Pseudo First-order Reaction Rate Constants Research Articles

Key role of carbon as an efficient electron bridge in CuO@C@Fe2O3 for enhancing H2O2 activation during photo-assisted Fenton-like reaction

The Fe3+/Fe2+ cycle has been identified as the rate-limiting step in the Fenton system, and many efforts have been made to promote the Fe3+ reduction via external electrons provided by various electron donors. However, how to design an efficient electron transport pathway and then inhibit the invalid electron shuttle has been largely underestimated. In this study, two kinds of heterogeneous Fenton catalysts of CuO@Fe2O3 and CuO@C@Fe2O3 were prepared. The key role of carbon in transporting electrons as an electron bridge and its enhancement mechanism in photo-assisted Fenton-like performances were explored in detail. Compared with CuO@Fe2O3, the removal efficiency of tetracycline (TC) and the corresponding pseudo-first order reaction rate constants over CuO@C@Fe2O3 increased significantly from 88.6% and 0.1054min-1 to 99.7% and 0.2058min-1, respectively. Based on a series of probe experiments, visible light irradiation can promote the reduction of Cu2+ to Cu+, then the carbon in CuO@C@Fe2O3 can effectively transfer electrons from Cu+ to Fe3+, enhancing the Fe3+/Fe2+ cycle and the following Fenton-like efficiency. Since more ·OH while less ∙O2- was produced over CuO@C@Fe2O3, which further supports the fact that the enhanced Fe3+/Fe2+ cycle was due to the transfer electron from Cu+ to Fe3+ instead of the Haber-Wiss mechanism. Hence, this study provides new insight for effectively improving the transfer efficiency and effective utilization of electrons in Fenton systems.

Comparative study of metal nanoparticles anchored TiO2 using polyoxometalate intermediate in photodegradation of azo dye pollutant in aquatic environments

Herein, metal nanoparticles (Au, Ag, and Pt) are locally deposited on TiO2 with an UV-switchable polyoxometalate intermediate to achieve highly active photocatalyst nanohybrids. The successful preparation of these nanohybrids was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), Zeta potential (ZP), and UV–visible spectroscopy. TEM images showed the anchoring of metal nanoparticles of an average size of 20 nm on the TiO2 surface. A comparative study revealed that the bandgap energy was reduced in the order of Pt@PW-TiO2 (2.90 eV) > Ag@PW-TiO2 (2.95 eV) > Au@PW-TiO2 (3.05 eV). Likewise, the photocatalytic efficiency of fabricated nanohybrids was investigated in the degradation of reactive blue 19 (RB19), an azo dye model, under UV–visible light illumination and different experimental conditions. Optimal photodegradation occurred at pH = 3.8 with 0.33 gL−1 of photocatalyst exposed to light for 60 min. Under optimal conditions, the maximum and minimum photodegradation abilities were observed using Pt and Au deposited hybrids. A kinetic study of RB19 photodegradation was also conducted, resulting in pseudo-first order reaction rate constants of 0.0203, 0.025, and 0.0808 min−1, respectively, for the Au@PW-TiO2, Ag@PW-TiO2, and Pt@PW-TiO2 nanohybrids. Finally, the most probable mechanism for RB19 degradation using prepared photocatalysts is presented.

Insights into the electron transfer mechanisms of peroxydisulfate activation by modified metal-free acetylene black for degradation of sulfisoxazole

Herein, a modified metal-free acetylene black (MMF-AB) catalyst was synthesized by a simple solvothermal-calcination method and designed successfully to activate peroxodisulfate (PDS) for the degradation of sulfisoxazole (SIZ). Due to the doping of N, S and O metal-free elements, the modified catalyst showed excellent catalytic performance with 100% SIZ removal within 30 min. Pseudo first-order reaction rate constants (evaluating catalytic efficiencies and activity) of MMF-AB (kobs = 0.105 min−1) was 3 times higher than pure-AB (kobs = 0.029 min−1). Interestingly, it was demonstrated that the reaction system is based on the transfer of electrons from SIZ to PDS to realize an electron-transfer-based mechanism by the evidence of premixing, electron paramagnetic resonance (EPR) spectroscopy, salt-bridge experiments and electrochemical analyses. The introduction of recyclable filtration device solved the secondary pollution caused by the dispersion of the powdered catalyst in the treated water, which further proved the practicality and superiority of the MMF-AB catalyst.

