The Disproportionation of Hydrogen Peroxide by Prototype Keggin Polyoxometalates
Abstract
Polyoxometalates (POMs) have been widely investigated as enzyme-mimetic compounds because of their ability to activate hydrogen peroxide for its disproportionation into water and oxygen (catalase reactivity), or use it as terminal oxidant for organic transformations (peroxidase reactivity). Here, we report how the prototype Keggin-type POMs H 3 [PW 12 O 40 ] ({PW 12 }) and H 3 [PMo 12 O 40 ] ({PMo 12 }) interact with hydrogen peroxide and lead to H 2 O 2 activation and conversion to water and oxygen. Experimental and computational approaches were combined to elucidate the reaction pathways and intermediates formed, showing that formation of hydroperoxyl radical species is the dominant path, while hydroxyl radicals, if formed, are consumed before they diffuse into the bulk solution. This understanding provides insight into one of the most widely used POM-based oxidation processes and enables knowledge-based control of reactivity.
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BibTeX
@misc{kadereit2026disproportionation,
title = {{The Disproportionation of Hydrogen Peroxide by Prototype Keggin Polyoxometalates}},
author = {Paul Kadereit and Paul Heim and Martin Diefenbach and Vera Krewald and Carsten Streb},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010962/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010962/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - The Disproportionation of Hydrogen Peroxide by Prototype Keggin Polyoxometalates
AU - Paul Kadereit
AU - Paul Heim
AU - Martin Diefenbach
AU - Vera Krewald
AU - Carsten Streb
PY - 2026
DA - 2026/10/23
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010962/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010962/v1
AB - Polyoxometalates (POMs) have been widely investigated as enzyme-mimetic compounds because of their ability to activate hydrogen peroxide for its disproportionation into water and oxygen (catalase reactivity), or use it as terminal oxidant for organic transformations (peroxidase reactivity). Here, we report how the prototype Keggin-type POMs H 3 [PW 12 O 40 ] ({PW 12 }) and H 3 [PMo 12 O 40 ] ({PMo 12 }) interact with hydrogen peroxide and lead to H 2 O 2 activation and conversion to water and oxygen. Experimental and computational approaches were combined to elucidate the reaction pathways and intermediates formed, showing that formation of hydroperoxyl radical species is the dominant path, while hydroxyl radicals, if formed, are consumed before they diffuse into the bulk solution. This understanding provides insight into one of the most widely used POM-based oxidation processes and enables knowledge-based control of reactivity.
ER -