Green synthesis of manganese ferrite magnetic nanoparticle and its modification with metallic-organic frameworks for the tetracycline adsorption from aqueous solutions: A mathematical study of kinetics, isotherms, and thermodynamics.

In the current investigation, MnFe2O4/ZIF-8 nanocomposite was generated as a magnetic nanoadsorber using the extract of Dracocephalum plant and characterized by XRD, FTIR, VSM, BET, FESEM, EDS-mapping, TEM, XPS, TPD-NH3, and TGA analyses. Also, to determine its efficiency in the adsorption process of tetracycline, the effect of pH (3-9), nanocomposite dose (0.025-2 g/L), initial pollutant concentration (5-100 mg/L), contact time (5-200 min), and temperature (5-50 °C) were studied. The results of the morphological properties of the magnetic nanocomposite confirmed the spherical shape of this nanoadsorber with an average size of 54 ± 31 nm. BET analysis showed that modification of MnFe2O4 material with ZIF-8 as a new nanoadsorber leads to excellent modification of SBET (143.8 m2/g) and VTotal (0.44 cm3/g). The highest removal efficiency of tetracycline in optimal conditions (pH = 7, contact time = 120 min, nanocomposite dose = 1.5 g/L, and temperature = 20 °C for a tetracycline concentration of 20 mg/L) was 90.11%. As the temperature increased, the removal efficiency increased from 40.46% to 95.06% during 120 min, which indicates that the adsorption reaction is endothermic. In addition, the data obtained from the isotherms of Langmuir (R2 = 0.958), Freundlich (R2 = 0.534), and Temkin (R2 = 0.747) showed that the tetracycline adsorption is monolayer and on the homogeneous surface of the synthesized magnetic nanoadsorber. The elimination process of tetracycline by nanoadsorber followed the pseudo-second order model (R2 = 0.998). Investigating the effect of interfering ions also confirmed the decrease in the adsorption efficiency. Also, the investigation of the reusability of the synthesized magnetic nanoadsorber in tetracycline adsorption indicates that after eight cycles, the efficiency decreases by %16.51. According to the results, the magnetic nanocomposite synthesized in this work can be a suitable and economical adsorber for the removal of tetracycline from aqueous environments.

Photocatalytic decomposition of metronidazole by zinc hexaferrite coated with bismuth oxyiodide magnetic nanocomposite: Advanced modelling and optimization with artificial neural network.

The objective of the present study was to employ a green synthesis method to produce a sustainable ZnFe12O19/BiOI nanocomposite and evaluate its efficacy in the photocatalytic degradation of metronidazole (MNZ) from aqueous media. An artificial neural network (ANN) model was developed to predict the performance of the photocatalytic degradation process using experimental data. More importantly, sensitivity analysis was conducted to explore the relationship between MNZ degradation and various experimental parameters. The elimination of MNZ was assessed under different operational parameters, including pH, contaminant concentration, nanocomposite dosage, and retention time. The outcomes exhibited high a desirability performance of the ANN model with a coefficient correlation (R2) of 0.99. Under optimized circumstances, the MNZ elimination efficiency, as well as the reduction in chemical oxygen demand (COD) and total organic carbon (TOC), reached 92.71%, 70.23%, and 55.08%, respectively. The catalyst showed the ability to be regenerated 8 times with only a slight decrease in its photocatalytic activity. Furthermore, the experimental data obtained demonstrated a good agreement with the predictions of the ANN model. As a result, this study fabricated the ZnFe12O19/BiOI nanocomposite, which gave potential implication value in the effective decontamination of pharmaceutical compounds.

Statistical computational optimization approach for photocatalytic-ozonation decontamination of metronidazole in aqueous media using CuFe2O4/SiO2/ZnO nanocomposite.

