Study of the Catalytic Properties of Co2+, Mn2+ and Ni2+ Dipicolinate Complexes Immobilized on Kaolinite.

• Grant number: 11/17660-8
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• Start date: November 01, 2011
• End date: November 30, 2013
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
• Principal Investigator: Emerson Henrique de Faria
• Grantee: Francielle Rodrigues Araújo
• Host Institution: Pró-Reitoria Adjunta de Pesquisa e Pós-Graduação. Universidade de Franca (UNIFRAN). Franca , SP, Brazil

Abstract

In recent years, much interest has been shown to hybrid materials based on clays. These materials are produced by different reactions and can give a rise to intercalation compounds with different applications, depending on the type of interaction between inorganic matrix and the intercalated species. Some molecules such as dyes, pharmaceuticals, polymers and complexes have been incorporated into inorganic matrices for applications in areas such as catalysis, luminescence, drug delivery systems, adsorption and photocatalysis. In particular, transition metal complexes have recognized technological importance for application as catalysts to of hydrocarbon oxidations. However, the complexes in homogeneous medium due to their nature have low yields and selectivity. Thus, an alternative for applications requiring high temperature during the process, high conversion and selectivity is based on the use of complex immobilized into inorganic matrices. In these, use is made of "heterogeneity", the process of immobilization the homogeneous complexes (with high catalytic activity) in inorganic matrices such as kaolinite, able to modify the kinetics and mechanism of oxidation reactions. Nevertheless, the application of complex in heterogeneous medium is even further limited by the low diffusion of substrates and products in these solid matrices. Factors such as heat resistance, mechanical and chemical stability of these can lead to obtain a range of applications much more flexible. For this purpose, hybrid materials have been explored and among them stands out the kaolinite-based materials due to high thermal stability of hybrids obtained. In this project, we proposes the use such a host matrix for the immobilization of complexes of transition metals (Co 2+, Mn 2+ and Ni 2+), and the guest ligand pyridine 2,6-dicarboxylic acid (dipicolinic acid). Two strategies will be used for the incorporation of the complexes in the interlayer spaces of the matrix: i) functionalization of the matrix with the pyridine dicarboxylic ligand followed by complexation with transition metals, ii) exfoliation of the matrix functionalized in ultrasonic bath in water medium followed by complexation with transition metals. Hybrids will be characterized structural and morfologically and through various spectroscopic techniques (electronic and nuclear magnetic resonance). These solids will be applied as catalysts in hydrocarbon oxidation reactions: cis-cyclooctene (evaluation activity), and cyclohexane (selectivity) but also to reaction of Baeyer-Villiger oxidation of cyclohexanone to µ-caprolactone.

Scientific publications

(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)

BARBOSA, LORRANA VIETRO; MARCAL, LIZIANE; NASSAR, EDUARDO J.; CALEFI, PAULO S.; VICENTE, MIGUEL A.; TRUJILLANO, RAQUEL; RIVES, VICENTE; GIL, ANTONIO; KORILI, SOPHIA A.; CIUFFI, KATIA J.; et al. Kaolinite-titanium oxide nanocomposites prepared via sol-gel as heterogeneous photocatalysts for dyes degradation. CATALYSIS TODAY, v. 246, p. 133-142, MAY 15 2015. (13/50216-0, 11/17660-8, 13/19523-3)

DE CARVALHO, ANALAURA LOVO; FERREIRA, BRENO F.; GOMES MARTINS, CARLOS H.; NASSAR, EDUARDO J.; NAKAGAKI, SHIRLEY; MACHADO, GUILHERME SIPPEL; RIVES, VICENTE; TRUJILLANO, RAQUEL; VICENTE, MIGUEL A.; GIL, ANTONIO; et al. Tetracarboxyphenylporphyrin-Kaolinite Hybrid Materials as Efficient Catalysts and Antibacterial Agents. Journal of Physical Chemistry C, v. 118, n. 42, p. 24562-24574, OCT 23 2014. (13/50216-0, 11/17660-8, 13/19523-3)

ARAUJO, FRANCIELLE R.; BAPTISTA, JOEL G.; MARCAL, LIZIANE; CIUFFI, KATIA J.; NASSAR, EDUARDO J.; CALEFI, PAULO S.; VICENTE, MIGUEL A.; TRUJILLANO, RAQUEL; RIVES, VICENTE; GIL, ANTONIO; et al. Versatile heterogeneous dipicolinate complexes grafted into kaolinite: Catalytic oxidation of hydrocarbons and degradation of dyes. CATALYSIS TODAY, v. 227, p. 105-115, MAY 15 2014. (13/50216-0, 12/07410-7, 11/17660-8)