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Chemosphere Jun 2023Recalcitrant and toxic organic pollutants from wastewaters are scarcely removed in conventional wastewater treatment plants. To preserve the water quality, organics need... (Review)
Review
Solar photoelectro-Fenton: A very effective and cost-efficient electrochemical advanced oxidation process for the removal of organic pollutants from synthetic and real wastewaters.
Recalcitrant and toxic organic pollutants from wastewaters are scarcely removed in conventional wastewater treatment plants. To preserve the water quality, organics need to be removed by developing powerful oxidation technologies. Our laboratory proposed in 2007 a potent electrochemical advanced oxidation process (EAOP) for wastewater remediation, so-called solar photoelectro-Fenton (SPEF). This review summarizes the advances of this emerging technology up to 2022, making evident its effectiveness and cost-efficiency for the destruction of usual organic pollutants. The simultaneous action of generated hydroxyl radicals and the photolysis by sunlight explains the high oxidation power of SPEF respect to other EAOPs. The review is initiated by describing the fundamentals of the process to remark the role of the produced oxidants and the benefits of using solar irradiation in its performance. The photoelectrochemical systems used (bench tank reactor and solar pre-pilot flow plant) and the assessment of the operating variables are discussed. The characteristics of the most common homogeneous SPEF for the degradation and mineralization of several synthetic solutions of industrial chemicals, herbicides, pharmaceuticals, and synthetic organic dyes, as well as of some real wastewaters, are further described. The influence of the photoelectrochemical cell, electrodes, solution pH, electrolyte composition, Fe and pollutant concentration, and current density is analyzed. The performance of a homogeneous SPEF-like process with active chlorine and heterogeneous SPEF processes with solid catalysts such as FeO and sodium vermiculite is also discussed. Finally, the advances of homogeneous SPEF combined with other techniques like solar photocatalysis, solar photoelectrocatalysis, anaerobic digestion, and nanofiltration are reported.
Topics: Wastewater; Sunlight; Environmental Pollutants; Electrochemical Techniques; Herbicides; Oxidation-Reduction; Hydrogen Peroxide; Water Pollutants, Chemical; Electrodes
PubMed: 37003440
DOI: 10.1016/j.chemosphere.2023.138532 -
Accounts of Chemical Research Dec 2022surface is covered by oceans, a large number of liquid aerosol particles fill the air, and clouds hold a tiny but critical fraction of Earth's water in the air to...
surface is covered by oceans, a large number of liquid aerosol particles fill the air, and clouds hold a tiny but critical fraction of Earth's water in the air to influence our climate and hydrology, enabling the lives of humans and ecosystems. The surfaces of these liquids provide the interface for the transfer of gases, for nucleation processes, and for catalyzing important chemical reactions. Coupling a range of spectroscopic tools to liquid microjets has become an important approach to better understanding dynamics, structure, and chemistry at liquid interfaces. Liquid microjets offer stability in vacuum and ambient pressure environments, thus also allowing X-ray photoelectron spectroscopy (XPS) with manageable efforts in terms of differential pumping. Liquid microjets are operated at speeds sufficient to allow for a locally equilibrated surface in terms of water dynamics and solute surface partitioning. XPS is based on the emission of core-level electrons, the binding energy of which is selective for the element and its chemical environment. Inelastic scattering of electrons establishes the probing depth of XPS in the nanometer range and thus its surface sensitivity.In this Account, we focus on aqueous solutions relevant to the surface of oceans, aqueous aerosols, or cloudwater. We are interested in understanding solvation and acid dissociation at the interface, interfacial aspects of reactions with gas-phase reactants, and the interplay of ions with organic molecules at the interface. The strategy is to obtain a link between the molecular-level picture and macroscopic properties and reactivity in the atmospheric context.We show consistency between surface tension and XPS for a range of surface-active organic species as an important proof for interrogating an equilibrated liquid surface. Measurements with organic acids and amines offer important insight into the question of apparent acidity or basicity at the interface. Liquid microjet XPS has settled the debate of the surface enhancement of halide ions, shown using the example of bromide and its oxidation products. Despite the absence of a strong enhancement for the bromide ion, its rate of oxidation by ozone is surface catalyzed through the stabilization of the bromide ozonide intermediate at the interface. In another reaction system, the one between Fe and HO, a similar intermediate in the form of highly valent iron species could not be detected by XPS under the experimental conditions employed, shedding light on the abundance of this intermediate in the environment but also on the constraints within which surface species can be detected. Emphasizing the importance of electrostatic effects, we show how a cationic surfactant attracts charged bromide anions to the interface, accompanied by enhanced oxidation rates by ozone, overriding the role of surfactants as a barrier for the access of gas-phase reactants. The reactivity and structure at interfaces thus result from a subtle balance between hygroscopic and hydrophobic interactions, electrostatic effects, and the structural properties of both liquids and solutes.
