Presence Of Sodium Persulfate Research Articles

Persulfate Activation Using Biochar from Pomegranate Peel for the Degradation of Antihypertensive Losartan in Water: The Effects of Pyrolysis Temperature, Operational Parameters, and a Continuous Flow Reactor

Biochar derived from pomegranate peel at different pyrolysis temperatures (450, 600, and 850 °C) was synthesized and characterized by BET, XRD, FTIR, and SEM-EDX. Its catalytic efficiency in the degradation of the antihypertensive losartan (LOS) in the presence of sodium persulfate was examined. The biochar pyrolyzed at 850 °C exhibited higher catalytic activity, which was correlated with the greater surface area and higher concentration of minerals on its surface. Interestingly, despite adsorption being favored at alkaline pH, pH 3 showed the highest LOS degradation. LOS decomposition followed pseudo-first-order kinetics. The addition of persulfate significantly increased LOS reduction, while the presence of inorganic and organic water matrix constituents such as sodium chloride, bicarbonate, and humic acid inhibited the oxidation. Experiments conducted with radical scavengers revealed that both hydroxyl and sulfate radicals, as well as singlet oxygen, participated in LOS decomposition, with the former being the dominant species. Using a continuous flow reactor, the system exhibited a satisfactory steady-state performance of 90% LOS removal for 114 h. Afterward, a moderate decrease in performance was observed, which can be attributed to the alteration of the catalyst’s surface and mineral dissolution due to acidity.

Degradation of dexamethasone in water using BDD anodic oxidation and persulfate: reaction kinetics and pathways

AbstractBACKGROUNDThe presence of micro‐pollutants in conventional wastewater treatment plants raises environmental concerns due to their insufficient removal. Non‐biological methods are needed to treat such compounds and this work demonstrates the use of electrochemical oxidation for the degradation of the drug dexamethasone (DEX).RESULTSA cell consisting of a boron‐doped diamond anode and a stainless steel or carbon cloth cathode was employed, with Na2SO4 being the electrolyte. DEX degradation rate, at the low level of mg L−1 (0.25–2 mg L−1), increases with increasing current (0.02–0.2 A m−2), as well as in the presence of sodium persulfate (50–250 mg L−1); the latter is electrochemically activated to produce additional oxidants and enhances degradation in a synergistic way. A rate constant of 0.194 min−1 was recorded for 0.5 mg L−1 DEX degradation at 0.2 A m−2 with 150 mg L−1 persulfate. The water matrix had little effect on performance compared to experiments in pure water; the only exception was the presence of chloride (50–250 mg L−1), which substantially improved rates due to the formation of active chlorine species (up to about five times). Carbon cloth accelerated DEX removal by up to three times compared to stainless steel and this was partly due to its adsorptive capacity; similarly, reactions involving DEX transformation products (TPs) also occurred faster. Seven TPs were identified and profiles were followed; reaction pathways involve hydroxylation, oxidation, decarboxylation and ring‐opening reactions, followed by fluorine release in the liquid phase.CONCLUSIONA hybrid technology based on electrochemical oxidation and persulfate activation is proposed for the treatment of residual pharmaceuticals in environmental matrices. © 2021 Society of Chemical Industry (SCI).

Recovery of molybdenum, cobalt and nickel from spent hydrodesulphurization catalyst through oxidizing roast followed by sodium persulfate leaching

The spent hydrodesulphurization (HDS) catalyst is an important secondary source for Ni, Mo, Co and Al metals. The high yield recovery of these metals is quite difficult due to the carbon accumulated on the catalyst surface and the stability of the metal oxides. Therefore, the leaching process in the presence of sodium persulfate (Na2S2O8) was carried out after the roasting pre-treatment to remove the carbon from the spent HDS catalyst structure and convert the metal oxides to the soluble form in this study. The optimum experimental conditions were determined as roasting temperature, 500 °C; roasting time, 120 min.; particle size, +75–30 μm; liquid/solid ratio, 12.5 mL/g; Na2S2O8 concentration, 0.4 M; leaching temperature, 50 °C; leaching time, 90 min and stirring speed, 400 r/min. Recovery of Mo (89.8%), Co (86.5%) and Ni (81.2%) from leach solution were achieved by precipitation method. The liquid film diffusion control mechanism best represents the proposed leaching process. On the other hand, the magnitude of Ea values (<20 kJ/mol) for Mo, Co, Ni and Al metals indicates that the leaching process is controlled by liquid film diffusion mechanism.

