Desidrogenação oxidativa do etilbenzeno a estireno na presença de CO2 usando catalisadores a base de CoFe2O4-MCM-41: adsorção preferencial nos sítios O-2-Fe3+ -O2- localizados nas posições octaédricas

• Ano de defesa: 2019
• Autor(a) principal: Soares, Moisés da Costa Borges
• Tipo de documento: Tese
• Tipo de acesso: Acesso aberto
• Idioma: por
• Instituição de defesa: Brasil; UFRN; PROGRAMA DE PÓS-GRADUAÇÃO EM QUÍMICA
• Palavras-chave em Português: Desidrogenação oxidativa; Etilbenzeno; Ferrita de cobalto; Papel do CO2; Mecanismo catalítico; CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
• Link de acesso: https://repositorio.ufrn.br/jspui/handle/123456789/27734

The present study describes the catalytic performance of cobalt ferrite supported on MCM-41 for the oxidative dehydrogenation of ethylbenzene and evaluates the role of CO 2 on the surface of the catalyst during the reaction using experimental data and density functional theory (DFT) calculations. A mechanism has been described indicating the role of the O -2 -Fe3+ -O 2- and O-2 - Co2+ -O 2- acid-base sites present in the tetrahedral and octahedral positions of the cobalt ferrite structure. The solids were characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), Mössbauer spectroscopy (MS), X-ray photoelectron spectroscopy (XPS), vibration-sample magnetometry (VSM), temperature-programmed reduction (H2-TPR), chemical adsorption of NO and pyridine followed by infrared (FTIR) analysis, temperature-programmed desorption of CO2 (TPD-CO2), N2 physisorption and transmission electron microscopy (TEM). The results of XRD, RS, MS and VSM, before and after catalytic tests, confirmed the formation of partially inverted cobalt ferrite and showed the role of CO2 in the reactivation of the acid-base sites during the catalytic cycle, observing that the ferrite phase of cobalt was maintained when the reaction was carried out in the presence of CO2 and reduced in the tests without CO2. N2 isotherms, low angle XRDs and TEM images showed the formation of MCM-41 support. The catalytic tests showed that CO2 is essential to obtain good conversion values of ethylbenzene and that cobalt ferrite is more active and stable than the traditional hematite catalyst. Thermogravimetric analyzes showed that CO2 favors the oxidation of deposited carbon during the reaction. The results of TPD-CO2 and FTIR-CO2 indicated the presence of weak basic sites and the preferential adsorption of CO2 as carbonate and bicarbonate bridges. The proposed catalytic cycle, through a theoretical approach (DFT), shows that the adsorption of ethylbenzene occurs preferentially at the octahedral sites O -2 -Fe3+ -O 2- - compared to the O -2 -Co2+ -O 2- sites, due to to a higher acidity of the iron sites compared to cobalt on the surface of the spinel, evidencing the role of CO2 in regenerating lattice oxygen and the iron phase of the spinel. By approaching the surfaces of complementary electrostatic potential, the adsorption of ethylbenzene occurs preferentially at the outermost FeOX (x> 4) sites (Lewis acid) and the dehydrogenation reaction occurs predominantly in the oxygens bound to iron (Lewis base).