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From H2O2 to OH: A First-Principles Investigation of the Heterogeneous Fenton-Like Reaction
Basil Raju Karimadom1,2, Dan Meyerstein1,2, Amir Mizrahi3
1Chemical Sciences Department and the Radical Reactions Research Center, Ariel University, P.O.B. 3 Ariel, Ariel 40700, Israel.
Heterogeneous Fenton-like reactions show potential for advanced oxidation processes. DFT calculations reveal surface hydroxyl radical reactivity is lower than in homogeneous systems, impacting pollutant degradation efficiency.
Area of Science:
- Environmental Chemistry
- Surface Science
- Computational Chemistry
Background:
- Heterogeneous Fenton and Fenton-like reactions offer advantages over homogeneous systems for advanced oxidation processes (AOPs).
- Widespread application of these heterogeneous reactions faces challenges requiring in-depth analysis.
- Understanding surface reaction mechanisms is crucial for optimizing AOPs.
Purpose of the Study:
- To investigate the heterogeneous Fenton-like reaction mechanism on a pristine Fe(110) surface using first-principles calculations.
- To analyze the adsorption and electronic properties of hydroxyl radicals (*OH) on the iron surface.
- To compare the reactivity of surface-bound *OH with aqueous hydroxyl radicals (OH-(aq)).
Main Methods:
- Spin-polarized Density Functional Theory (DFT) calculations were employed to simulate the reaction in an aqueous medium.
- Calculated adsorption energies of *OH at various surface coverages on the Fe(110) surface.
- Analyzed electronic structures and charge transfer to understand surface oxidation states.
Main Results:
- *OH adsorption destabilizes Fe-O bonding at higher coverages, leading to partial oxidation of surface Fe atoms via charge transfer.
- Surface deprotonation of *OH is energetically favorable, resulting in co-existing *OH and *O- species.
- Surface-bound *OH is less reactive (0.15 V vs SHE at pH 14) than OH-(aq), reducing organic pollutant degradation efficacy.
Conclusions:
- Fe atoms in heterogeneous Fenton-like reactions with ZVI are not fully oxidized, unlike in homogeneous Fenton reactions.
- The reduced reactivity of surface *OH limits the efficiency of heterogeneous Fenton-like processes for pollutant degradation.
- Further research into surface corrosion and reactions on oxide/hydroxide layers is essential.
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