Photocatalytic-persulfate- oxidation for diclofenac removal from aqueous solutions: Modeling, optimization and biotoxicity test assessment

In this paper, the influence of several aquatic factors (the nature of catalyst, the initial pH and the initial concentration of the pollutant) on the photocatalytic degradation of diclofenac (DFC), one of the most widely prescribed anti-inflammatory non-steroidal drug, was studied. Also, in order to examine the intensification process, the variation of the photocatalytic DFC degradation in the presence of sodium persulfate (PPS) was analyzed. It was found that, compared to titanium dioxide (TiO2), the zinc oxide (ZnO) photocatalyst performed exceptionally well, with a 96.13% DFC degradation efficiency after 150 min. The photodegradation of DFC by ZnO catalyst fitted well the Langmuir–Hinshelwood kinetic model. The maximum efficiency is 97.27% for simulated solar-UVA/ZnO/PPS and 77% for simulated solar-UVA/ZnO. In order to determine the optimal conditions leading to the maximization of DFC removal, an artificial neural network (ANN) modeling approach combined with genetic algorithm (GA) was applied. The best ANN determined had a correlation of 0.999 and it was further used in the process optimization where a 99.7% degradation efficiency was identified as the optimum under the following conditions: DFC initial concentration 37,9 mg L−1, pH 5,88 and PPS initial concentration 500 mg L−1. The effectiveness of the process and the toxicity of the pharmaceutical pollutants and their by-products were also evaluated and confirmed by the biological tests using liver and kidney of Mus musculus mice.

Fabrication and Application of Magnetically Catalytic Imprinting Nanozymes

AbstractNanozymes exhibit excellent enzyme‐like activities but lack specificity. Here, molecularly imprinted polymers (MIPs) based on polypyrrole (PPy) and using methylene blue (MB) as template were grown on Fe3O4 nanozymes to enhance the catalytic selectivity. The obtained composite Fe3O4@PPy MIPs were characterized using a scanning electron microscope, transmission electron microscope, powder X‐ray diffractometer, and vibrating sample magnetometer. The PPy‐encapsulated Fe3O4 nanozymes retained their catalytic ability and almost completely removed MB within 30 min in the presence of sodium persulfate. In comparison with bare Fe3O4 nanozymes, the Fe3O4@PPy MIPs showed superior catalytic selectivity for MB. The apparent rate constants (kapp) for MB, rhodamine B, and methyl orange were 0.073, 0.035, and 0.012 min−1, respectively. Even after five recycling steps, the obtained Fe3O4@PPy MIPs could degrade more than 80% of MB.

Degradation of pesticide thiamethoxam by heat – activated and ultrasound – activated persulfate: Effect of key operating parameters and the water matrix

This work studied the degradation of pesticide thiamethoxam (TMX) by heat-activated and ultrasound-activated persulfate systems. The effect of different parameters on degradation in ultrapure water, such as initial pH (3–10), sodium persulfate (SPS) concentration (50−1000mg/L), TMX concentration (1−10mg/L), temperature (20−70°C) and ultrasound power density (20−42W/L) were examined. For the heat-activated system, TMX degradation increased with increasing temperature and SPS concentration and was favored at pH 6; the activation energy was computed at 108.7kJ/mol based on the Arrhenius law. Ultrasound alone was capable of partially degrading TMX, but the process was favored in the presence of SPS. For the ultrasound-activated system, degradation increased with increasing SPS concentration and power density at pH 6. The effect of temperature was controversial since the beneficial effect of high temperatures on SPS activation is offset by the reduced sonochemical activity due to the “cushioning” effect. Regardless of the activation system, the presence of chloride, bicarbonate and humic acid impeded TMX removal. Besides, TMX degradation was reduced in actual matrices, i.e. wastewater and bottled water, showing the competition between TMX and other matrix constituents for free radicals. For either system, mineralization was slower than TMX degradation, implying the formation of persistent by-products.