Hydroxyl radical-driven transformations of bisphenol A and 2,4-dinitroanisole: Experimental and computational analysis.

This study used experimental and computational analysis to investigate the advanced oxidation of bisphenol A (BPA) and 2,4-dinitroanisole (DNAN). The pseudo first-order reaction rate constants depended on the molar peroxide ratio and were between 0.13 and 0.28 min-1 for BPA and between 0.018 and 0.032 min-1 for DNAN. The kinetic differences appear to be due in part to the energy requirements for oxidation, which depended on the reaction mechanism but were typically lower for BPA than they were for DNAN. Density functional theory (DFT) was used to develop transformation pathways that included experimentally-detected byproducts. The most energetically favored pathway for BPA oxidation begins with the formation of hydroxylated derivatives, while for DNAN, the most energetically favorable degradation pathway begins with the substitution of the methoxy group. Overall, these findings demonstrate the power of combining experimental and computational tools to reveal transformation mechanisms during water treatment. PRACTITIONER POINTS: Advanced oxidation transformations for two emerging water pollutants, bisphenol A and dinitroanisole, was investigated. The observed reaction kinetics depended on molar peroxide ratio in a manner that is in keeping with previous findings. Density functional theory-based analysis revealed reaction energy requirements and degradation pathways.

Photocatalytic degradation of gentamicin using TiO2 nanoparticle driven by UV light irradiation

Antibiotics have contributed to enhance life expectancy in underdeveloped countries by reducing mortality rate, but the hazards connected with antibiotic pollution are largely harming people. The photocatalytic degradation of gentamicin utilizing Titanium oxide nanoparticles (TiO2nps) using visible and UV light has been studied. TiO2nps was synthesized using the co-precipitation method and calcined at 600 °C. XRD study confirmed the phase formation and Raman study confirmed the structure of TiO2nps. UV–Vis’s absorption study was performed in which a broad peak was obtained between 300 and 600 nm. The degradation percentage for the photocatalytic study was found to be 51 %, 84 %, and 95 % under dark, visible light, and UV light, respectively. The pseudo-first order reaction rate constant was calculated for the sample exposed to UV light, and was found to be 0.0158. In the cyclic study, high degradation percentage of more than 80 % was obtained even after four cycle of degradation.

Generation of adsorbed atomic hydrogen by Pd(II) doped Fe(OH)2 enables ultra-fast reductive dechlorination of trichloroethylene

Trichloroethylene (TCE) is a notorious persistent pollutant in groundwater, while most reductive dechlorination processes result in the formation of toxic less-chlorinated by-products. In this work, adsorbed atomic hydrogen (H*) was produced by Pd(II) doped Fe(OH)2, which was used for ultra-fast reductive dechlorination of TCE without the formation of less-chlorinated by-products. When the Fe(OH)2 dosage is 0.5 mM and the Pd(II) dosage is 20 μM, TCE (42 μM) is completely removed in 60 min with the pseudo first-order reaction rate constant of 7.74 h−1. Radical quenching experiment and electrochemical analysis both confirmed that adsorbed H* rather than absorbed H* contribute to the reduction of TCE. Density function theory calculation demonstrated that small Pd clusters were more beneficial to TCE dechlorination than large Pd clusters. The pseudo first-order rate constant for TCE reduction in real groundwater was as high as 0.018 min–1, demonstrating the potential application of Pd/Fe(OH)2 in groundwater remediation.

