Fenton chemistry encompasses reactions of hydrogen peroxide in the presence of iron to generate highly reactive species such as the hydroxyl radical and possibly others. In this review, the complex mechanisms of Fenton and Fenton-like reactions and the important factors influencing these reactions, from both a fundamental and practical perspective, in applications to water and soil treatment, are discussed. The review covers modified versions including the photoassisted Fenton reaction, use of chelated iron, electro-Fenton reactions, and Fenton reactions using heterogeneous catalysts. Sections are devoted to nonclassical pathways, by-products, kinetics and process modeling, experimental design methodology, soil and aquifer treatment, use of Fenton in combination with other advanced oxidation processes or biodegradation, economic comparison with other advanced oxidation processes, and case studies.

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Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry

Sulfate radical-based advanced oxidation processes (SR-AOPs) employing heterogeneous catalysts to generate sulfate radical (SO4 −) from peroxymonosulfate (PMS) and persulfate (PS) have been extensively employed for organic contaminant removal in water. This article aims to provide a state–of–the–art review on the recent development in heterogeneous catalysts including single metal, mixed metal, and nonmetal carbon catalysts for organic contaminants removal, with particular focus on PMS activation. The hybrid heterogeneous catalyst/PMS systems integrated with other advanced oxidation technologies is also discussed. Several strategies for the identification of principal reactive radicals in SO4 −–oxidation systems are evaluated, namely (i) use of chemical probe or spin trapping agent coupled with analytical tools, and (ii) competitive kinetic approach using selective radical scavengers. The main challenges and mitigation strategies pertinent to the SR-AOPs are identified, which include (i) possible formation of oxyanions and disinfection byproducts, and (ii) dealing with sulfate produced and residual PMS. Potential future applications and research direction of SR-AOPs are proposed. These include (i) novel reactor design for heterogeneous catalytic system based on batch or continuous flow (e.g. completely mixed or plug flow) reactor configuration with catalyst recovery, and (ii) catalytic ceramic membrane incorporating SR-AOPs.

Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: Current development, challenges and prospects

Synthesis of metallic nanoparticles using plant extracts.

Recently sulfate radical-based advanced oxidation processes (SR-AOPs) attract increasing attention due to their capability and adaptability in decontamination. The couple of cobalt and peroxymonosulfate (PMS) is an efficient way to produce reactive sulfate radicals. This article reviews the state-of-the-art progress on various heterogeneous cobalt-based catalysts for PMS activation, including cobalt oxides, cobalt-ferrite and supported cobalt by diverse substrates. We summarize the intrinsic properties of these catalysts and their fundamental behaviors in PMS activation, as well as synthetic approaches. In addition, influencing factors and synergistic techniques of Co/PMS systems in organic degradation and possible environmental applications are also discussed. Finally, we propose perspectives on challenges related to cobalt-based catalysts, heterogeneous Co/PMS systems and their potential applications in practical environmental cleanup.

Cobalt-catalyzed sulfate radical-based advanced oxidation: A review on heterogeneous catalysts and applications

Chemistry of persulfates in water and wastewater treatment: A review

Iron and silver nanoparticles were synthesized using a rapid, single step, and completely green biosynthetic method employing aqueous sorghum extracts as both the reducing and capping agent. Silver ions were rapidly reduced by the aqueous sorghum bran extracts, leading to the formation of highly crystalline silver nanoparticles with an average diameter of 10 nm. The diffraction peaks were indexed to the face-centered cubic (fcc) phase of silver. The absorption spectra of colloidal silver nanoparticles showed a surface plasmon resonance (SPR) peak centered at a wavelength of 390 nm. Amorphous iron nanoparticles with an average diameter of 50 nm were formed instantaneously under ambient conditions. The reactivity of iron nanoparticles was tested by the H2O2-catalyzed degradation of bromothymol blue as a model organic contaminant.

Biosynthesis of Iron and Silver Nanoparticles at Room Temperature Using Aqueous Sorghum Bran Extracts

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE).

A green single-step synthesis of iron nanoparticles using tea (Camellia sinensis) polyphenols is described that uses no additional surfactants/polymers as capping or reducing agents. The expedient reaction between polyphenols and ferric nitrate occurs within a few minutes at room temperature and is indicated by color changes from pale yellow to dark greenish/black in the formation of iron nanoparticles. The synthesized iron nanoparticles were characterized using transmission electron microscopy (TEM), UV-visible and X-ray diffraction pattern (XRD). The obtained nanoparticles were utilized to catalyze hydrogen peroxide for treatment of organic contamination and results were compared with Fe-EDTA and Fe-EDDS. Bromothymol blue, a commonly deployed pH indicator, is used here as a model contaminant for free radical reactions, due to its stability in the presence of H2O2 and its absorbance in the visible range at pH 6. The concentration of bromothymol blue is conveniently monitored using ultraviolet-visible (UV-Vis) spectroscopy during treatment with iron-catalyzed H2O2. Various concentrations of iron are tested to allow for the determination of initial rate constants for the different iron sources.

Degradation of bromothymol blue by ‘greener’ nano-scale zero-valent iron synthesized using tea polyphenols

Degradation of volatile organic compounds with thermally activated persulfate oxidation.

The present invention relates to methods of making and using and compositions of metal nanoparticles formed by green chemistry synthetic techniques. For example, the present invention relates to metal nanoparticles formed with solutions of plant extracts and use of these metal nanoparticles in removing contaminants from soil and groundwater and other contaminated sites. In some embodiments, the invention comprises methods of making and using compositions of metal nanoparticles formed using green chemistry techniques.

George E. Hoag

Papers

Biosynthesis of Iron and Silver Nanoparticles at Room Temperature Using Aqueous Sorghum Bran Extracts

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE).

Degradation of bromothymol blue by ‘greener’ nano-scale zero-valent iron synthesized using tea polyphenols

Degradation of volatile organic compounds with thermally activated persulfate oxidation.

Green synthesis of nanometals using plant extracts and use thereof