Manganese-sulfonato porphyrin adsorbed on amino kaolinite as heterogeneous catalyst for oxidation and polymerization reactions

Autor(es)

Ferreira, Breno F. ; do Prado, Marcus V. ; Marcal, Liziane ; Ciuffi, Katia J. ; Vicente, Miguel A. ; Gil, Antonio ; de Faria, Emerson H.

• Tipo de documento: Artigo Científico
• Fonte: APPLIED CLAY SCIENCE; v. 235, p. 10-pg., 2023-02-27.

Resumo

Due to its medical applications, poly-caprolactone (PCL) is one of the most studied polymers. Herein, adsorption was used as a route to synthesize a new kaolinite/metalloporphyrin-based material for application in capro-lactone (e-CL) polymerization. Kaolinite (Kaol) was modified with tris(hydroxymethyl)aminomethane (TRIS), and the resulting Kaol-TRIS was used as adsorbent for 5,10,15,20-tetrakis(4-sulfonatophenyl)manganese(III) porphyrinate (MnTSPP). Kaol-MnTSPP was also prepared for comparison purposes. Kaolinite grafting with TRIS molecules increased the Kaol basal value from 7.2 to 12.7 angstrom. MnTSPP immobilization on Kaol-TRIS decreased the intensity and broadened the Kaol-TRIS reflection peaks, evidencing Kaol-TRIS exfoliation. Math-ematical equation models of Sips and Langmuir were used to fit the adsorption data, indicating a monolayer adsorption model (maximal adsorption = 8.78 mg center dot g- 1). Kaol-TRIS-MnTSPP stability and efficiency as a catalyst of cis-cyclooctene (C8) and cyclohexane oxidations were tested. Kaol-TRIS-MnTSPP obtained from 600 mg center dot L-1 MnTSPP aqueous solution provided the highest C8 conversion to cyclooctenoxide (81%). MnTSPP did not leach from Kaol-TRIS-MnTSPP, evidencing that TRIS acted as a binder for MnTSPP and enhanced its attachment to the matrix. In contrast, purified Kaol interacted with MnTSPP weakly: MnTSPP completely leached from Kaol-MnTSPP after the first catalytic cycle. Finally, Kaol-TRIS-MnTSPP was used to initiate e-CL polymerization. Monitoring of the reaction by infrared absorption spectroscopy showed that the bands around 3438 cm-1, attributed to free hydroxyls in the e-CL monomer aliphatic structure, became less intense. This indicated that the e-CL cyclic monomer structure was lost, with subsequent polymerization. This work has proven that the chemical modification of Kaol with subsequent adsorption of a metalloporphyrin is an important route for synthesizing initiator catalysts of polymerization reactions in the synthesis of new materials. (AU)

• Processo FAPESP: 17/15482-1 - Novas estratégias para o reaproveitamento de subprodutos de curtumes para a obtenção de materiais porosos funcionais de alto valor agregado
• Beneficiário: Emerson Henrique de Faria
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 13/19523-3 - Materiais biohíbridos funcionais baseados em argilas lamelares e/ou fibrosas com aplicações multifacetadas
• Beneficiário: Emerson Henrique de Faria
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 11/03335-8 - Ferroporfirinas como catalisadores em reações de oxidação do ciclohexano e reação de "Bayer-Villiger: sistemas heterogêneos
• Beneficiário: Katia Jorge Ciuffi Pires
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 05/00720-7 - Síntese, caracterização e atividade catalítica de sistemas biomiméticos e não-biomiméticos em reações de oxidação de hidrocarbonetos, utilizando o peróxido de hidrogênio como oxidante
• Beneficiário: Katia Jorge Ciuffi Pires
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 20/06712-6 - Ferroporfirinas-titânio suportadas em argilas ou sílicas como fotocatalisadores para produção de peróxido de hidrogênio
• Beneficiário: Katia Jorge Ciuffi Pires
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 12/11673-3 - Obtenção de filmes finos por spin e dip-coating usando a metodologia sol-gel
• Beneficiário: Eduardo José Nassar
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 16/01501-1 - Catalisadores multifuncionais para processos oxidativos avançados empregando matrizes biogênicas ou argilas
• Beneficiário: Katia Jorge Ciuffi Pires
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 98/11022-3 - Oxidacao catalitica biomimetica.
• Beneficiário: Katia Jorge Ciuffi Pires
• Modalidade de apoio: Auxílio à Pesquisa - Regular