Topics: Humans; Bromides; Ecosystem; Hydrogen Peroxide; Ozone; Water
PubMed: 36472357
DOI: 10.1021/acs.accounts.2c00604 -
Ecotoxicology and Environmental Safety Apr 2023Advanced oxidation processes (AOPs) are a class of highly efficient pollution remediation technologies that produce oxidising radicals under specific conditions to... (Review)
Review
Advanced oxidation processes (AOPs) are a class of highly efficient pollution remediation technologies that produce oxidising radicals under specific conditions to degrade organic pollutants. The Fenton reaction is a commonly applied AOP. To combine the advantages of AOPs and biodegradation in the remediation of organic pollutants, some studies have developed coupled systems between Fenton AOPs and white rot fungi (WRF) for environmental organic pollutant remediation and have achieved some success. Moreover, a promising system, termed as advanced bio-oxidation processes (ABOPs), mediated by the quinone redox cycling of WRF, has attracted increasing attention in the field. In this ABOP system, the radicals and HO produced through the quinone redox cycling of WRF can strengthen Fenton reaction. Meanwhile, in this process, the reduction of Fe to Fe ensures the maintenance of Fenton reaction, leading to a promising application potential for the remediation of environmental organic pollutants. ABOPs combine the advantages of bioremediation and advanced oxidation remediation. Further understanding the coupling of Fenton reaction and WRF in the degradation of organic pollutants will be of great significance for the remediation of organic pollutants. Therefore, in this study, we reviewed recent remediation techniques for organic pollutants involving the coupled application of WRF and the Fenton reaction, focusing on the application of new ABOPs mediated by WRF, and discussed the reaction mechanism and conditions of ABOPs. Finally, we discussed the application prospects and future research directions of the joint application of WRF and advanced oxidation technologies for the remediation of environmental organic pollutants.
Topics: Hydrogen Peroxide; Environmental Pollutants; Oxidation-Reduction; Environmental Restoration and Remediation; Fungi; Water Pollutants, Chemical
PubMed: 36889210
DOI: 10.1016/j.ecoenv.2023.114697 -
Philosophical Transactions of the Royal... Jul 2013Nitric oxide (NO) is a reactive gas that plays an important role in atmospheric chemistry by influencing the production and destruction of ozone and thereby the... (Review)
Review
Nitric oxide (NO) is a reactive gas that plays an important role in atmospheric chemistry by influencing the production and destruction of ozone and thereby the oxidizing capacity of the atmosphere. NO also contributes by its oxidation products to the formation of acid rain. The major sources of NO in the atmosphere are anthropogenic emissions (from combustion of fossil fuels) and biogenic emission from soils. NO is both produced and consumed in soils as a result of biotic and abiotic processes. The main processes involved are microbial nitrification and denitrification, and chemodenitrification. Thus, the net result is complex and dependent on several factors such as nitrogen availability, organic matter content, oxygen status, soil moisture, pH and temperature. This paper reviews recent knowledge on processes forming NO in soils and the factors controlling its emission to the atmosphere. Schemes for simulating these processes are described, and the results are discussed with the purpose of scaling up to global emission.
Topics: Atmosphere; Denitrification; Hydrogen-Ion Concentration; Models, Theoretical; Nitric Oxide; Nitrification; Nitrogen Cycle; Oxygen; Soil; Soil Microbiology; Temperature; Water
PubMed: 23713124
DOI: 10.1098/rstb.2013.0126 -
Journal of the American Chemical Society Dec 2019The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A...
