Ultrasonic-assisted photocatalytic degradation of various organic contaminants using ZnO supported on a natural polymer of sporopollenin.

Water resource pollution by organic contaminants is an environmental issue of increasing concern. Here, sporopollenin/zinc oxide (SP/ZnO) was used as an environmentally friendly and durable catalyst for sonophotocatalytic treatment of three organic compounds: direct blue 25 (DB 25), levofloxacin (LEV), and dimethylphtalate (DMPh). The resulting catalyst had a 2.65 eV bandgap value and 9.81 m2/g surface area. The crystalline structure and functional groups of SP/ZnO were confirmed by X-ray diffraction (XRD) and Fourier transforms infrared spectroscopy (FTIR) analyses. After 120 min of the sonophotocatalysis, the degradation efficiencies of DB 25, LEV, and DMPh by SP/ZnO were 86.41, 75.88, and 62.54%, respectively, which were higher than that of the other investigated processes. The role of reactive oxygen species were investigated using various scavengers, enhancers, photoluminescence, and o-phenylenediamine. Owing to its stability, the catalyst exhibited good reusability after four consecutive cycles. In addition, the high integrity of the catalyst was confirmed by scanning electron microscopy (SEM), XRD, and FTIR analyses. After four consecutive examinations, the leaching of zinc in the aqueous phase was < 3 mg/L. Moreover, gas chromatography-mass spectrometry (GC-MS) analyses indicated that the contaminants were initially converted into cyclic compounds and then into aliphatic compounds, including carboxylic acids and animated products. Thus, this study synthesized an environmentally friendly and reusable SP/ZnO composite for the degradation of various organic pollutants using a sonophotocatalytic process.

Solubility and Decomposition of Organic Compounds in Subcritical Water.

In this article, studies on organic solubility and stability in subcritical water reported during the past 25 years have been reviewed. Data on the solubility and decomposition of organic compounds in subcritical water, a green solvent, are needed in environmental remediation, chemistry, chemical engineering, medicine, polymer, food, agriculture, and many other fields. For solubility studies, the experimental systems used to measure solubility, mathematical equations derived and applied for the modeling of the experimentally determined solubility data, and the correlation between the predicated and experimental data have been summarized and discussed. This paper also reviewed organic decomposition under subcritical water conditions. In general, the solubility of organics is significantly enhanced with increasing water temperature. Likewise, the percentage of organic decomposition also increases with higher temperature.

Degradation of emerging contaminant coumarin based on anodic oxidation, electro-Fenton and subcritical water oxidation processes.

The degradation of emerging contaminant coumarin was separately investigated in anodic, electro-Fenton and subcritical water oxidation processes. With respect to the anodic and electro-Fenton oxidation, the influence of constant current, treatment time and initial concentration of coumarin was studied. Regarding subcritical water oxidation, the effect of the oxidant concentration, temperature, treatment time and initial coumarin concentration was investigated. In anodic and electro-Fenton oxidation processes, coumarin degradation proceeded in a similar manner, achieving 99% degradation, after 180 min at a constant current of 200 mA. In both set-ups, further increasing the applied current lowered the degradation efficiency due to the formation of by-products and the increasing occurrence of side-reactions. The highest degradation of 88% was achieved in subcritical conditions, specifically at 200 °C, using 150 mM H2O2 and after 37.5 min of treatment. Under subcritical conditions, temperature was the most prominent parameter, followed by the H2O2 concentration. Under all methodologies, increasing treatment time had a small positive effect on coumarin degradation, indicating that time is not the most influential parameter. A comparison of the three methodologies in terms of performance as well as energy consumption and simplicity of operation highlighted the advantages of subcritical water oxidation.

CoFe2O4 nanoparticles decorated onto graphene oxide and graphitic carbon nitride layers as a separable catalyst for ultrasound-assisted photocatalytic degradation of Bisphenol-A.

The advanced oxidation process (AOP) through ultrasound-assisted photocatalytic degradation has attracted much attention in removing emerging contaminants. Herein, CoFe2O4-GO and CoFe2O4-g-C3N4 nanocomposites were synthesized using the ultrasound-assisted co-precipitation method. TEM, XRD, XPS, EDS, SEM, and FT-IR techniques characterized the structural, morphological, and chemical properties of the synthesized nanocomposites. The analyses showed that CoFe2O4 structure was nano-sized and distributed more homogeneously in graphene oxide (GO) layers with oxygenated functional groups than graphitic carbon nitride (g-C3N4). While the efficiency of composite catalysts, as photocatalysts, for degradation of bisphenol-A (BPA) was low in the visible region in the presence of persulfate, their catalytic efficacy was higher with sonolytic activation. The addition of persulfate as an oxidant remarkably enhanced the target pollutant degradation and TOC removal of BPA solution. Both composite catalysts showed 100 % BPA removal with the synergistic effect of visible region photocatalytic oxidation and sonocatalytic oxidation in the presence of persulfate at pH 6.8. In ultrasound-assisted photocatalytic oxidation of BPA, the highest mineralization efficiencies were obtained at 2 h treatment time, pH 6.8, 16 mM PS, catalyst dosages of 0.1 g/L CoFe2O4-GO, and 0.4 g/L CoFe2O4-g-C3N4 as 62 % and 55 %, respectively. An effective catalyst was obtained by reducing e-/h+ recombination and charge transfer resistance by decorating the GO layers with CoFe2O4.