The increasing use of pharmaceuticals and the ongoing release of drug residues into the environment have resulted in significant threats to environmental sustainability and water safety. In this sense, developing a robust and easy-recovered magnetic nanocomposite with eminent photocatalytic activity is very imperative for detoxifying pharmaceutical compounds. Herein, a systematic study was conducted to investigate the photocatalytic ozonation for eliminating metronidazole (MET) from aqueous media utilizing the CuFe2O4/SiO2/ZnO heterojunction under simulated sunlight irradiation. The composite material was fabricated by a facile hydrothermal method and diagnosed by multiple advanced analytical techniques. Modelling and optimization of MET decontamination by adopting the central composite design (CCD) revealed that 90 % of MET decontamination can be achieved within 120 min of operating time at the optimized circumstance (photocatalyst dose: 1.17 g/L, MET dose: 33.20 mg/L, ozone concentration: 3.99 mg/min and pH: 8.99). In an attempt to scrutinize the practical application of the CuFe2O4/SiO2/ZnO/xenon/O3 system, roughly 56.18% TOC and 73% COD were removed under the optimized operational circumstances during 120 min of degradation time. According to the radical quenching experiments, hydroxyl radicals (HO•) were the major oxidative species responsible for the elimination of MET. The MET degradation rate maintained at 83% after seven consecutive runs, manifesting the efficiency of CuFe2O4/SiO2/ZnO material in the MET removal. Ultimately, the photocatalytic ozonation mechanism over the CuFe2O4/SiO2/ZnO heterojunction of the fabricated nanocomposites was rationally proposed for MET elimination. In extension, the results drawn in this work indicate that integrating photocatalyst and ozonation processes by the CuFe2O4/SiO2/ZnO material can be applied as an efficient and promising method to eliminate tenacious and non-biodegradable contaminants from aqueous environments.

Efficient purification of aqueous solutions contaminated with sulfadiazine by coupling electro-Fenton/ultrasound process: optimization, DFT calculation, and innovative study of human health risk assessment.

In the current work, the hybrid process potential of ultrasound (US) and electro-Fenton (EF), named sono-electro-Fenton (SEF), was fully investigated for sulfadiazine (SDZ) degradation. The decontamination in the integration approach was revealed to be greater than in individual procedures, i.e., EF process (roughly 66%) and US process (roughly 15%). The key operating process factors (i.e., applied voltage, H2O2 content, pH, initial concentration of SDZ, and reaction time) affecting SDZ removal were evaluated and optimized using Box-Behnken Design (BBD). In addition, an adaptive neuro-fuzzy inference system (ANFIS) as an efficient predictive model was applied to forecast the decontamination efficiency of SDZ through the SEF process based on the same findings produced from BBD. The results revealed that the predictability of SDZ elimination by the ANFIS and BBD approaches exhibited an excellent agreement (a greater R2 of 0.99%) among the both models. Density functional theory was also employed to forecast the plausible decomposition elucidation by the bond-breaking mechanism of organic substances. Plus, the main side products of SDZ degradation during the SEF process were tracked. Eventually, the non-carcinogenic risk assessment of different samples of natural water containing SDZ that was treated by adopting US, EF, and SEF processes was examined for the first time. The findings indicated that the non-carcinogenic risk (HQ) values of all the purified water sources were computed in the permissible range.

Statistical modeling optimization for antibiotics decomposition by ultrasound/electro-Fenton integrated process: Non-carcinogenic risk assessment of drinking water.

