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Ironporphyrins as catalysts in oxidation reaction of cyclohexane and Baeyer-Villeger: heterogeneous systems


The development of chemical processes within the Green chemistry context will ensure environmental sustainability. In this sense, the preparation and characterization of active, selective and recyclable heterogeneous catalysts must be accomplished. Indeed, many of the currently employed industrial reactions must be optimized, and conditions must be adjusted by studying not only the reaction conditions, but also the properties of the heterogeneous catalysts. The Bayer Villiger (BV) and the cyclohexane oxidation reactions are two extremely important processes from an industrial viewpoint, since they serve as a means for the production of highly valuable chemicals. However, the industrial routes utilized nowadays employ toxic reagents or oxidants, leading to low product selectivity. Therefore, these reactions must be improved, so that they can be more effectively and selectively applied by the chemical industry. Synthetic metalloporphyrins have been effectively used as biomimetic models of enzymes, such as monooxygenases, in a series of oxidation reactions. Nevertheless, few studies have reported on their application as catalysts for the BV reaction. Our group pioneered the use of these catalysts in heterogeneous systems for accomplishment of the BV reaction, which has given us broad perspective on the study of these biomimetic (or bioinspired) catalysts. This research project aims to develop and apply catalysts consisting of inorganic matrices prepared by the sol-gel process or comprised of natural clays (kaolinite) containing second-generation ironporphyrins or transition metal ions, iron in particular, as active phases. These catalysts shall be applied in the selective catalytic oxidation of hydrocarbons, cyclohexane, and ketones (BV reaction), so that the ideal conditions for the use of hydrogen peroxide as oxidant can be established. So our main target is the construction of stable, selective, and recyclable catalysts whose active phase remains in the system, instead of being lixiviated, meeting the requirements of Green chemistry. To this end, a thorough study relating the textural and morphological properties of the obtained catalyst with their catalytic efficiency will be carried out. (AU)

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Scientific publications (6)
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
RICCI, GUSTAVO PIMENTA; GARCIA, LARISSA OLIVEIRA; NASSAR, EDUARDO JOSE; NAKAGAKI, SHIRLEY; STIVAL, JOAO FELIPE; DA ROCHA, ZENIS NOVAES; VICENTE, MIGUEL ANGEL; TRUJILLANO, RAQUEL; JIMENEZ, ALEJANDRO; RIVES, VICENTE; MARCAL, LIZIANE; DE FARIA, EMERSON HENRIQUE; CIUFFI, KATIA JORGE. Non-hydrolytic sol-gel synthesis of mesoporous iron-aluminum oxide and their properties in the oxidation of hydrocarbons by hydrogen peroxide. Microporous and Mesoporous Materials, v. 325, OCT 2021. Web of Science Citations: 0.
DE ARAUJO, DENIS T.; CIUFFI, KATIA J.; NASSAR, EDUARDO J.; VICENTE, MIGUEL A.; TRUJILLANO, RAQUEL; RIVES, VICENTE; BERNAL, ELENA P.; DE FARIA, EMERSON H. Grafting of L-proline and L-phenylalanine amino acids on kaolinite through synthesis catalyzed by boric acid. APPLIED SURFACE SCIENCE ADVANCES, v. 4, JUN 1 2021. Web of Science Citations: 0.
BALDAN, JR., HUGO; DA SILVA, EVANE; SALTARELLI, MICHELLE; CRISPIM, DENISE; NASSAR, EDUARDO J.; TRUJILLANO, RAQUEL; RIVES, VICENTE; VICENTE, MIGUEL A.; GIL, ANTONIO; KORILI, SOPHIA A.; DE FARIA, EMERSON H.; CIUFFI, KATIA J. Inorganic-organic hybrids based on sepiolite as efficient adsorbents of caffeine and glyphosate pollutants. APPLIED SURFACE SCIENCE ADVANCES, v. 1, n. SI NOV 1 2020. Web of Science Citations: 2.
DA SILVA, ALEXANDRE FERNANDO; DE PADUA, GABRIEL SILVA; DE ARAUJO, DENIS TALARICO; VIEIRA, CARLOS ALEXANDRE; DE FARIA, EMERSON H. Immobilization of L-alanine into natural kaolinite via amidation catalyzed by boric acid for the development of biohybrid materials. Journal of Solid State Chemistry, v. 287, JUL 2020. Web of Science Citations: 0.
DE ARAUJO, D. T.; DE PADUA, G. S.; PEIXOTO, V. G.; CIUFFI, K. J.; NASSAR, E. J.; VICENTE, M. A.; TRUJILLANO, R.; RIVES, V; PEREZ-BERNAL, M. E.; DE FARIA, E. H. Luminescent properties of biohybrid (kaolinite-proline) materials synthesized by a new boric acid catalyzed route and complexed to Eu3+. APPLIED CLAY SCIENCE, v. 192, JUL 2020. Web of Science Citations: 0.
DE SOUSA, EDUARDO P.; DE ARAUJO, DENIS T.; PEIXOTO, VINILSON G.; FERREIRA, BRENO F.; DE FARIA, EMERSON H.; MOLINA, EDUARDO F. Effect of sodium bentonite content on structural-properties of ureasil poly (ethylene oxide)-PEO hybrid: A perspective for water treatment. APPLIED CLAY SCIENCE, v. 191, JUN 15 2020. Web of Science Citations: 0.

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