ABSTRACT: Hazardous organic wastes from industrial, military, and commercial activities represent one of the greatest challenges to human beings. Advanced oxidation processes (AOPs) are alternatives to the degradation of those organic wastes. However, the knowledge about the exact mechanisms of AOPs is still incomplete. Here we report a phenomenon in the AOPs: induced effects, which is a common property of combustion reaction. Through analysis EDTA oxidation processes by Fenton and UV-Fenton system, the results indicate that, just like combustion, AOPs are typical induction reactions. One most compelling example is that pre-feeding easily oxidizable organic matter can promote the oxidation of refractory organic compound when it was treated by AOPs. Connecting AOPs to combustion, it is possible to achieve some helpful enlightenment from combustion to analyze, predict and understand AOPs. In addition, we assume that maybe other oxidation reactions also have induced effects, such as corrosion, aging and passivation. Muchmore research is necessary to reveal the possibilities of induced effects in those fields.
Project description:We report a supramolecular strategy to promote radical-mediated Fenton oxidation by the rational design of a folded host-guest complex based on cucurbituril (CB). In the supramolecular complex between CB and a derivative of 1,4-diketopyrrolo[3,4-<i>c</i>]pyrrole (DPP), the carbonyl groups of CB and the DPP moiety are brought together through the formation of a folded conformation. In this way, the electrostatic effect of the carbonyl groups of CB is fully applied to highly improve the reactivity of the DPP radical cation, which is the key intermediate of Fenton oxidation. As a result, the Fenton oxidation is extraordinarily accelerated by over 100 times. It is anticipated that this strategy could be applied to other radical reactions and enrich the field of supramolecular radical chemistry in radical polymerization, photocatalysis, and organic radical battery and holds potential in supramolecular catalysis and biocatalysis.
Project description:In the present work, ultrasound irradiation, photocatalysis with TiO<sub>2</sub>, Fenton/Photo-Fenton reaction, and the combination of those techniques were investigated for the decolorization of industrial dyes in order to study their synergy. Three azo dyes were selected from the weaving industry. Their degradation was examined via UV illumination, Fenton and Photo-Fenton reaction as well as ultrasound irradiation at low (20 kHz) and high frequencies (860 kHz). In these experiments, we investigated the simultaneous action of the ultrasound and UV irradiation by varying parameters like the duration of photocatalysis and ultrasound irradiation frequency. At the same time, US power, temperature, amount of TiO<sub>2</sub> photocatalyst and amount of Fenton reagent remained constant. Due to their diverse structure, each azo dye showed different degradation levels using different combinations of the above-mentioned Advanced Oxidation Processes (AOPs). The Photo-Fenton reagent is more effective with US 20 kHz and US 860 kHz for the azo dyes originated from the weaving industry at pH = 3 as compared to pH = 6.8. The combination of the Photo-Fenton reaction with 860 kHz ultrasound irradiation for the same dye gave an 80% conversion at the same time. Experiments have shown a high activity during the first two hours. After that threshold, the reaction rate is decreased. FT-IR and TOC measurements prove the decolorization due to the destruction of the chromophore groups but not complete mineralization of the dyes.
Project description:We describe the use of catalytically self-propelled microjets (dubbed micromotors) for degrading organic pollutants in water via the Fenton oxidation process. The tubular micromotors are composed of rolled-up functional nanomembranes consisting of Fe/Pt bilayers. The micromotors contain double functionality within their architecture, i.e., the inner Pt for the self-propulsion and the outer Fe for the in situ generation of ferrous ions boosting the remediation of contaminated water.The degradation of organic pollutants takes place in the presence of hydrogen peroxide, which acts as a reagent for the Fenton reaction and as main fuel to propel the micromotors. Factors influencing the efficiency of the Fenton oxidation process, including thickness of the Fe layer, pH, and concentration of hydrogen peroxide, are investigated. The ability of these catalytically self-propelled micromotors to improve intermixing in liquids results in the removal of organic pollutants ca. 12 times faster than when the Fenton oxidation process is carried out without catalytically active micromotors. The enhanced reaction-diffusion provided by micromotors has been theoretically modeled. The synergy between the internal and external functionalities of the micromotors, without the need of further functionalization, results into an enhanced degradation of nonbiodegradable and dangerous organic pollutants at small-scale environments and holds considerable promise for the remediation of contaminated water.