Degradation of Sulfamethoxazole Using Iron-Doped Titania and Simulated Solar Radiation

This work examined the photocatalytic destruction of sulfamethoxazole (SMX), a widely used antibiotic, under simulated solar radiation using iron-doped titanium dioxide as the photocatalyst. Amongst the various iron/titania ratios examined (in the range 0%–2%), the catalyst at 0.04% Fe/TiO2 molar ratio exhibited the highest photocatalytic efficiency. The reaction rate followed pseudo-first-order kinetics, where the apparent kinetic constant was reduced as the initial concentration of SMX or humic acid increased. The photodecomposition of SMX was favored in natural pH but retarded at alkaline conditions. Unexpectedly, the presence of bicarbonates (in the range of 0.125–2 g/L) improved the removal of SMX, however, experiments conducted in real environmental matrices showed that process efficiency decreased as the complexity of the water matrix increased. The presence of sodium persulfate as an electron acceptor enhanced the reaction rate. However, only a small synergy was observed between the two individual processes. On the contrary, the addition of tert-butanol, a well-known hydroxyl radical scavenger, hindered the reaction, indicating the significant contribution of these radicals to the photocatalytic degradation of SMX. The photocatalyst retained half of its initial activity after five successive experiments.

Sodium persulfate-promoted site-selective synthesis of mononitroarylamines under transition-metal-free conditions

A practical preparation of nitroarylamines from protected arylamines was herein disclosed. In this system, sodium nitrite acted as a nitration reagent in the presence of sodium persulfate without any transition-metal catalysts. This efficient site-selective protocol took place at room temperature for a short time through a free radical pathway.

Mild, Efficient, and Metal-Free Radical 1,2-Dithiocyanation of Alkynes and Alkenes at Room Temperature.

A transition metal-free process has been reported for 1,2-dithiocyanation of alkynes in the presence of sodium persulfate and potassium thiocyanate reagent combination in a short reaction time under ambient air. Styrene derivatives are equally applicable under the same reaction conditions. Monothiocyanated vinyl derivatives were also synthesized from 2-ethynylpyridine and dimethyl acetylene dicarboxylate. The reaction proceeds by the radical/polar pathway as evidenced from our experiments and literature. After removal of the solvent from the reaction mixture by evaporation, the crude product was purified without conventional workup.

Degradation of antibiotic ampicillin on boron-doped diamond anode using the combined electrochemical oxidation - Sodium persulfate process

In this work, the electrochemical oxidation of antibiotic ampicillin (AMP) on a boron-doped diamond anode in the presence of sodium persulfate (SPS) was investigated (EO/SPS process). Experiments were conducted at AMP concentrations between 0.8 and 3 mg/L, SPS concentrations between 100 and 500 mg/L, current densities between 5 and 110 mA/cm2, in three water matrices (ultrapure water, bottled water and secondary treated wastewater), using 0.1 M Na2SO4 as the supporting electrolyte. AMP degradation follows a pseudo-first order kinetic expression with the apparent rate constant increasing with (i) increasing SPS concentration (from 0.08 min−1 to 0.36 min−1 at 0 and 500 mg/L SPS, respectively, 1.1 mg/L AMP, 25 mA/cm2), (ii) increasing current (from 0.08 min−1 to 0.6 min−1 at 5 and 110 mA/cm2, respectively, 1.1 mg/L AMP, 250 mg/L SPS), and (iii) decreasing AMP concentration (from 0.16 min−1 to 0.31 min−1 at 3 and 0.8 mg/L, respectively, 250 mg/L SPS, 25 mA/cm2). The presence of various anions (mainly bicarbonates) in bottled water did not impact AMP degradation. The observed kinetic constant decreased by 40% in the presence of 10 mg/L humic acid. On the other hand, process efficiency was enhanced almost 3.5 times in secondary effluent due to the electrogeneration of active chlorine species that promote indirect oxidation reactions in the bulk solution. The efficacy of the EO/SPS process was compared to and found to be considerably greater than a process where SPS was activated by simulated solar irradiation at an intensity of 7.3 × 10−7 E/(L.s) (SLR/SPS process). Coupling the two processes (EO/SLR/SPS) resulted in a cumulative, in terms of AMP degradation, effect. The combined process was tested for AMP degradation, mineralization and inhibition to Vibrio fischeri in wastewater; fast AMP removal was accompanied by low mineralization and incomplete toxicity removal.

Redox-triggered hydrogels revealing switchable stiffness properties and shape-memory functions

Metal-ion terpyridine-crosslinked acrylamide hydrogels or metal-ion-bridged carboxymethylcellulose hydrogels reveal redox-switchable stiffness and shape-memory properties.