Comparative degradation of 5-fluorouracil in aqueous solution by using H2O2-modified subcritical water, photocatalytic oxidation and electro-Fenton processes.

This study investigated the degradation of the antineoplastic agent 5-fluorouracil (5-FU) widely applied to treat different cancers using different advanced oxidation processes such as electro-Fenton (EF), photocatalysis with TiO2, and H2O2-modified subcritical water oxidation. The treatment with the EF process was the most efficient compared to others. Interestingly, in the EF process, the oxidative degradation of 5-FU behaved differently depending on the anode used. At low currents (20 and 40 mA), Pt and DSA anodes performed better than BDD and Ti4O7 anodes. In contrast, at the higher current of 120 mA, the production of heterogeneous hydroxyl radicals (M(•OH)) became important and contributed significantly to the oxidation of 5-FU in addition to homogeneous •OH generated in the bulk solution. These latter have high O2-evolution overpotential leading to the high amount of physisorbed M(•OH) compared to Pt and DSA. The oxidative degradation of 5-FU was then performed by titanium dioxide-based photocatalytic oxidation and subcritical water oxidation processes, both of which showed a lower degradation efficiency and failed to achieve complete mineralization. Finally, a comparison was performed in laboratory-scale, taking into account the following performance indicators: the degradation efficiency, the mineralization power, the cost of equipment and reagents, and the energy required for the treatment of 5-FU.

Preparation and Application of a Hydrochar-Based Palladium Nanocatalyst for the Reduction of Nitroarenes.

In the present study, a novel heterogeneous catalyst was successfully fabricated through the decoration of palladium nanoparticles on the surface of designed Fe3O4-coffee waste composite (Pd-Fe3O4-CWH) for the catalytic reduction of nitroarenes. Various characterization techniques such as XRD, FE-SEM and EDS were used to establish its nano-sized chemical structure. It was determined that Pd-Fe3O4-CWH is a useful nanocatalyst, which can efficiently reduce various nitroarenes, including 4-nitrobenzoic acid (4-NBA), 4-nitroaniline (4-NA), 4-nitro-o-phenylenediamine (4-NPD), 2-nitroaniline (2-NA) and 3-nitroanisole (3-NAS), using NaBH4 in aqueous media and ambient conditions. Catalytic reactions were monitored with the help of high-performance liquid chromatography. Additionally, Pd-Fe3O4-CWH was proved to be a reusable catalyst by maintaining its catalytic activity through six successive runs. Moreover, the nanocatalyst displayed a superior catalytic performance compared to other catalysts by providing a shorter reaction time to complete the reduction in nitroarenes.

Degradation, solubility and chromatographic studies of Ibuprofen under high temperature water conditions.

Ibuprofen (IBP) is an emerging environmental contaminant having low aqueous solubility which negatively affects the application of advanced oxidation and adsorption processes. It was determined that as the temperature increased to 473 K, the mole fraction solubility increased considerably from 0.02 × 10-3 to 212.88 × 10-3 (10600-fold). Calculation of the thermodynamic properties indicated an endothermic process, ΔsolH > 0, with relatively high ΔsolS values. Spectroscopic, thermal and chromatographic analyses established the IBP stability at subcritical conditions. In the second part of the study, the degradation of IBP in H2O2-modified subcritical was studied and the effect of each process variable was investigated. The optimum degradation of 88% was reached at an IBP concentration of 15 mg L-1, temperature of 250 °C, 105 min treatment time and 250 mM H2O2. The process was optimized by response surface methodology and a mathematical model was proposed and validated. Temperature was determined as the most influential parameter, followed by H2O2 concentration. At temperatures higher than 230 °C, a small but noticeable reduction in degradation % suggested that the OH· radicals are consumed at a higher rate than they are produced, through side reactions with other radicals and/or IBP by-products. Finally, potential by-products were determined by gas chromatographic-mass spectrometric analysis and potential by-products were proposed.

Stability and Extraction of Vanillin and Coumarin under Subcritical Water Conditions.