Hydrogen Evolution Reaction By Metal-Free Poly-Neutral Red Electrocatalyst

While electric power supply by renewable sources such as solar and wind has become viable for their significant cost reduction, its intermittency demands urgent development of large scale storage technologies. Although conversion of electrical energy into storable hydrogen via electrolysis of water is ideal, noble metals and their oxides are used as electrocatalysts for their activities and stabilities. Alternative electrocatalysts out of abundant elements are needed for sustainable technological development.Recently, some metal-free organic conductive polymers with hydrogen-bonding capabilities were found to exhibit high electrocatalytic activities towards hydrogen evolution reaction (HER) [1,2]. We have succeeded electropolymerization of neutral red (NR) resulting in a formation of conductive poly-NR (PNR) that shows a relatively high HER catalytic activity [3]. PNR possesses hydrogen-bonding N atoms as annelated in the phenazine aromatic system as well as those in the amino substituents. Electrochemical analysis combined with in situ spectroscopy as well as DFT calculation was performed to clarify the mechanism and kinetics of HER electrocatalysis by PNR.This films of PNR were obtained by electropolymerization on F-doped SnO2 coated conductive glass (FTO, Asahi Glass) and SIGRATHERM® GFA5 Carbon felt with potential cycling between -0.2 and 1.2 V (vs. Ag/AgCl) at 50 mV s-1 for 50 times in a 5 mM NR - 0.1 M H2SO4 aqueous solution under N2. Polyaniline (PANI) was also obtained by the same method for comparison. The HER catalysis was evaluated by linear sweep voltammetry (LSV) in a 1 M trifluoromethanesulfonic acid (TfOH) under N2. The film samples were characterized by Fourier transform infrared spectroscopy (FT-IR), UV-visible spectroscopy. In-situ UV-visible spectroelectrochemical monitoring of the reaction intermediate was carried out to determine the rate of HER.PNR undergoes a pseudo-reversible reduction that shifts -61.8 mV/pH under acidic conditions and HER takes off right at this point (Fig. 1, a). Coupling of the same number of protons / electrons is expected as the electrochemical stoichometry from the observed Nernstian relationship, namely, resulting in a singly reduced PNR-H or doubly reduced PNR-H2 as depicted in Fig. 1 b. Protonation of N atoms was reasonably expected and also supported by the DFT calculation. The hydrogen atoms stabilized in the reaction intermediate can be associated to release H2 (Tafel mechanism) to complete the cycle of electrocatalysis of HER.Reduction of PNR in fact is associated with a color change. The broad reddish absorption of PNR peaking at around 500 nm attenuates to change the color to a pale yellow by constantly applying -0.15 V vs. RHE to produce PNR-H and/or PNR-H2 state as shown in Fig. 1c. Gradual recovery of the original red PNR was observed under open circuit under N2, associated with the H2 release. Thus, the rate of the spectral change is analyzed to determine the rate of the Tafel process. Pseudo-first order reaction rate law can be applied as proton is abundant and its concentration is constant, so that the rate of HER (r H2) is simply described as the rate of consumption of PNR-H and/or PNR-H2 as, r H2=-dC PNR-H2/dt =-kt (1)The ratio of PNR-H and PNR-H2 as compared to their initial amount (x PNR-red) was defined from the absorbance at 545 nm before and after reduction as, x PNR-red = C PNR-red/C 0-PNR-red = exp (-kt) (2)Good fitting of the experimental data was obtained to yield a pseudo-first order reaction rate constant of 9.98×10-4 s-1 for this rate-limiting step.

Heterogeneous activation of peroxymonosulfate by Co3O4 loaded biochar for efficient degradation of 2,4-dichlorophenoxyacetic acid

Carbon-based catalysts have the advantage of biological cleaning and cost-effectiveness in water treatment. This work used a two-step calcination method to prepare a novel nanometer composite material (CBC-1), where flake-like Cobalt oxide (Co 3 O 4 ) loaded on rice husk biochar. CBC-1 was used to activate PMS and degrade 2,4-dichlorophenoxyacetic acid (2,4-D) in the water phase. SEM, XRD, FT-IR, BET, XPS, EPR and other characterization methods showed that both sulfate radical and hydroxyl radical were involved in 2,4-D degradation. Both the high hydroxyl (-OH) content and Co (II) of the catalyst are beneficial to the activation of PMS. The pseudo-first order reaction rate constant of CBC-1 was 5.3 and 16 times that of pure Co 3 O 4 and biochar. This research provides new ideas for the application of carbon-based materials in the water treatment process and achieves the goals of treating waste water polluted by pesticides effectively and resource utilization of agricultural waste. • Provided a new view for the waste utilization of rice husk. • Enhanced the catalytic activity of Co 3 O 4 with rice husk biochar added. • CBC-1/PMS system exhibited satisfactory degradation efficiency of 2,4-D within 10 min. • The higher hydroxyl content of CBC-1 is helpful for enhancing the catalytic ability.

