Oxygen Vacancy Associated Surface Fenton Chemistry: Surface Structure Dependent Hydroxyl Radicals Generation and Substrate Dependent Reactivity

Fenton (H2O2/Fe2+) system is a simple and efficient advanced oxidation technology (AOT) for the treatment of organic micropollutants in water and soil. However, it suffers from some drawbacks including high amount of the catalyst, acid pH requirement, sludge formation and slow regeneration of Fe2+ ions. If these drawbacks are surmounted, Fenton system can be the best choice AOT for the removal of persistent organics from water and soil. In this work, it was attempted to replace the homogeneous catalyst with a heterogeneous natural iron-based catalyst for the decomposition of H2O2 into oxidative radical species, mainly hydroxyl (HO•) and hydroperoxyl radicals (HO2•). The natural iron-based catalyst is hematite-rich (α-Fe2O3) and contains a nonnegligible amount of magnetite (Fe3O4) indicating the coexistence of Fe (III) and Fe(II) species. A pseudo-first order kinetics was determined for the decomposition of H2O2 by the iron-based solid catalyst with a rate constant increasing with the catalyst dose. The catalytic decomposition of H2O2 into hydroxyl radicals in the presence of the natural Fe-based catalyst was confirmed by the hydroxylation of benzoic acid into salicylic acid. The natural Fe-based catalyst/H2O2 system was applied for the degradation of riluzole in water. It was demonstrated that the smaller the particle size of the catalyst, the larger its surface area and the greater its catalytic activity towards H2O2 decomposition into hydroxyl radicals. The degradation of riluzole can occur at all pH levels in the range 3.0–12.0 with a rate and efficiency greater than H2O2 oxidation alone, indicating that the natural Fe-based catalyst can function at any pH without the need to control the pH by the addition of chemicals. An improvement in the efficiency and kinetics of the degradation of riluzole was observed under UV irradiation for both homogeneous and heterogeneous Fenton systems. The results chromatography analysis demonstrate that the degradation of riluzole starts by the opening of the triazole ring by releasing nitrate, sulfate, and fluoride ions. The reuse of the catalyst after heat treatment at 500 °C demonstrated that the heat-treated catalyst retained an efficiency >90% after five cycles. The results confirmed that the natural sources of iron, as a heterogeneous catalyst in a Fenton-like system, is an appropriate replacement of a Fe2+ homogeneous catalyst. The reuse of the heterogeneous catalyst after a heat-treatment represents an additional advantage of using a natural iron-based catalyst in Fenton-like systems.

Comparison of mineral and soluble iron Fenton's catalysts for the treatment of trichloroethylene

Sulfate radicals (SO4•−) and hydroxy radicals (HO•) are the major radicals used in advanced oxidation technologies (AOTs) for the removal of contaminants. Although SO4•− reacts with organic or inorganic compounds with rate constants comparatively lower than that of HO•, AOTs based on SO4•− (abbreviated as SR‐AOTs) have gained lots of attention due to the selective oxidation and non‐pH‐dependence. A series of systems using persulfate (PS) or peroxymonosulfate (PMS) instead of H2O2 is designated as a sulfate radical‐Fenton system or sulfur‐replaced Fenton system (SR‐Fenton). Comparisons and analogies between Fenton (Fenton‐like) systems and SR‐Fenton systems are made and some new SR‐AOTs systems without PS or PMS are introduced. The possibility for the substitution of HO• by SO4•− for AOTs is discussed. Most likely in the future, efforts will be concentrated on product‐oriented AOTs with the purpose of recovery of chemical products rather than mineralization of organic contaminants, producing greenhouse gas CO2. Moreover, such SR‐Fenton system may be more atomically economical. © 2014 Society of Chemical Industry

On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe2+ /H2 O2 ) and Fenton-like (Mn+ /H2 O2 ; Mn+ =Fe3+ , Co2+ , Cu2+ , Mn2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe2+ /H2 O2 ≫H2 O2 ≫Cu2+ /H2 O2 >Mn+ /H2 O2 (Mn+ =Fe3+ , Co2+ , Mn2+ ) ~ Mn+ (Mn+ =Fe2+ , Fe3+ , Co2+ , Cu2+ , Mn2 ). The superior capability of Fe2+ /H2 O2 in causing the degradation of sildenafil indicates that Fe2+ efficiently decomposes H2 O2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H2 O2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, ie, Fe3+ , Co2+ , Cu2+ , and Mn2+ . A unique oxidation by-product was detected in the reaction between Fe2+ /H2 O2 with sildenafil, and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shows to be a convenient platform to promptly monitor on-surface oxidation reactions.

