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Catalytic Oxidation: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Catalytic oxidation is an oxidation in which a catalyst mediates electron and/or oxygen-atom transfer from an oxidant to a substrate and is regenerated in the catalytic cycle [1][2]. In catalysis and oxidation reactions the concept is bounded by a net increase in the oxidation state of the substrate and by turnover of the catalytic species, whether a metal surface, a molecular metal complex, or a mediator. Essential features are an oxidant (O2, H2O2, or an anodic equivalent), a catalyst that activates that oxidant or the substrate, and a sequence of electron-transfer steps that returns the catalyst to its resting state [2][3]. Heterogeneous variants include plasmon-enhanced oxidation at silver nanostructures and interface-confined ferrous centers that activate oxygen at a metal–oxide boundary [1][4]. Homogeneous biomimetic systems couple a metal catalyst to a coupled electron-transfer chain so that molecular oxygen or hydrogen peroxide can be used without stoichiometric metal consumption [3]. The concept is distinguished from stoichiometric oxidation by regeneration of the oxidant-activating species, and from catalytic reduction by the direction of electron flow. Conceptual limits exclude combustions in which the catalyst only ignites an uncontrolled radical chain and exclude oxygen-atom transfers that do not change the substrate’s formal oxidation state.

  • catalytic oxidation
  • electron transfer
  • oxygen activation
  • heterogeneous catalyst

Catalysis and Oxidation Reactions • Catalysis • Chemical Engineering • Physical Sciences

References

  1. Phillip Christopher; Hongliang Xin; Suljo Linic; Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures. Nat. Chem. 2011, 3, 467-472, 10.1038/nchem.1032.
  2. Chi He; Jie Cheng; Xin Zhang; Mark Douthwaite; Samuel Pattisson; Zhengping Hao; Recent Advances in the Catalytic Oxidation of Volatile Organic Compounds: A Review Based on Pollutant Sorts and Sources. Chem. Rev. 2019, 119, 4471-4568, 10.1021/acs.chemrev.8b00408.
  3. Julio Piera; Jan‐E. Bäckvall; Catalytic Oxidation of Organic Substrates by Molecular Oxygen and Hydrogen Peroxide by Multistep Electron Transfer—A Biomimetic Approach. Angew. Chem. Int. Ed. 2008, 47, 3506-3523, 10.1002/anie.200700604.
  4. Qiang Fu; Wei-Xue Li; Yunxi Yao; Hongyang Liu; Hai-Yan Su; Ding Ma; Xiang-Kui Gu; Limin Chen; Zhen Wang; Hui Zhang; et al. Interface-Confined Ferrous Centers for Catalytic Oxidation. Science 2010, 328, 1141-1144, 10.1126/science.1188267.
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