Construction of Fe3O4@β-CD/g-C3N4 nanocomposite catalyst for degradation of PCBs in wastewater through photodegradation and heterogeneous Fenton oxidation

Herein, a multifunctional magnetic β-cyclodextrin/graphitic carbon nitride catalyst (Fe3O4@β-CD/g-C3N4) was fabricated for PCBs degradation in wastewater. The catalysts were investigated using various characterization methods including X-ray diffractometry, field emission scanning electron microscopy, vibrating sample magnetometry and UV–Vis diffuse reflectance spectroscopy et al. As-synthesized Fe3O4@β-CD/g-C3N4 displayed the superior catalytic activity, and the degradation efficiency of six PCBs was 77%–98% at 55 min, with pseudo-first order reaction rate constants were in the range of 0.027–0.065 min−1. The super synergy of photodegradation and heterogeneous Fenton oxidation was 2.1–4.6 times more efficient than that photodegradation or heterogeneous Fenton oxidation alone. Fe3O4@β-CD/g-C3N4 could be reused for at least 6 cycles without significant deterioration to its catalytic activity. Several reaction intermediates were identified using GC-MS/MS. The products of the last stage of the reaction were alkanes, aldehyde, ketone and ester, which were formed via ring opening, dechlorinating and isomerization reactions. For PCBs degradation, •OH played a major role, •O2− played a secondary role, 1O2, h± and e− played minor roles based on reactive species trapping experiments. The catalytic performance of the Fe3O4@β-CD/g-C3N4 − H2O2 − visible light system towards degradation of PCBs in river water and municipal wastewater was 89–100% and 69–92%, respectively, which means the Fe3O4@β-CD/g-C3N4 has great potential for environmental remediation.

Response surface methodology-based fabrication of boron-doped diamond electrodes for electrochemical degradation of guaifenesin in aqueous solutions

In this study, a boron doped diamond (BDD) electrode (RSM2), fabricated at a boron/carbon (B/C) ratio = 0.75%, a carbon/hydrogen (C/H) ratio = 1.00%, and a reaction chamber pressure (P) = 5.00 torr, exhibited the best performance in terms of electrochemical degradation of guaifenesin [guaiacol glyceryl ether (GGE)] and total organic carbon (TOC) removal among 11 BDD electrodes prepared according to the response surface methodology (RSM). Associated with the B/C, C/H, and P parameters, BDD's diamond crystallite structure, graphite-sp2 C, and grain size influenced the performance of the fabricated BDD electrodes. At 0.125 A cm−2 and 25 °C, the pseudo-first order reaction rate constants of the GGE and TOC removals were 0.33 and 0.031 min−1, respectively, and such removals were better in 0.5 M Na2SO4 than in real hospital wastewater. Both direct and indirect oxidation of GGE occurred during electrolysis. Solution pH affected the indirect oxidation of GGE by •OH, SO4•−, or persulfate electrochemically generated during electrolysis. Several intermediates, including guaiacol, quinones, (aromatic and aliphatic) acids, and hexane-2,5-dione were detected and used to picture the GGE degradation pathways.

BiOBr/PBCD-B-D dual-function catalyst with oxygen vacancies for Acid Orange 7 removal: Evaluation of adsorption-photocatalysis performance and synergy mechanism

The fabrication of a dual-function material is an effective strategy to promote the degradation of pollutants through the synergy of adsorption and photocatalysis. Herein, we introduce an amphiphilic hyper-crosslinked porous cyclodextrin polymer (PBCD-B-D) into bismuth oxide bromide (BiOBr) via a one-pot solvothermal method to construct three-dimensional (3D) spherical flower-shaped BiOBr/PBCD-B-D (BOP) composites for removing the organic dye Acid Orange 7 (AO7). The prepared BiOBr composite loaded with 24% PBCD-B-D (BOP-24) displayed an optimal adsorption–photocatalytic effect. Under different concentration gradients, the pseudo first-order reaction rate constant of BOP-24 was 2–5 times that of BiOBr after visible-light irradiation. The unique cavity structure of PBCD-B-D resulted in a strong inclusion ability, which could concentrate organic pollutants and shorten the mass transfer distance. The introduction of PBCD-B-D to BiOBr led to an increase in the specific surface area and pore volume, which not only provided a large number of adsorption sites and active centers but also produced oxygen vacancies to improve charge separation. In addition, a possible degradation pathway was proposed for AO7 based on 3D excitation-emission matrix fluorescence spectra and analysis by liquid chromatography-mass spectrometry. This work combines the advantages of both adsorption and photocatalytic technologies for environmental remediation, and opens an avenue for dual-function high-surface-area adsorbent/photocatalysts via a one-pot in situ method.