Oxidative damage to fibronectin: II. The effect of H 2O 2 and the hydroxyl radical

The European Young Chemist Award 2012

Photocatalytic Methane Conversion: Insight into the Mechanism of C(sp ³ )–H Bond Activation

Novel iron bound to soil organic matter catalyzes H2O2 to oxidize long-chain alkanes effectively in soil

Hydrogen atom transfer (HAT) and single electron transfer (SET) are two fundamental pathways for antiradical/antioxidant processes; however, a systematic in-tandem operational evaluation of the same system is lacking. Herein, we present a comparative study of the HAT and SET processes applied to a library of well-characterized hybrid materials SiO2@GA, SiO2@GLA, SiO2@GLAM, and the doubly hybrid material {GLA@SiO2@GLAM}. Hydroxyl radicals (•OH), produced by a Fenton system, react via the single electron transfer (SET) pathway and hydrogen atom transfer, through oxygen- and carbon-atoms, respectively, while the stable-radical DPPH via the HAT pathway through oxygen-atoms. Electron paramagnetic resonance spectroscopy (EPR), eminently suited for in situ detection and quantification of free radicals, was used as a state-of-the-art tool to monitor •OH using the spin-trapping-EPR method. We found that the SiO2@GA hybrid exhibited the highest SET •OH-scavenging activity i.e., [2.7 mol of •OH per mol of grafted GA]. Then, SiO2@GLA, SiO2@GLAM, and GLA@SiO2@GLAM can scavenge 1.2, 1.3, and 0.57 mol of •OH per mol of anchored organic, respectively. The HAT efficiency for SiO2@GA was [2.0 mol of DPPH per mol of grafted GA], while SiO2@GLA, SiO2@GLAM, and GLA@SiO2@GLAM exhibited a HAT efficiency of 1.1 DPPH moles per mol of anchored organic. The data are analyzed based on the molecular structure of the organics and their -R-OH moieties. Accordingly, based on the present data we suggest that for hydroxyl (•OH) radicals, the mechanisms involved are SET from an oxygen atom and HAT from a carbon atom. In contrast, for DPPH radicals, the HAT mechanism is exclusively operating and involves hydrogen atom abstraction from OH groups.

Characteristics of an oxidant formed during iron (II) autoxidation

Review: 33 refs.

The renaissance of organic radical chemistry – deja vu all over again

The reaction of the hydroxyl radical, generated by a Fenton system, with pyrimidine deoxyribonucleotides was investigated by using the e.s.r. technique of spin trapping. The spin trap t-nitrosobutane was employed to trap secondary radicals formed by the reaction of the hydroxyl radical with these nucleotides. The results presented here show that hydroxyl-radical attack on thymidine, 2-deoxycytidine 5-monophosphate and 2-deoxyuridine 5-monophosphate produced nucleotide-derived free radicals. The results indicate that .OH radical attack occurs predominantly at the carbon-carbon double bond of the pyrimidine base. The e.s.r. studies showed a good correlation with previous results obtained by authors who used x- or gamma-ray irradiation to generate the hydroxyl radical. A thiobarbituric acid assay was also used to monitor the damage produced to the nucleotides by the Fenton system. These results showed qualitative agreement with the spin-trapping studies.

Oxidation removal of gaseous Hg0 using enhanced-Fenton system in a bubble column reactor

Influencing factors of EPR detection of hydroxyl radicals in the Fenton system: The complicated roles of pH, zero-valent iron, and typical ligands.