Project description:In this work, the degradation of chloroquine (CLQ), an antiviral and antimalarial drug, using electro-Fenton oxidation was investigated. Due to the importance of hydrogen peroxide (H2O2) generation during electro-Fenton oxidation, effects of pH, current density, molecular oxygen (O2) flow rate, and anode material on H2O2 generation were evaluated. H2O2 generation was enhanced by increasing the current density up to 60 mA/cm2 and the O2 flow rate up to 80 mL/min at pH 3.0 and using carbon felt cathode and boron-doped diamond (BDD) anode. Electro-Fenton-BDD oxidation achieved the total CLQ depletion and 92% total organic carbon (TOC) removal. Electro-Fenton-BDD oxidation was more effective than electro-Fenton-Pt and anodic oxidation using Pt and BDD anodes. The efficiency of CLQ depletion by electro-Fenton-BDD oxidation raises by increasing the current density and Fe2+ dose; however it drops with the increase of pH and CLQ concentration. CLQ depletion follows a pseudo-first order kinetics in all the experiments. The identification of CLQ degradation intermediates by chromatography methods confirms the formation of 7-chloro-4-quinolinamine, oxamic, and oxalic acids. Quantitative amounts of chlorides, nitrates, and ammonium ions are released during electro-Fenton oxidation of CLQ. The high efficiency of electro-Fenton oxidation derives from the generation of hydroxyl radicals from the catalytic decomposition of H2O2 by Fe2+ in solution, and the electrogeneration of hydroxyl and sulfates radicals and other strong oxidants (persulfates) from the oxidation of the electrolyte at the surface BDD anode. Electro-Fenton oxidation has the potential to be an alternative method for treating wastewaters contaminated with CLQ and its derivatives.
Project description:We examined the effects of ultrasound and Fenton reagent on ultrasonic coupling Fenton oxidation (U+F) pre-treatment processes for the disintegration of wastewater treatment plant sludge. The results demonstrated that U+F treatment could significantly increase soluble chemical oxygen demand (SCOD), total organic carbon (TOC), and extracellular polymeric substances (EPS) concentrations in sludge supernatant. This method was more effective than ultrasonic (U) or Fenton oxidation (F) treatment alone. U+F treatment increased the release of SCOD by 2.1- and 1.4-fold compared with U and F alone, respectively. U+F treatment increased the release of EPS by 1.2-fold compared with U alone. After U+F treatment, sludge showed a considerably finer particle size and looser microstructure based on fluorescence microscopy, and the concentration of hydroxyl radicals (OH•) increased from 0.26?mM by F treatment to 0.43?mM by U+F treatment based on fluorescence spectrophotometer. This demonstrated that U+F treatment improves the release of organic matter from sludge.
Project description:The UV-induced advanced oxidation processes (AOPs, including UV/Cl2, UV/NH2Cl, UV/ClO2 and UV/H2O2 ) degradation kinetics and energy requirements of iopamidol as well as DBPs-related toxicity in sequential disinfection were compared in this study. The photodegradation of iopamidol in these processes can be well described by pseudo-first-order model and the removal efficiency ranked in descending order of UV/Cl2 > UV/H2O2 > UV/NH2Cl > UV/ClO2 > UV. The synergistic effects could be attributed to diverse radical species generated in each system. Influencing factors of oxidant dosage, UV intensity, solution pH and water matrixes (Cl- , NH4 + and nature organic matter) were evaluated in detail. Higher oxidant dosages and greater UV intensities led to bigger pseudo-first-order rate constants (Kobs) in these processes, but the pH behaviors exhibited quite differently. The presence of Cl- , NH4 + and nature organic matter posed different effects on the degradation rate. The parameter of electrical energy per order (EE/O) was adopted to evaluate the energy requirements of the tested systems and it followed the trend of UV/ClO2 > UV > UV/NH2Cl > UV/H2O2 > UV/Cl2 . Pretreatment of iopamidol by UV/Cl2 and UV/NH2Cl clearly enhanced the production of classical disinfection by-products (DBPs) and iodo-trihalomethanes (I-THMs) during subsequent oxidation while UV/ClO2 and UV/H2O2 exhibited almost elimination effect. From the perspective of weighted water toxicity, the risk ranking was UV/NH2Cl > UV/Cl2 > UV > UV/H2O2 > UV/ClO2 . Among the discussed UV-driven AOPs, UV/Cl2 was proved to be the most cost-effective one for iopamidol removal while UV/ClO2 displayed overwhelming advantages in regulating the water toxicity associated with DBPs, especially I-THMs. The present results could provide some insights into the application of UV-activated AOPs technologies in tradeoffs between cost-effectiveness assessment and DBPs-related toxicity control of the disinfected waters containing iopamidol.
