxidation reaction is related with the iron content and not with the pre-concentration of the contaminant on the carbon surface through adsorption process.

Estimation of surface area and pore volume of activated carbons by methylene blue and iodine numbers

micropore volume and total pore volume using multiple regression. The models obtained from the calibrations were used in predicting these physical properties of a test group of activated carbon samples produced from several raw materials. In all cases, the predicted values were in good agreement with the expected values. The method allows extracting more information from the methylene blue and iodine adsorption studies than normally obtained with this type of material.

PREPARAÇÃO E CARACTERIZAÇÃO DE CARVÃO ATIVADO PRODUZIDO A PARTIR DE RESÍDUOS DO BENEFICIAMENTO DO CAFÉ

Coffee fruit processing is one of the most polluting activities in agriculture due to the large amount of waste generated in the process. In this work, coffee parchment was employed as precursor for the production of carbons activated with ZnCl2 (CAP). The material was characterized using N2 adsorption/desorption at 77 K, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The material showed a surface area of 521.6 m2 g-1 and microporous structure. CAP was applied as adsorbent for the removal of methylene blue dye in aqueous medium. The adsorption capacity was found to be about 188.7 mg g-1.

Nióbia magnética como adsorvente de contaminantes orgânicos em meio aquoso: efeito da temperatura e do pH

This work describes novel materials based on pure iron oxide and iron oxide/niobia composite to produce a magnetic adsorbent. These materials were prepared with synthetic iron oxide and characterized by powder XRD, SEM, FTIR, TPR and Mossbauer spectroscopy. Results showed that the main iron oxides formed were goethite (aFeOOH) and maghemite (gFe2O3) with small particle size. The iron oxide and iron oxide/niobia composite showed high adsorption ability for organic compounds. The positive enthalpy indicated an endothermic adsorption process suggesting physical adsorption.

Produção de carvão a partir de resíduo de erva-mate para a remoção de contaminantes orgânicos de meio aquoso

In this work we present a new adsorbent material, obtained by mate waste pyrolisis. The resulting charcoal presented high specific area when compared with other pyrolized materials and also high capacity to remove organic contaminants from aqueous solution. The charcoal showed specific area of 344, 191 and ~0.3 m2 g-1 for sample Mate 1, Mate 2 and Mate 3, respectively. According to the corresponding adsorption isotherm these materials present good adsorption capacity for reactive textile and methylene blue dyes and the herbicide atrazine. Adsorption maxima were respectively 16, 230 and 35 mg g-1 for such substances, when sample Mate 1 was used.In this work we present a new adsorbent material, obtained by mate waste pyrolisis. The resulting charcoal presented high specific area when compared with other pyrolized materials and also high capacity to remove organic contaminants from aqueous solution. The charcoal showed specific area of 344, 191 and ~0.3 m g for sample Mate 1, Mate 2 and Mate 3, respectively. According to the corresponding adsorption isotherm these materials present good adsorption capacity for reactive textile and methylene blue dyes and the herbicide atrazine. Adsorption maxima were respectively 16, 230 and 35 mg g for such substances, when sample Mate 1 was used.

Characterization of Brazilian green propolis throughout the seasons by headspace GC/MS and ESI-MS

BACKGROUND A screening of the chemical composition of eight commercial classes of raw Brazilian green propolis throughout the seasons was carried out. A multivariate exploratory analysis of chemical composition obtained by gas chromatography associated with mass spectrometry with headspace extraction (HS-GC/MS), and by mass spectrometry with electrospray ionization (ESI-MS) was carried out using principal component analysis (PCA). RESULTS Differences in the volatile and polyphenolic profiles of propolis samples were verified during the seasons. Within each season, the high quality commercial classes of propolis presented similar characteristics, while the low quality classes presented distinct compositions. In spring and summer, propolis of the trimming class, commonly considered of low quality by beekeepers, presented a composition similar to the superior quality propolis. CONCLUSION Seasonality influences the chemical composition of the commercial classes of raw Brazilian green propolis. Headspace-GC/MS and ESI-MS assisted by PCA are effective to characterize volatile and non-volatile compounds of the propolis samples, and to correlate it to the seasons.

Experimental and theoretical investigation of epoxide quebrachitol derivatives through spectroscopic analysis.

Two synthetic epoxide derivatives, important intermediates in organic synthesis, were obtained from L-quebrachitol, and their conformations were proposed based on spectroscopic analysis. Density functional theory (DFT) calculations of infrared and NMR spectra were shown to be reliable enough for organic chemistry applications. The observed structures were determined with the aid of the DFT spectroscopic data, stressing the relevance and utility of combined experimental/theoretical studies and also the usefulness of the (13)C NMR B3LYP/6-31G(d,p) calculations.

Estudo dos efeitos do silício e do fósforo na redução da disponibilidade de metais pesados em área de mineração

This study was developed with a soil contaminated by heavy metals, with the purpose of evaluating the action of silicon and phosphorus as protection agents through simple extractions by DTPA. The collected samples were prepared and incubated with five doses of silicon and five doses of phosphorus, with four replicates, amounting to 100 experimental units. After 30 and 60 days, samples of each treatment were collected, submitted to pH analyses and simple extraction by DTPA. The amounts of DTPA-extracted metals depended on the doses of silicon and phosphorus and on the pH. Treatments with silicon and phosphorus was efficient in decreasing the availability of heavy metals in soil.

Changes in isoelectric point as affected by anion adsorption on two brazilian oxisols

Abstract Iron and aluminum oxides are widespread in tropical environments and increase soils isoelectric point (IP). Anion adsorption modifies the IP and the surface charge of oxidic materials. This study evaluated IP changes on A‐ and B‐horizon samples of two Brazilian Oxisols upon reaction with acetate, citrate, oxalate, phosphate and sulfate (1 mmol L−1; soil–solution 1∶100; pH 5.5; ionic strength 30 mmol L−1 as NaCl). Most anions seemed to be specifically adsorbed, because the IP decreased after the reaction with the ligands. The IP of natural and of the acetate‐, citrate‐, oxalate‐, phosphate‐, and sulfate‐treated samples followed the order: Red Latosol‐A: 2.89,2.86, <2.50, 2.63, 2.79, 2.86; Red Latosol‐B: 5.92, 5.89, 2.79, 3.42, 3.36, 5.84; Red‐yellow Latosol‐A: 2.89, 2.79, <2.50, <2.50, 2.66, 2.89; and Red‐yellow Latosol‐B: 6.38, 6.29, 3.06, 4.36, 3.69, 6.15. The decrease in IP caused by citrate, oxalate, and Phosphate is relevant because this interferes with charge‐dependent soil reactions.