The present work proposes an ultrasound (US) assisted electro-Fenton (EF) process for eliminating penicillin G (PNG) and ciprofloxacin (CIP) from aqueous solutions and the process was further optimized by response surface methodology (RSM)- Box-Behnken design (BBD). The impact of pH, hydrogen peroxide (H2O2) concentration, applied voltage, initial pollutant concentration, and operating time were studied. The capability application of the electro-Fenton (EF) and US processes was compared separately and in combination under the optimum conditions of pH of 4, a voltage of 15 V, the initial antibiotic concentration of 20.7 mg/L, H2O2 concentration of 0.8 mg/L, and the operating time of 75 min. The removal efficiency of PNG and CIP using the sono-electro-Fenton (SEF) process, as the results revealed, was approximately 96% and 98%, respectively. The experiments on two scavengers demonstrated that ⦁OH contributes significantly to the CIP and PNG degradation by SEF, whereas ⦁O-2 corresponds to only a negligible amount. The total organic carbon (TOC) and chemical oxygen demand (COD) analyses were used to assess the mineralization of CIP and PNG. The efficiency of COD and TOC removal was reached at 73.25% and 62.5% for CIP under optimized operating circumstances, and at 61.52% and 72% for PNG, respectively. These findings indicate that a sufficient rate of mineralization was obtained by SEF treatment for the mentioned pollutants. The reaction kinetics of CIP and PNG degradation by the SEF process were found to follow a pseudo-first-order kinetic model. In addition, the human health risk assessment of natural water containing CIP and PNG that was purified by US, EF, and SEF processes was done for the first time. According to the findings, the non-carcinogenic risk (HQ) caused by drinking purified water by all three systems was calculated in the acceptable range. Thus, SEF is a proper system to remove various antibiotics in potable water and reduces their human health risks.

Efficient photocatalytic degradation of metronidazole in wastewater under simulated sunlight using surfactant- and CuS-activated zeolite nanoparticles.

Hexadecyltrimethylammonium-bromide-activated zeolite nanoparticles coated with copper sulfide (ZEO/HDTMA-Br/CuS) was evaluated as a photocatalyst under sunlight for the degradation of metronidazole (MET). The surface and structural characteristics of ZEO/HDTMA-Br/CuS and other materials used in this study were analyzed using field emission-scanning electron microscopy, Fourier transform infrared and ultraviolet-visible diffuse reflectance spectroscopies, X-ray diffraction, Brunauer-Emmett-Teller surface area and Barrett-Joyner-Halenda pore size and volume analyses, and pH of zero charge test. ZEO/HDTMA-Br/CuS exhibited excellent surface and structural catalytic properties. For a comprehensive study of the degradation process, several parameters, such as the pH (3-11), MET concentration (10-30 mg/L), ZEO/HDTMA-Br/CuS dose (0.005-0.1 g/L), reaction time (5-200 min), and H2O2 concentration (50-200 mg/L), were optimized. ZEO/HDTMA-Br/CuS achieved 100% degradation efficiency when 10 mg/L MET was used under the optimum conditions: pH = 7, ZEO/HDTMA-Br/CuS dose = 0.01 g/L, and reaction time = 180 min. The degradation efficiency increased when the concentration of H2O2 was increased from 50 to 150 mg/L and decreased with further increase to 200 mg/L, indicating that the efficiency of MET degradation highly depends on the concentration of H2O2 in an aqueous solution. The degradation kinetics analysis revealed that the degradation is of the pseudo first-order. Thus, ZEO/HDTMA-Br/CuS proved to be an exceptional catalyst for the photodegradation of MET in aqueous media.

Effect of UVC and UVA Photocatalytic Processes on Tetracycline Removal Using CuS-Coated Magnetic Activated Carbon Nanocomposite: A Comparative Study.

In this study, we synthesized a novel MAC nanocomposite using almond's green hull coated with CuS. The whole set of experiments have been conducted inside a batch (discontinuous reactor system) at room temperature. The effectiveness of different parameters in tetracycline removal pH (3, 5, 7, and 9), pollutant concentration (5-100 mg/L), nanocomposite dosage (0.025-1 g/L), and contact time (5-60 min) using newly synthesized nanocomposite were investigated. Based on the results, in the optimal conditions of pH = 9, nanocomposite dosage of 1 g/L, pollutant concentration of 20 mg/L, contact time of 60 min, and room temperature, 95% removal efficiency was obtained. In MAC/CuS/UVC process, the removal of COD and TOC were 76.89% and 566.84% respectively meanwhile, these values in MAC/CuS/UVA process were 74.19% and 62.11%, respectively. The results of nanocomposite stability and magnetic recovery illustrated that the removal efficiency was reduced by 1.5% in the presence of UVC and 5% in the presence of UVA lights during all six cycles. Therefore, this nanocomposite was highly capable of recycling and reuse. It can be concluded that considering the high potential of the synthesized nanocomposite, the photocatalytic efficiency of the MAC/CuS/UVC process in tetracycline synthesis was higher than MAC/CuS/UVA process.

