• density functional calculations;
  • heterogeneous catalysis;
  • microporous materials;
  • molecular modeling;
  • oxidation;
  • reaction mechanisms


In this work we apply state-of-the-art electronic-structure-based computational methods based on hybrid-exchange density functional theory to study the mechanism of the aerobic oxidation of hydrocarbons catalysed by Mn-doped nanoporous aluminophosphates (Mn-AlPOs). We compare our results with available experimental data. We show that the catalytic efficiency of Mn-AlPOs in oxidation reactions is intrinsically linked to 1) the Mn redox activity, in particular between 2+ and 3+ oxidation states, and 2) the coordinative insaturation of tetrahedral Mn embedded in AlPO frameworks, which facilitates the reaction by stabilising oxo-type radicals through the formation of Mn complexes. Our mechanism demonstrates the crucial role of both MnIII and MnII in the reaction mechanism: MnIII sites undergo an initial reaction cycle that leads to the production of the alkyl hydroperoxide intermediate, which can only be transformed into the oxidative products (alcohol, aldehyde and acid) by MnII. A preactivation step is required to yield the reduced MnII sites able to decompose the hydroperoxide intermediates; this step takes place through a transformation of the hydrocarbon into the corresponding peroxo-derivative, stabilised by forming a complex with MnIII and yielding at the same time reduced MnII sites. Both species enter a subsequent propagation cycle in which MnII catalyses the dissociation of the hydroperoxide that proceeds until the formation of the oxidative products by two parallel pathways, through alkoxy- or hydroxy-radical-like intermediates, whilst the MnIII–peroxo complex enables further production of the hydroperoxide intermediate.