Persulfate enhanced photoelectrochemical oxidation of organic pollutants using self-doped TiO2nanotube arrays: Effect of operating parameters and water matrix

This study investigated the influence of adding peroxydisulfate (PDS) to a photoelectrocatalysis (PEC) system using self-doped TiO2 nanotube arrays (bl-TNAs) for organic pollutant degradation. The addition of 1.0 mM PDS increased the bisphenol-A (BPA) removal efficiency of PEC (PEC/PDS) from 65.0% to 85.9% within 1 h. The enhancement could be attributed to the high formation yield of hydroxyl radicals (·OH), increased charge separation, and assistance of the sulfate radicals (SO4·−). The PDS concentration and applied potential bias were influential operating parameters for the PEC/PDS system. In addition, the system exhibited a highly stable performance over a wide range of pH values and background inorganic and organic constituents, such as chloride ions, bicarbonate, and humic acid. Further, the degradation performance of the organic pollutant mixture, including BPA, 4-chlorophenol (4-CP), sulfamethoxazole (SMX), and carbamazepine (CBZ), was evaluated in 0.1 M (NH4)2SO4 solution and real surface water. The degradation efficiency increased in the order of CBZ < SMX < 4-CP < BPA in the PEC and PEC/PDS systems with both water matrices. Compared with the PEC system, the PEC/PDS (1.0 mM) system showed a threefold higher pseudo first-order reaction rate constant for BPA among pollutant mixtures in surface water. This was attributed to enhanced ·OH production and the selective nature of SO4·−. The pseudo first-order reaction rate constants of other pollutants, i.e., 4-CP, SMX, and CBZ increased ca. twofold in the PEC/PDS system. The results of this study showed that the PEC/PDS system with bl-TNAs is a viable technology for oxidative treatment.

Fabrication of electrochemically-modified BiVO4-MoS2-Co3O4composite film for bisphenol A degradation

A new electrochemically-modified BiVO4-MoS2-Co3O4 (represented as E-BiVO4-MoS2-Co3O4) thin film electrode was successfully synthesized for environmental application. MoS2 and Co3O4 were grown on the surface of BiVO4 to obtain BiVO4-MoS2-Co3O4. E-BiVO4-MoS2-Co3O4 film was achieved by further electrochemical treatment of BiVO4-MoS2-Co3O4. The as-prepared E-BiVO4-MoS2-Co3O4 exhibited significantly enhanced photoelectrocatalytic activity. The photocurrent density of E-BiVO4-MoS2-Co3O4 thin film is 6.6 times that of BiVO4 under visible light irradiation. The degradation efficiency of E-BiVO4-MoS2-Co3O4 for bisphenol A pollutant was 81.56% in photoelectrochemical process. The pseudo-first order reaction rate constant of E-BiVO4-MoS2-Co3O4 film is 3.22 times higher than that of BiVO4. And its reaction rate constant in photoelectrocatalytic process is 14.5 times or 2 times that in photocatalytic or electrocatalytic process, respectively. The improved performance of E-BiVO4-MoS2-Co3O4 was attributed to the synergetic effects of the reduction of interfacial charge transfer resistance, the formation of oxygen vacancies and sub-stoichiometric metal oxides and higher separation efficiency of photogenerated electron-hole pairs. E-BiVO4-MoS2-Co3O4 is a promising composite material for pollutants removal.

The latency of peroxisomal catalase in terms of effectiveness factor for pancreatic and glioblastoma cancer cell lines in the presence of high concentrations of H2O2: Implications for the use of pharmacological ascorbate in cancer therapy

Previous research has identified variation in cancer cell line response to high levels of extracellular H2O2 (eH2O2) exposure. This directly contributes to our understanding cellular efficacy of pharmacological ascorbate (P-AscH-) therapy. Here we investigate the factors contributing to latency of peroxisomal catalase of a cell and the importance of latency in evaluating cell exposure to eH2O2. First, we develop a mathematical framework for the latency of catalase in terms of an effectiveness factor, ηeff, to describe the catalase activity in the presence of high levels of eH2O2. A simplified relationship emerges, ηeff=3mp/(k2CCatprp) when mprp/Dij≪1, where mp,rp, and k2CCatp are the experimentally determined peroxisome permeability, average peroxisome radius, and the pseudo first-order reaction rate constant, respectively. CCatp is the catalase concentration in the peroxisome and k2=1.7x107M−1s−1. Next, previously published parameters are used to determine the latency effect of the cell lines: normal pancreatic cells (H6c7), pancreatic cancer cells (MIA PaCa-2), and glioblastoma cells (LN-229, T98G, and U-87), all which vary in their susceptibility to exposure to high eH2O2. The results show that effectiveness is not significantly different except for the most susceptible, MIA PaCa-2 cell line, which is higher when compared to all other cell lines. This result is counterintuitive and further implies that latency, as a single parameter, is ineffective in forecasting cell line susceptibility to P-AscH- therapy equivalent eH2O. Thus, further research remains necessary to identify why cancer cells vary in susceptibility to P-AscH- therapy.