Sono-activated persulfate oxidation of bisphenol A: Kinetics, pathways and the controversial role of temperature

The sonochemical degradation of bisphenol A (BPA) in the presence of sodium persulfate (SPS) was investigated at 20kHz. Experiments were performed at 110–450μg/L BPA and 1–100mg/L SPS concentration and an ultrasound power density between 4 and 60W/L. The liquid bulk temperature was either kept constant at 30°C or left uncontrolled and gradually increased up to 80°C. BPA degradation occurs due to the combined action of hydroxyl radicals generated by the ultrasound and sulfate radicals generated by SPS sonolysis and this was confirmed with experiments with methanol and t-butanol as radical scavengers. Considerable thermal SPS activation can also occur at increased temperatures (60–80°C) although the enhanced formation of sulfate radicals is compensated by a decrease in sonochemical activity. Kinetics can be approached by a pseudo-first order expression with the apparent rate constant decreasing with increasing BPA concentration; this implies that the actual order is below first. The rate increases with increasing power density and SPS concentration and decreases at alkaline conditions (i.e. pH=9) and in the presence of inorganic and organic constituents (e.g. bicarbonate, humic acid etc) typically found in environmental matrices.Liquid chromatography time of flight mass spectrometry (LC–TOF–MS) analysis revealed the formation of twelve transformation by-products that accompany BPA sonodegradation in the presence of SPS. Based on their evolution profiles, a reaction mechanism is proposed consisting of two major pathways: (i) hydroxylation that can occur mainly in the aromatic ring through HO, SO4− radical attack and to a lesser extent in methyl groups, through hydrogen abstraction by HO radicals, with subsequent O2 addition, and (ii) scission of the bond between the isopropylidene carbon and the phenyl group.

Synthesis and characterization of new vinyl acetate grafting onto epoxidized linseed oil in aqueous media

ABSTRACTModified poly (vinyl acetate) copolymers with epoxidized linseed oil (ELO) as co‐monomer have been prepared. The polymerization was performed in aqueous medium without any additional protective colloid in the presence of sodium persulfate as catalyst. The effect of vinyl acetate (VAc)/ELO feed ratio, reaction temperature, reaction time, and catalyst amount has been studied. FTIR spectroscopy showed that the reaction between ELO and VAc resulted in slight decrease and shift in ELO characteristic bands of oxirane groups; and new bands were detected in the copolymer spectra attributed to PVAc and ELO functional groups. Moreover, new signals attributable to the copolymer were observed in the 1H NMR spectra (δ 4.07 and 1.62 ppm) and in the 13C NMR spectra (δ 15.29 and 31.0 ppm). Analysis by differential scanning calorimetry (DSC) showed a single Tg for the copolymerization product of VAc and ELO and two Tg for the PVAc/ELO blend, indicating the chemical reaction between VAc and ELO. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42089.

Sensitizer-catalyst assemblies for water oxidation.

Two molecular assemblies with one Ru(II)-polypyridine photosensitizer covalently linked to one Ru(II)(bda)L2 catalyst (1) (bda = 2,2'-bipyridine-6,6'-dicarboxylate) and two photosensitizers covalently linked to one catalyst (2) have been prepared using a simple C-C bond as the linkage. In the presence of sodium persulfate as a sacrificial electron acceptor, both of them show high activity for catalytic water oxidation driven by visible light, with a turnover number up to 200 for 2. The linked photocatalysts show a lower initial yield for light driven oxygen evolution but a much better photostability compared to the three component system with separate sensitizer, catalyst and acceptor, leading to a much greater turnover number. Photocatalytic experiments and time-resolved spectroscopy were carried out to probe the mechanism of this catalysis. The linked catalyst in its Ru(II) state rapidly quenches the sensitizer, predominantly by energy transfer. However, a higher stability under photocatalytic condition is shown for the linked sensitizer compared to the three component system, which is attributed to kinetic stabilization by rapid photosensitizer regeneration. Strategies for employment of the sensitizer-catalyst molecules in more efficient photocatalytic systems are discussed.

ChemInform Abstract: Approach to Polysubstituted 4‐Pyridones from N‐Aryl Acetoacetamides via a N to C 1,3‐Acyl Migration Mediated by Sodium Persulfate.

AbstractIn the presence of sodium persulfate, N‐aryl acetoacetamides undergo self‐condensation and novel 1,3‐acyl migration to afford biologically important polysubstituted 4‐pyridones.

