Multifunctional heterogeneous catalysts: Tetrakis(pentafluorophenyl) porphinato]iron(III) immobilized on amine-functionalized Diatomaceous Earth for catalytic and adsorption applications

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do Prado, Marcus Vinicius ; Gonzalez, Beatriz ; Vicente, Miguel A. ; Trujillano, Raquel ; Nassar, Eduardo Jose ; Gil, Antonio ; Santamaria, L. ; Korili, Sophia A. ; Marcal, Liziane ; de Faria, Emerson H. ; Ciuffi, Katia J.

• Document type: Journal article
• Source: JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING; v. 11, n. 3, p. 11-pg., 2023-03-21.

Abstract

The use of Diatomaceous Earth (DE) as a promising support of a synthetic metalloporphyrin is reported, trying to heterogenize metalloporphyrin catalysts to mimicking enzyme site isolation and improving reaction selectivity. New multifunctional hybrid materials consisting of DE amino-functionalized with aminopropyltriethoxysilane (DE-APTES), followed by grafting with [meso-tetrakis(pentafluorophenyl)porphinato]iron(III) (DE-APTES-FeTFPP), were prepared and fully characterized. FeTFPP was grafted into DE-APTES via the amine groups (band at 1570 cm(-1)). The brown color of the materials indicated that FeTFPP was immobilized in the matrix; a Soret band characteristic of ironporphyrin located in a confined space, was found at 416 nm. Leaching studies confirmed that the ironporphyrin was entrapped and not just adsorbed on the silica surface. DE was composed of typical quartz and cristobalite crystalline phases and amorphous silica. The intensity of its characteristic reflection at 22 degrees (2 theta) decreased in the presence of FeTFPP, evidencing that the ironporphyrin influ-enced the organization of the material. Catalytic tests using DE-APTES-FeTFPP in cyclooctene epoxidation to cyclooctene oxide (56 % yield, with complete selectivity for the epoxide) and cyclohexane oxidation (4 % yield of oxidized products, with ketone/alcohol selectivity similar to 3:1), evidenced the versatility of the catalyst and the multifunctionality of the resulting hybrid materials and the ability of DE as a promising natural support for ironporphyrin catalysts. Finally, the capacity of the materials as CO2 adsorbents was evaluated in the temperature range 100-200 degrees C. DE-APTES showed a maximum adsorption capacity of 1.26 mmol/g at 100 degrees C, 18 times higher than the value found under the same conditions for the non-functionalized support. (AU)

• FAPESP's process: 05/00720-7 - Synthesis, characterization and catalytic activity of biomimetic and non-biomimetic systems, in hydrocarbon oxidation, using hydrogen peroxide as oxidant
• Grantee: Katia Jorge Ciuffi Pires
• Support Opportunities: Regular Research Grants
• FAPESP's process: 11/03335-8 - Ironporphyrins as catalysts in oxidation reaction of cyclohexane and Baeyer-Villeger: heterogeneous systems
• Grantee: Katia Jorge Ciuffi Pires
• Support Opportunities: Regular Research Grants
• FAPESP's process: 12/11673-3 - Thin films obtained by spin and dip-coating using sol-gel methodology
• Grantee: Eduardo José Nassar
• Support Opportunities: Regular Research Grants
• FAPESP's process: 16/01501-1 - Multifunctional catalysts for advanced oxidation processes employing biogenic matrices or clays
• Grantee: Katia Jorge Ciuffi Pires
• Support Opportunities: Regular Research Grants
• FAPESP's process: 20/06712-6 - Ironporphyrins-titanium supported on clay or silica matrices for photocatalytic production of hydrogen peroxide
• Grantee: Katia Jorge Ciuffi Pires
• Support Opportunities: Regular Research Grants