Significant enhancement of photo-Fenton degradation of ofloxacin over Fe-Dis@Sep due to highly dispersed FeC6 with electron deficiency

An efficient strategy for enhancing iron efficiency in heterogeneous Fenton reaction via the pyrolysis of ferrocene chemically modified sepiolite (Sep) was proposed in this study. Highly dispersed FeC6 on sepiolite (Fe-Dis@Sep) was synthesized as an efficient photo-Fenton catalyst for the visible light degradation of ofloxacin (OFX). It exhibits an excellent Fenton activity and stability towards OFX degradation. The pseudo-first order reaction rate constant of Fe-Dis@Sep was 5.1-fold higher than that of the supported catalyst with aggregated iron oxides prepared by traditional impregnation method (Fe-Agg@Sep). Based on TEM images and density functional theory (DFT) calculation, the enhanced Fenton activity of Fe-Dis@Sep was attributed to the unique incorporation of FeC6 on Sep via Si-O-C-Fe bond which not only favor the high dispersion of FeC6 with an electron deficiency but also promote Fe(III) to Fe(II) cycle via the formation of surface Fe-H2O2 complex. OH and O2- were identified as active species for OFX degradation in Fe-Dis@Sep-H2O2-Vis system. 98.7% of F and 97.0% of N in OFX was converted into F− and NO3− with a TOC removal efficiency of 89.35%. The possible degradation pathway of OFX was also proposed according to HPLC-MS results. Finally, the Fenton reaction mechanism over Fe-Dis@Sep was discussed.

Surface weak acid-base pair of FeOOH/Al2O3 for enhanced peroxymonosulfate activation in degradation of humic substances from water

Three oxides (SiO2, Al2O3 and FeOOH/Al2O3) made of earth-abundant elements (O, Si, Al and Fe) were prepared to activate peroxymonosulfate (PMS). Humic acid (HA) as a representative of humic substances in water was used to evaluate their PMS activation performance. FeOOH/Al2O3 exhibited the highest catalytic activity towards HA degradation with a pseudo-first order reaction rate constant of 0.0204 min−1, but almost no HA was degraded over SiO2. The results of Electron Spin Resonance (ESR) analysis and radical quenching experiments verified that singlet oxygen (1O2) was the sole reactive species for HA degradation. The relationship between surface properties of tested oxides and their PMS activation efficiency was investigated. According to the characterization results of powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), nitrogen adsorption-desorption experiment, temperature programmed desorption of adsorbed CO2 (CO2-TPD) and Pyridine-FTIR spectroscopy, the surface acid-base property was proven to be responsible to excellent PMS activation performance of FeOOH/Al2O3 for 1O2 generation. A dual-reaction-site mechanism was proposed and the contribution of weak Lewis acid site and weak basic site to HA degradation in PMS-FeOOH/Al2O3 system was discussed based on all the experimental results.

A resource-utilization way of the waste printed circuit boards to prepare silicon carbide nanoparticles and their photocatalytic application.

A resource-utilization strategy of the waste PCBs was developed: preparation of high value-added silicon carbide (SiC) nanoparticles using the waste PCBs as both silica and carbon precursors. The preparation process contained three optimized steps: acid wash pretreatment with 3 mol L-1 nitric acid at 60 °C for 96 h, low-temperature pyrolysis at 500 °C to allow the epoxy resin to decompose into carbon, and high-temperature pyrolysis at 1600 °C (in situ carbothermal reduction) to gain pure SiC nanoparticles. The pseudo first-order reaction rate constant (k) of the p-n heterojunction of SiC/TiO2 towards the photocatalytic degradation of methylene blue was 0.0219 min-1, 3.42 and 3.98 times that of TiO2 and no acid washed-SiC/TiO2, respectively.