Crosslink Polymerization Kinetics and Mechanism of Hydrogels Composed of Acrylic Acid and 2-Acrylamido-2-methylpropane Sulfonic Acid

Crosslink polymerization kinetics of poly(acrylic acid-co-2-acrylamido-2-methylpropane sulfonic acid), AA/AMPS hydrogels, was investigated by using dilatometry in the presence of sodium persulfate as initiator and N, N′-methylene bis(acrylamide) as crosslinker. It was found that the reaction for the crosslink polymerization of AA/AMPS hydrogels had orders of 0.58, 1.14, and 0.86 with respect to the initiator, AMPS, and AA, respectively. From the Arrhenius plots, the activation energy of the crosslink polymerization was found to be about 140 and 89 kJ·mol −1 in the presence and absence of the crosslinker, respectively, in the temperature range from 45 to 65 °C. It was noted that the crosslinker had effects on the reaction order of the initiator and the activation energy due to the formation of cross-linked networks, which was verified by Fourier transfer infrared (FTIR) spectrum. To further confirm the influences of the cross-linked network structure on kinetic parameters of the crosslink polymerization, a mechanism was proposed, which highlights the different termination routes between free radical polymerization and crosslink polymerization. These results suggest that dilatometry provides a convenient tool for crosslink polymerization study, and confirm that the cross-linked networks are formed in the crosslink polymerization.

Synthesis of Hollow-Structured Nano- and Microspheres from Pectin in a Nanodroplet Emulsion

Hollow-structured nano- and microspheres with diameters ranging from 24 microm to 160 nm were successfully produced from chemically modified pectin (Ma-Pec) through a two-step synthesis. In a first step, the Pec was modified with glycidyl methacrylate (GMA) in a heterogeneous phase system, indeed consisting of water-soluble Pec and water-insoluble GMA, via an interfacial reaction at the interface of the GMA-water phase system after 12 h under continuous stirring of 1000 rpm at 60 degrees C. In a second step, the spheres were prepared in a water-in-benzyl alcohol nanodroplet emulsion at 12000 rpm under a bubbling stream of nitrogen in the presence of sodium persulfate, as initiator, and TEMED, as catalytic agent. FT-IR spectra revealed that the vinyl groups (CC) coming from the GMA were attached onto backbone of the polysaccharide. 13C-CP/MAS NMR spectra demonstrated that the spheres were formed via carbon-carbon pi-bonds on Ma-Pec in the water phase, for the duration of the dispersion stage. The dark center (an empty core) and edge of the hollow spheres could be easily identified by SEM micrographs. This type of polymer structure represents a class of unique material with particular importance in terms of state-of the-art applications in both nano- and microencapsulation of drugs, for example, protection shields of biologically active agents.

Metalloporphyrin-sensitized photooxidation of water to oxygen on the surface of colloidal iridium oxides: photochemical and pulse radiolytic studies

Derivatives of TSPP (tetrakis(4-sulfonatophenyl)porphyrin) were prepared and tested as photosensitizers for oxidation of water to oxygen on the surface of colloidal iridium oxide. Triplet quantum yields, energies, and lifetimes were measured by laser flash photolysis. Rate constants for quenching the porphyrin triplet state with O{sub 2} and with persulfate ions were also determined. The rates of interaction between the porphyrin radical cations and colloidal IrO{sub x} particles were measured by pulse radiolysis for several of the compounds. The one-electron oxidation potentials of the porphyrins, measured by cyclic voltammetry, were varied between 0.7 and 1.4 V vs. NHE by using different metal centers and by substitution on the phenyl rings. Illumination of a porphyrin in the presence of sodium persulfate and an IrO{sub x} colloid resulted in generation of O{sub 2} in a process that was strongly dependent upon pH and upon the nature of the photosensitizer in the same manner as the kinetics determined by pulse radiolysis. The rate of O{sub 2} production under any conditions could be explained on the basis of thermodynamic criteria relating to either of the individual quenching or water oxidation steps. Zn porphyrins (0.9 < E{sub {1/2}} < 1.02 V) effected O{sub 2} production onlymore » in alkaline solution, whereas PdTSPP (E{sub {1/2}} = 1.1 V) gave efficient O{sub 2} evolution even in neutral solution. Further increase in E{sub 1/2}, as achieved with InTSPP (E{sub {1/2}} = 1.16 V), lowers the threshold pH for O{sub 2} evolution, and pulse radiolysis experiments confirmed that the radical cation of this porphyrin is the most reactive toward the catalyst, reacting at diffusion-controlled rates even in acidic solutions. However, the rate of O{sub 2} formation with InTSPP was very low due to the inefficient photochemistry arising from the incomplete quenching of this less-reducing porphyrin triplet state by persulfate ions.« less