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RevistaACS Catalysis
Año2011
Volumen1 (11)
Páginas1475-1486
Internacional

Aerobic oxidation of hydrocarbons catalyzed by Mn-doped nanoporous aluminophosphates (IV): regeneration mechanism

Autores:Luis Gómez-Hortiguela Sáinz, Furio Corà , C. Richard A. Catlow
Grupos de investigación:Tamices Moleculares

Electronic structure methods based on periodic DFT with hybrid-exchange functionals are applied to study the reaction mechanism of the aerobic oxidation of hydrocarbons catalyzed by Mn-doped nanoporous aluminophosphates. Here, we focus on the regeneration of the active sites that closes the oxidation cycle. At this stage, the catalyst pores are accumulated with CH3CH2OOH (hydroperoxide) and MnIII···OOCH2CH3 complexes resulting from the propagation reactions. CH3CH2OOH intermediates can only be decomposed into the oxidation products by MnII sites; thus, a reaction pathway in which Mn sites in MnIII···OOCH2CH3 are reduced is essential for the oxidation cycle to proceed. We demonstrate that two different regeneration mechanisms take place at different times of the oxidation reaction: at the beginning, MnIII···OOCH2CH3 complexes are transformed into a molecule of aldehyde and MnIII···OH complexes by an intramolecular H transfer from the methylene C to the terminal O in the peroxo radical in a slow process that requires a high activation energy of 141 kJ/mol. Mn sites in MnIII···OH can then be regenerated by a H-transfer from a new hydrocarbon molecule to a framework O nearest neighbor to Mn, followed by coupling between the resulting alkyl radical and the OH ligand to give a molecule of ethanol and MnII sites. At later stages of the oxidation, when alcohol molecules are accumulated within the pores of the catalyst, Mn sites in MnIII···OOCH2CH3 can be regenerated by a more favorable mechanism with a double H-abstraction from the alcohol. First, a H atom in the methylene C of CH3CH2OH is transferred to the CH3CH2OO ligand to give CH3CH2OOH and CH3CH·OH radicals, followed by H transfer from this radical to a framework O to yield finally a molecule of aldehyde and MnII sites. The occurrence of alternative regeneration mechanisms along the oxidation reaction explains the variation of the alcohol-to-aldehyde ratio observed experimentally as a function of the reaction time.

Palabras clave:oxidation; heterogeneous catalysis; nanoporous aluminophosphates; zeolites; regeneration; aerobic; reaction mechanism
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