Ciprofloxacin degradation in UV/chlorine advanced oxidation process: Influencing factors, mechanisms and degradation pathways

Ciprofloxacin (CIP) is a widely used third generation fluoroquinolone antibiotics, and has been often detected in wastewater treatment plants. Finding an effective way to remove them from wastewater is of great concern. Ultraviolet (UV)/chlorine advanced oxidation process (AOP) has many advantages in micropollutant removal. In this study, CIP degradation in UV/chlorine process was investigated. Only 41.2% of CIP was degraded by UV photolysis and 30.5% by dark chlorination in 30 min, while 98.5% of CIP was degraded by UV/chlorine process in 9 min. HCO3− had markedly inhibition, NO3− and SO42- had slight inhibition, and Cl− had a marginal inhibition on CIP degradation in UV/chlorine system. The degradation of CIP in UV/chlorine process was mainly attributed to the attack of reactive species. The relative contributions of hydrated electrons (eaq), hydroxyl radicals (HO), chlorine atoms (Cl), and UV photolysis were investigated. Under neutral condition in aqueous solution, CIP degradation had highest pseudo first-order reaction rate constant, in which eaq had the highest contribution, followed by Cl, HO, and UV photolysis. The intermediates and byproducts were identified and the degradation pathway was proposed. The total organic chlorine (TOCl) and biotoxicity were further assessed. CIP and natural organic matters (NOMs) were removed efficiently in real water. UV/chlorine showed the potential for the wastewater treatment containing CIP.

Implementation of continuously electro-generated Fe3O4 nanoparticles for activation of persulfate to decompose amoxicillin antibiotic in aquatic media: UV254 and ultrasound intensification

In the present investigation, the treatment of amoxicillin (AMX)-polluted water by the activated persulfate (PS) was considered. As a novel research, continuously electro-generated magnetite (Fe3O4) nanoparticles (CEMNPs) were utilized as the activator of PS in an electrochemical medium. The PS/CEMNPs displayed a remarkable enhancement in the decomposition of AMX molecules up to 72.6% compared with lonely PS (24.8%) and CEMNPs (13.4%). On the basis of pseudo-first order reaction rate constants, the synergy percent of about 70% was achieved due to the combination of PS with CEMNPs. The adverse influence of free radical-scavenging compounds on the efficiency of the PS/CEMNPs process was in the following order: carbonate < chloride < tert-butyl alcohol < ethanol. Overall, these results proved the main role of free radical species in degrading AMX. The implementation of ultrasound (US) enhanced the performance of the PS/CEMNPs process. Nevertheless, the highest degradation efficiency of about 94% was achieved when UV254 lamp was joined the PS/CEMNPs system. Under UV254 and US irradiation, the results showed significant potential of the PS/CEMNPs process for degrading AMX antibiotic and generating low toxic effluent based on the activated sludge inhibition test. However, more time is needed to achieve the acceptable mineralization.

Aqueous photodegradation of substituted chlorobenzenes: Kinetics, carbon isotope fractionation, and reaction mechanisms

Substituted chlorobenzenes are the basic substructure of many surface water contaminants. In this study, the isotope fractionation and reaction mechanisms involved during the aqueous direct and indirect photodegradation of CH3-, Cl-, and NO2- substituted chlorobenzenes were investigated in laboratory experiments. Only 4-nitrochlorobenzene showed slow but isotopically fractionating direct photolysis. During indirect photodegradation using UV/H2O2-generated OH radicals, the pseudo first-order reaction rate constants increased in the order of the NO2- < Cl- < CH3- substituted chlorobenzenes. The most pronounced carbon enrichment factors were observed for nitrochlorobenzenes (up to −4.8 ± 0.5‰), whereas the lowest were for chlorotoluenes (≤−1.0 ± 0.1‰). As the substituents became more electron-withdrawing, the activation energy barrier increased, leading to slower reaction rates, and the transition state changed to a more symmetrical or less reactant-like structure, resulting in larger apparent kinetic isotope effects. The results suggest that the rate-determining step in the reaction with OH radicals was the addition of the electrophile to the benzene ring. Even though further research is needed to quantify isotope fractionation during other transformation processes, these results showed evidence that compound specific isotope analysis can be used as a diagnostic tool for the fate of substituted chlorobenzenes in water.