Efficient oxidation/mineralization of pharmaceutical pollutants using a novel Iron (III) oxyhydroxide nanostructure prepared via plasma technology: Experimental, modeling and DFT studies.

High-performance novel iron oxyhydroxide (limonite) nanostructure, with improved surface reactive sites, was prepared via one-pot, eco-friendly, free precursor and cold glow discharge N2-plasma technique. Natural and plasma treated (PTNL/N2) limonite samples were characterized by FESEM, XPS, XRD, FTIR, AAS, EDX, BET/BJH and pHpzc to confirm the successful synthesis. Central composite design (CCD) and artificial neural network (ANN, topology of 4:8:1) methods were utilized to study the oxidation/mineralization of phenazopyridine (PhP) as a hazardous contaminant by heterogeneous catalytic ozonation process (HCOP). The obtained results indicated that PTNL/N2 had the highest catalytic performance in PhP degradation (98.6% in 40 min) and mineralization (80.4% in 120 min). The degradation mechanism in different processes was investigated by dissolved ozone concentration, various organic scavengers (BQ and TBA) and inorganic salts (NaNO3, NaCl, Na2CO3 and NaH2PO4). Moreover, reusability-stability, Fe and nitrogen (NO3- and NH4+) ions release were assessed during different AOPs. Furthermore, toxicity tests indicated that the HCOP using PTNL/N2 was able to detoxify the PhP solutions efficiently. Finally, Density Functional Theory (DFT) studies were employed to introduce the most plausible contaminant degradation pathway, reactive sites and byproducts. This research provided a new insight into the improvement of wastewater treatment studies by a combination of experiment and computer simulation.

Fabrication of novel magnetic CuS/Fe3O4/GO nanocomposite for organic pollutant degradation under visible light irradiation.

The magnetic nanocomposites composed of copper sulphide, iron oxide, and graphene oxide (CuS/Fe3O4/GO) were synthesized through a facile sol-gel combined with hydrothermal techniques for photodegradation of methylene blue (MB) as a model organic pollutant. The as-prepared samples were characterized by powder X-ray diffraction (XRD), vibrating sample magnetometer (VSM), differential reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), and energy dispersive X-ray analysis (EDX) and results confirmed successful synthesis of magnetic nanocomposite. Presence of Fe3O4 and GO in nanocomposite induced a synergistic effect in CuS performance as CS88F6G6 (i.e. 88% CuS, 6% Fe3O4, and 6% GO). The photocatalytic degradation efficiency of MB reached up to 90.3% after exposure to visible light irradiation for 80 min. The composite nanosheets are photostable, reusable, and magnetically recoverable, revealing potential application in removal of organic pollutants.

Adsorption-photocatalytic processes for removal of pentachlorophenol contaminant using FeNi3/SiO2/ZnO magnetic nanocomposite under simulated solar light irradiation.

The adsorption followed by photocatalytic degradation process was examined for the pentachlorophenol (PCP) removal from aqueous solution. These processes were accomplished by using FeNi3/SiO2/ZnO magnetic nanocomposite as an adsorbent-photocatalytic agent and under the irradiation of solar light. The magnetic nanocomposite used was first synthesized and then was characterized using transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), vibrating-sample magnetometer (VSM), and X-ray diffraction (XRD) spectroscopy. The PCP removal efficiency was tested for various factors, including pH, PCP concentration, and nanocomposite dose at different contact times. The characterization results of TEM, FE-SEM, and VSM analysis showed that the synthesized nanoparticles are amorphous and tend to agglomerate due to their high super-paramagnetic property. In addition, the EDX technique showed that the Zn and O elements had the highest weight percent in the synthesized nanocomposite, respectively. On the other hand, XRD analysis revealed that the crystalline size of the nanoparticles was about 42 nm. The kinetic of PCP degradation followed the pseudo-first-order model with R2 = 0.978. According to the results of the isotherm study, the adsorption of PCP onto the nanoparticles followed the Freundlich model. The results of adsorption-photocatalytic degradation experiments showed that 100% removal of PCP was obtained at optimum conditions of pH = 3, nanocomposite dose = 0.5 g/L, contact time = 180 min, and initial PCP concentration of 10 mg/L. Through the results obtained from this study, the adsorption process followed by solar light photocatalytic degradation process using FeNi3/SiO2/ZnO magnetic nanocomposite is found to be an efficacious treatment method for the removal of PCP contaminant from water and wastewater.

