Comment on “Theoretical investigations on hydrogen peroxide decomposition in aquo” by T. Tsuneda and T. Taketsugu, Phys. Chem. Chem. Phys., 2018, 20, 24992

2021 ◽  
Author(s):  
Willem H. Koppenol
Keyword(s):  
Hydrogen Peroxide ◽  
Ab Initio ◽  
Fenton Reaction ◽  
Chem Phys ◽  
Hydrogen Peroxide Decomposition ◽  
Peroxide Decomposition ◽  
Theoretical Investigations ◽  
Phys Chem Chem Phys

In an ab initio study, Tsuneda and Taketsugu (Phys. Chem. Chem. Phys., 2018, 20, 24992–24999) discuss the Fenton reaction, the reaction of Fe2+ with H2O2.

Reply to the ‘Comment on “Theoretical investigations on hydrogen peroxide decomposition in aquo”’ by W. H. Koppenol, Phys. Chem. Chem. Phys., 2021, 23, DOI: 10.1039/D1CP03545B

2021 ◽  
Author(s):  
Takao Tsuneda ◽  
Tetsuya Taketsugu
Keyword(s):  
Hydrogen Peroxide ◽  
Decomposition Reaction ◽  
Chem Phys ◽  
Simple Test ◽  
Ion Hydration ◽  
Hydrogen Peroxide Decomposition ◽  
Gibbs Energies ◽  
Peroxide Decomposition ◽  
Theoretical Investigations ◽  
Phys Chem Chem Phys

The H2O2 decomposition reaction mechanism based on the production of a de facto Fe+ ion hydration complex is strongly supported by a simple test based on the Gibbs energies considering the O–O bond dissociation of H2O2.

scholarly journals Theoretical investigations on hydrogen peroxide decomposition in aquo

2018 ◽  
Vol 20 (38) ◽  
pp. 24992-24999 ◽  
Author(s):  
Takao Tsuneda ◽  
Tetsuya Taketsugu
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Oh Radical ◽  
Iron Ions ◽  
Hydrogen Bond Network ◽  
Iron Ion ◽  
Hydrogen Peroxide Decomposition ◽  
Peroxide Decomposition ◽  
Theoretical Investigations ◽  
Bond Network

Hydrogen peroxide (H2O2) decomposition mechanisms in the absence and presence of iron ions in aqueous solution, which contain no OH radical formation, are theoretically determined. H2O2 decomposition in the presence of iron ions is driven by electron transfer to the iron ion and proceeds by hydrogen transfers in the hydrogen bond network around H2O2.

A Systematic DFT Study of Two Elementary Steps Involving Hydrogen Peroxide and the Hydroxyl Radical in the Fenton Reaction

2018 ◽  
Author(s):  
Danilo Carmona ◽  
David Contreras ◽  
Oscar A. Douglas-Gallardo ◽  
Stefan Vogt-Geisse ◽  
Pablo Jaque ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Ab Initio ◽  
Fenton Reaction ◽  
Basis Set ◽  
Basis Sets ◽  
Dft Methods ◽  
Elementary Steps ◽  
Oxygen Oxygen ◽  
Complete Basis Set

The Fenton reaction plays a central role in many chemical and biological processes and has various applications as e.g. water remediation. The reaction consists of the iron-catalyzed homolytic cleavage of the oxygen-oxygen bond in the hydrogen peroxide molecule and the reduction of the hydroxyl radical. Here, we study these two elementary steps with high-level ab-initio calculations at the complete basis set limit and address the performance of different DFT methods following a specific classification based on the Jacob´s ladder in combination with various Pople's basis sets. Ab-initio calculations at the complete basis set limit are in agreement to experimental reference data and identified a significant contribution of the electron correlation energy to the bond dissociation energy (BDE) of the oxygen-oxygen bond in hydrogen peroxide and the electron affinity (EA) of the hydroxyl radical. The studied DFT methods were able to reproduce the ab-initio reference values, although no functional was particularly better for both reactions. The inclusion of HF exchange in the DFT functionals lead in most cases to larger deviations, which might be related to the poor description of the two reactions by the HF method. Considering the computational cost, DFT methods provide better BDE and EA values than HF and post--HF methods with an almost MP2 or CCSD level of accuracy. However, no systematic general prediction of the error based on the employed functional could be established and no systematic improvement with increasing the size in the Pople's basis set was found, although for BDE values certain systematic basis set dependence was observed. Moreover, the quality of the hydrogen peroxide, hydroxyl radical and hydroxyl anion structures obtained from these functionals was compared to experimental reference data. In general, bond lengths were well reproduced and the error in the angles were between one and two degrees with some systematic trend with the basis sets. From our results we conclude that DFT methods present a computationally less expensive alternative to describe the two elementary steps of the Fenton reaction. However, choice of approximated functionals and basis sets must be carefully done and the provided benchmark allows a systematic validation of the electronic structure method to be employed

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