DFT study on the catalytic decomposition of hydrogen peroxide by iron complexes of nitrilotriacetate

2023/06/20 by Hsing‐Yin Chen, Yu‐Fen Lin
Chemistry · Environmental Science · Materials Science · #Advanced oxidation water treatment #Metal-Catalyzed Oxygenation Mechanisms #Porphyrin and Phthalocyanine Chemistry

paper · doi:10.1002/jcc.27179

openalex publication_date 2023/06/20 · openalex created_date 2023/06/21 · openalex updated_date 2026/07/28

Abstract

Abstract The Fenton system in the presence of nitrilotriacetate (NTA) ligand is studied by DFT approach. The calculations show that complexation of Fe(II) with NTA significantly facilitates the H 2 O 2 activation. The ferric‐hydroperoxo intermediate NTAFe(III)OOH predominantly decays via the disproportionation into NTAFe(II)OH 2 and NTAFe(IV)O involving the formation of a μ‐1,2‐hydroperoxo‐bridged biferric intermediate. In this mechanism, the bridged hydroperoxo is reduced by hydroperoxo ligand rather than by Fe(III). On the one hand, the NTAFe(III)OOH is sluggish to undergo hydrogen abstraction; on the other hand, it is a good nucleophile that may perform aldehyde deformylation. The present calculations suggest that both ˙OH and Fe(IV)O are generated in the NTA‐assisted Fenton system. However, the polycarboxylate ligand provides a favorable environment for H 2 O 2 to accumulate around iron ion through hydrogen bonding. This promotes the quenching of Fe(IV)O by H 2 O 2 , rationalizing why the Fe(IV)O species is hardly detected in the NTA‐assisted Fenton system.

Citations

• Lenguaje y revolución en "Mister Witt en el cantón"
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Reactivity of HO2/O−2 Radicals in Aqueous Solution
• Catalytic Decomposition of Hydrogen Peroxide by Fe(III) in Homogeneous Aqueous Solution: Mechanism and Kinetic Modeling
• A consistent and accurateab initioparametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
• Density-functional thermochemistry. III. The role of exact exchange

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