Photocatalytic degradation of penicillin G from simulated wastewater using the UV/ZnO process: isotherm and kinetic study.

PURPOSE: Pharmaceutical contaminants, including antibiotics, present in the environment, especially water resources, are a main concern for human and environmental health due to their stability and non-degradability. Accordingly, the purpose of this study was to investigate the photocatalytic removal of penicillin G antibiotic from simulated wastewater using a photocatalytic process [UV/ZnO] in an isotherm and kinetic study. METHODS: In the current research, the ZnO nanoparticles [ZnO NPs] were initially characterized by scanning electron microscope [SEM] and X-ray diffraction [XRD]. Then, its efficiency was investigated in the photocatalytic degradation process of penicillin G. The evaluated parameters in the adsorption process penicillin G antibiotic were pH [1-5], penicillin G concentration [10-30 mgL-1], NP dosage [0.5-4.5 gL-1] and contact time [5 to 200 min]. Then, the effect of pH [3, 5, 7, 9, 11, and], penicillin G concentration [10-30 mgL-1], NP dosage [0.01-1.5 gL-1] and contact time [5 to 200 min] in the photocatalytic degradation (UV/ZnO) was studied. The residual penicillin G concentration was measured using a spectrophotometery at a wavelength of 283 nm. RESULTS: The results indicated that the penicillin G removal efficiency of photocatalytic process [UV/ZnO] using ZnO was 74.65% at the concentration of 10 mgL-1, the pH value of 5, the ZnO NP dosage of 0.1 gL-1 and the contact time of 180 min, as well as the kinetics of degradation followed the pseudo-first-order kinetic model. CONCLUSION: It can be concluded that the use of this process is appropriate an effective for the removal of the antibiotic pollutants.

Correction to: Photocatalytic degradation of penicillin G from simulated wastewater using the UV/ZnO process: isotherm and kinetic study.

[This corrects the article DOI: 10.1007/s40201-020-00442-7.].

A comprehensive study on the application of FeNi3@SiO2@ZnO magnetic nanocomposites as a novel photo-catalyst for degradation of tamoxifen in the presence of simulated sunlight.

Pharmaceutical compounds at trace concentrations are found in the environment, especially in drinking water and food, posing significant negative effects on humans as well as on animals. This paper aimed to examine the diagnostic catalytic properties and efficacy of a novel synthesized photocatalyst, namely FeNi3@SiO2@ZnO magnetic nanocomposite, for the removal of tamoxifen (TMX) from wastewater under simulated sunlight. According to the results, it was found that TMX was completely degraded operating under optimized conditions (i.e. pH = 7, catalyst dose = 0.01 g/L, initial TMX concentration = 20 mg/L and reaction time = 60 min). The reaction kinetics of TMX degradation followed a pseudo-first order kinetics model. The final by-products from the TMX photodegradation were water, carbon dioxide, acetic acid, nitroacetic acid methyl ester, 2-methyl-2-pentenal, and 4-methyl-2-pentanol. In addition, the synthesized photocatalyst could successfully performed five consecutive photodegradation cycles. The obtained results revealed that the synthesized FeNi3@SiO2@ZnO magnetic nanocomposite holds a great potential to be applied as a photocatalyst for the degradation of TMX on an industrial scale.