The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this article, we describe the first enantioselective, diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a bistosyl urea as the bifunctional nucleophile and fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the dichlorination reported previously. Furthermore, the -stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.
Topics: Alkenes; Amination; Catalysis; Diamines; Organoselenium Compounds; Oxidants; Oxidation-Reduction; Stereoisomerism; Urea
PubMed: 31742399
DOI: 10.1021/jacs.9b11261 -
Molecules (Basel, Switzerland) Jun 2022The chemistry of polyvalent iodine compounds has piqued the interest of researchers due to their role as important and flexible reagents in synthetic organic chemistry,... (Review)
Review
The chemistry of polyvalent iodine compounds has piqued the interest of researchers due to their role as important and flexible reagents in synthetic organic chemistry, resulting in a broad variety of useful organic molecules. These chemicals have potential uses in various functionalization procedures due to their non-toxic and environmentally friendly properties. As they are also strong electrophiles and potent oxidizing agents, the use of hypervalent iodine reagents in palladium-catalyzed transformations has received a lot of attention in recent years. Extensive research has been conducted on the subject of C-H bond functionalization by Pd catalysis with hypervalent iodine reagents as oxidants. Furthermore, the iodine(III) reagent is now often used as an arylating agent in Pd-catalyzed C-H arylation or Heck-type cross-coupling processes. In this article, the recent advances in palladium-catalyzed oxidative cross-coupling reactions employing hypervalent iodine reagents are reviewed in detail.
Topics: Catalysis; Indicators and Reagents; Iodides; Iodine; Oxidants; Oxidation-Reduction; Palladium
PubMed: 35745020
DOI: 10.3390/molecules27123900 -
Journal of Hazardous Materials Feb 2023Microplastics (MPs) are contaminants of emerging concern that accumulate in various environments, where they pose threats to both the ecosystem and public health. Since... (Review)
Review
Microplastics (MPs) are contaminants of emerging concern that accumulate in various environments, where they pose threats to both the ecosystem and public health. Since MPs have been detected in drinking water resources and wastewater effluents, more efficient treatment is needed at wastewater treatment plants (WWTPs) and drinking water treatment plants (DWTPs). This review discusses the potential of biological, photochemical, Fenton (-like) systems, ozonation, and other oxidation processes in the treatment of MPs in terms of their indicators of oxidation such as mass loss and surface oxidation. The oxidation processes were further analyzed in terms of limitations and environmental implications. Most previous studies examining MPs degradation using conventional treatments-such as UV disinfection, ozonation, and chlorination-employed significantly higher doses than the common doses applied in DWTPs and WWTPs. Owing to such dose gaps, the oxidative transformation of MPs observed in many previous studies are not likely to occur under practical conditions. Some novel oxidation processes showed promising MPs treatment efficiencies, while many of them have not yet been applied on a larger scale due to high costs and the lack of extensive basic research. Health and environmental impacts related to the discharge of oxidized MPs in effluents should be considered carefully in different aspects: the role as vectors of external pollutants, release of organic compounds (including organic byproducts from oxidation) and fragmentation into smaller particles as MPs circulate in the ecosystem as well as the possibility of bioaccumulation. Future research should also focus on ways to incorporate developed oxidation processes in DWTPs and WWTPs to mitigate MPs contamination.