Project description:A rapid Fenton treatment at second-scale intervals was investigated for further removal of organic compounds in the effluent of bio-treated dyeing and finishing wastewater (BDFW). The decolorization kinetics was studied using a stopped-flow spectrophotometer (SFS) at second-scale intervals. A combined first-order model was found to fit well for the decrease of both methylene blue and rhodamine B in SFS as well as SCOD (soluble chemical oxygen demand) and DOC (dissolved organic carbon) in real BDFW in batch test during Fenton oxidation. A full-scale plant with treatment capacity of 400,000 m3·d-1 was designed and has been run continuously based on the results of the stopped-flow study to treat the effluent of BDFW using Fenton oxidation in 16 pipeline reactors, each with a volume of 6.9 m3 and 24 s of reaction time since 2014. The COD, SCOD and DOC decreased from 140, 110 and 35 mg·L-1 to 77, 71 and 26 mg·L-1 respectively, which can meet the latest strict discharge limitations. The natural fluorescent substances detected in the BDFW were completely removed. The main organic pollutants in the BDFW can be significantly reduced using both gas chromatography-mass spectrometry and ultrahigh-performance liquid chromatography-hybrid quadrupole time-of-flight mass spectrometry. The rapid Fenton reaction applied in pipeline reactors at second intervals has several advantages over the conventional Fenton's process such as much shorter reaction time at second scale intervals, no need to build extra pH adjustment or reaction tanks, simple operation, low capital cost, etc.
Project description:Catalytic oxidation reactions often suffer from drawbacks such as low yields and poor selectivity. Particularly, selective oxidation of alcohols becomes more difficult when a compound contains more than one oxidizable functional group. In order to deliver a methodology that addresses these issues, herein we report an efficient, aerobic, chemoselective and simplified approach to oxidize a broad range of benzyl and propargyl alcohols containing diverse functional groups to their corresponding aldehydes and ketones in excellent yields under mild reaction conditions. Optimal yields were obtained at room temperature using 1?mmol substrate, 10?mol?% copper(I) iodide, 10?mol?% 4-dimethylaminopyridine (DMAP), and 1?mol?% 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) in acetonitrile, under an oxygen balloon. The catalytic system can be applied even when sensitive and oxidizable groups such as alkynes, amines, and phenols are present; starting materials and products containing such groups were found to be stable under the developed conditions.
Project description:Potassium (K) ion-exchanged ZSM-5 zeolites were investigated for catalytic soot combustion. X-ray absorption fine-structure (XAFS), Raman, in situ IR and NH3-temperature programmed desorption (NH3-TPD) confirmed the location of K+ at the ion-exchanged sites. Temperature-programmed oxidation (TPO) reactions showed that K-ZSM-5 decreased ignition tempeatures of soot combustion and increased selectivity to CO2. The improved activity for soot combustion by increasing K+-exchanged amounts via decreasing the Si/Al ratio reinforced the K+ ions participating in soot combustion. 18O2 isotopic isothermal reactions suggested the activation of gaseous oxygen by the K+ ions. This demonstrated a new appliction of alkali metal exchanged zeolites and the strategy for enhancement of catalytic soot combustion activity.
Project description:The hydroxyl radical (·OH) is a powerful oxidant that is produced in a wide range of environments via the Fenton reaction (Fe<sup>2+</sup> ?+?H<sub>2</sub>O<sub>2</sub>???Fe<sup>3+</sup> ?+?·OH?+?OH<sup>-</sup>). The reactants are formed from the reduction of Fe<sup>3+</sup> and O<sub>2</sub>, which may be promoted by organic reductants, such as hydroquinones. The aim of this study was to investigate the extent of ·OH formation in reactions between 2,6-dimethoxyhydroquinone (2,6-DMHQ) and iron oxide nanoparticles. We further compared the reactivities of ferrihydrite and goethite and investigated the effects of the O<sub>2</sub> concentration and pH on the generation of ·OH. The main finding was that the reactions between 2,6-DMHQ and iron oxide nanoparticles generated substantial amounts of ·OH under certain conditions via parallel reductive dissolution and catalytic oxidation reactions. The presence of O<sub>2</sub> was essential for the catalytic oxidation of 2,6-DMHQ and the generation of H<sub>2</sub>O<sub>2</sub>. Moreover, the higher reduction potential of ferrihydrite relative to that of goethite made the former species more susceptible to reductive dissolution, which favored the production of ·OH. The results highlighted the effects of surface charge and ligand competition on the 2,6-DMHQ oxidation processes and showed that the co-adsorption of anions can promote the generation of ·OH.