Complementary mechanistic properties of Fe- and Mn-doped aluminophosphates in the catalytic aerobic oxidation of hydrocarbons

Literature Information

Publication Date 2013-03-14
DOI 10.1039/C3CP51079D
Impact Factor 3.676
Authors

Luis Gómez-Hortigüela, Furio Corà, C. Richard A. Catlow


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Abstract

A comparative computational study of the reaction mechanisms for hydrocarbon oxidations catalysed by Mn- and Fe-doped nanoporous aluminophosphates shows distinctive features for each transition metal depending on its electronic configuration. Preactivation of Mn catalysts is easier due to the higher stability of MnII, but its oxidation during propagation requires activation barriers. In contrast, preactivation of Fe is more difficult and avoids a direct Fe reduction because of the low stability of FeII. FeII is only produced at the end of the propagation cycle, favoured by an energetic compensation caused by the simultaneous exothermic oxidation of an alcohol molecule. Fe-catalysed propagation is kinetically favoured since it requires lower activation barriers, and is further assisted by higher adsorption energies of the reactants and lower desorption energies of the products on the active site. The mechanistic information gained can be used for the rational design of improved oxidation catalysts.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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