Topics: Microplastics; Plastics; Ecosystem; Drinking Water; Water Pollutants, Chemical; Water Purification; Wastewater; Ozone; Oxidative Stress
PubMed: 36372022
DOI: 10.1016/j.jhazmat.2022.130313 -
Environmental Science & Technology Nov 2023Ozone is a commonly applied disinfectant and oxidant in drinking water and has more recently been implemented for enhanced municipal wastewater treatment for potable... (Review)
Review
Ozone is a commonly applied disinfectant and oxidant in drinking water and has more recently been implemented for enhanced municipal wastewater treatment for potable reuse and ecosystem protection. One drawback is the potential formation of bromate, a possible human carcinogen with a strict drinking water standard of 10 μg/L. The formation of bromate from bromide during ozonation is complex and involves reactions with both ozone and secondary oxidants formed from ozone decomposition, i.e., hydroxyl radical. The underlying mechanism has been elucidated over the past several decades, and the extent of many parallel reactions occurring with either ozone or hydroxyl radicals depends strongly on the concentration, type of dissolved organic matter (DOM), and carbonate. On the basis of mechanistic considerations, several approaches minimizing bromate formation during ozonation can be applied. Removal of bromate after ozonation is less feasible. We recommend that bromate control strategies be prioritized in the following order: (1) control bromide discharge at the source and ensure optimal ozone mass-transfer design to minimize bromate formation, (2) minimize bromate formation during ozonation by chemical control strategies, such as ammonium with or without chlorine addition or hydrogen peroxide addition, which interfere with specific bromate formation steps and/or mask bromide, (3) implement a pretreatment strategy to reduce bromide and/or DOM prior to ozonation, and (4) assess the suitability of ozonation altogether or utilize a downstream treatment process that may already be in place, such as reverse osmosis, for post-ozone bromate abatement. A one-size-fits-all approach to bromate control does not exist, and treatment objectives, such as disinfection and micropollutant abatement, must also be considered.
Topics: Humans; Bromates; Drinking Water; Bromides; Ecosystem; Ozone; Water Purification; Hydroxyl Radical; Oxidants; Water Pollutants, Chemical
PubMed: 37363871
DOI: 10.1021/acs.est.3c00538 -
Nature Communications Dec 2022Given the widespread significance of vicinal diamine units in organic synthesis, pharmaceuticals and functional materials, as well as in privileged molecular catalysts,...
Given the widespread significance of vicinal diamine units in organic synthesis, pharmaceuticals and functional materials, as well as in privileged molecular catalysts, an efficient and practical strategy that avoids the use of stoichiometric strong oxidants is highly desirable. We herein report the application of ligand-to-metal charge transfer (LMCT) excitation to 1,2-diazidation reactions from alkenes and TMSN via a coordination-LMCT-homolysis process with more abundant and greener iron salt as the catalyst. Such a LMCT-homolysis mode allows the generation of electrophilic azidyl radical intermediate from Fe-N complexes poised for subsequent radical addition into carbon-carbon double bond. The generated carbon radical intermediate is further captured by iron-mediated azidyl radical transfer, enabling dual carbon-nitrogen bond formation. This protocol provides a versatile platform to access structurally diverse diazides with high functional group compatibility from readily available alkenes without the need of chemical oxidants.
Topics: Iron; Alkenes; Ligands; Oxidants; Catalysis; Carbon
PubMed: 36564406
DOI: 10.1038/s41467-022-35344-9 -
ChemSusChem Oct 2022The dissolution of elemental noble metals (NMs) such as gold, platinum, palladium, and copper is necessary for their recycling but carries a high environmental burden...
The dissolution of elemental noble metals (NMs) such as gold, platinum, palladium, and copper is necessary for their recycling but carries a high environmental burden due to the use of strong acids and toxic reagents. Herein, a new approach was developed for the rapid dissolution of elemental NMs in organic solvents using mixtures of triphenylphosphine dichloride or oxalyl chloride and hydrogen peroxide, forming metal chloride salts directly. Almost quantitative dissolution of metallic Au, Pd, and Cu was observed within minutes at room temperature. For Pt, dissolution was achieved, albeit more slowly, using the chlorinating oxidant alone but was inhibited on addition of hydrogen peroxide. After leaching, transfer of Pt and Pd chloride salts from the organic phase into a 6 m HCl aqueous phase facilitated their separation by precipitation of Pt using a simple diamide ligand. In contrast, the retention of Au chloridometalate in the organic phase allowed its selective separation from Ni and Cu from a leachate solution obtained from electronic CPUs. This new approach has potential application in the hydrometallurgical leaching and purification of NMs from ores, spent catalysts, and electronic and nano-wastes.
Topics: Electronic Waste; Palladium; Copper; Chlorides; Platinum; Hydrogen Peroxide; Solubility; Ligands; Diamide; Salts; Recycling; Gold; Solvents; Oxidants
PubMed: 35929761
DOI: 10.1002/cssc.202201285