In order to facilitate the development of the green subcritical water chromatography technique for vanillin and coumarin, the stability of the compounds under subcritical water conditions was investigated in this work. In addition, their extraction from natural products was also studied. The stability experiments were carried out by heating the mixtures of vanillin and water or coumarin and water at temperatures ranging from 100 °C to 250 °C, while subcritical water extractions (SBWE) of both analytes from vanilla beans and whole tonka beans were conducted at 100 °C to 200 °C. Analyte quantification for both stability and extraction studies was carried out by HPLC. After heating for 60 min, vanillin was found to be stable in water at temperatures up to 250 °C. While coumarin is also stable at lower temperatures such as 100 °C and 150 °C, it undergoes partial degradation after heating for 60 min at 200 °C and higher. The results of this stability study support green subcritical water chromatographic separation and extraction of vanillin and coumarin at temperatures up to 150 °C. The SBWE results revealed that the extraction efficiency of both analytes from vanilla beans and tonka beans is significantly improved with increasing temperature.

Synthesis of ZrO2 nanoparticles on pumice and tuff for sonocatalytic degradation of rifampin.

ZrO2-pumice and ZrO2-tuff nanocomposites were synthesized via a modified sol-gel method and used as efficient catalysts for sonocatalytic degradation of rifampin (RIF). The physico-chemical properties of the prepared catalysts were examined using XRF, SEM, EDX, FT-IR and BET analyses and compared to pure pumice and tuff samples. Subsequently, the efficacy of catalysts in degradation of RIF was assessed under various experimental conditions. Both ZrO2-pumice and ZrO2-tuff (1.5 g L-1) exhibited promising catalytic activity for sonocatalytic degradation of RIF at its initial concentration of 20 mg L-1, natural pH and under ultrasonic irradiation power of 300 W. In this condition, about 95% and 83% of RIF was removed through US/ZrO2-pumice and US/ZrO2-tuff processes, respectively. Furthermore, the influence of the addition of a number of scavengers, enhancers and gases on the degradation of RIF was studied. The pronounced degradation effectiveness of the catalysts under ultrasound irradiation could be assigned to their synergetic ability to produce reactive species and subsequent radical reactions. The intermediate products formed in the solution from degradation of RIF were also identified and a decomposition pathway was proposed using GC-MS, COD, TOC and IC analyses.

Sonocatalytic degradation of an anthraquinone dye using TiO2-biochar nanocomposite.

TiO2-biochar (TiO2-BC) nanocomposite was synthesized by sol-gel method. The characteristics of the prepared nanocomposite were examined using X-ray fluorescence, scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy and N2 adsorption-desorption analysis. The performance of synthesized TiO2-BC nanocomposite as efficient sonocatalyst was studied for the degradation of Reactive Blue 69 (RB69). Sonocatalytic degradation of RB69 in the presence of TiO2-BC nanocomposite could be explained by the mechanisms of hot spots and sonoluminescence. The optimized values for main operational parameters were determined as pH of 7, TiO2-BC dosage of 1.5g/L, RB69 initial concentration of 20mg/L and ultrasonic power of 300W. Furthermore, the effect of OH, h+ and O2- scavengers on the RB69 degradation efficiency was studied. Gas chromatography-mass spectroscopy analysis was used to identify intermediate compounds formed during the RB69 degradation. The results of repeated applications of TiO2-BC in the sonocatalytic process verified its stability in long-term usage.

Sonocatalytic degradation of Reactive Yellow 39 using synthesized ZrO2 nanoparticles on biochar.

ZrO2-biochar (ZrO2-BC) nanocomposite was prepared by a modified sonochemical/sol-gel method. The physicochemical properties of the prepared nanocomposite were evaluated using scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray fluorescence, Fourier transform infrared spectroscopy and Brunauer-Emmett-Teller model. The sonocatalytic performance of ZrO2-BC was investigated in sonochemical degradation of Reactive Yellow 39 (RY39). The high observed sonocatalytic activity of the ZrO2-BC sample could be interpreted by the mechanisms of sonoluminescence and hot spots. Parameters including ZrO2-BC dosage, solution pH, initial RY39 concentration and ultrasonic power were selected as the main operational parameters and their influence on RY39 degradation efficiency was examined. A 96.8% degradation efficiency was achieved with a ZrO2-BC dosage of 1.5g/L, pH of 6, initial RY39 concentration of 20mg/L and ultrasonic power of 300W. In the presence of OH radical scavengers, RY39 degradation was significantly inhibited, providing evidence for the key role of hydroxyl radicals in the process. The sonodegradation intermediates were identified using gas chromatography-mass spectroscopy and the possible decomposition route was proposed.

Ultrasound-assisted removal of Acid Red 17 using nanosized Fe3O4-loaded coffee waste hydrochar.

The Fe3O4-loaded coffee waste hydrochar (Fe3O4-CHC) was synthesized using a simple precipitation method. The as-prepared adsorbent was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and Fourier transform infrared spectroscopy (FT-IR). The EDX analysis indicated the presence of Fe in the structure of Fe3O4-CHC. The specific surface area of hydrochar increased from 17.2 to 34.7m2/g after loading of Fe3O4 nanoparticles onto it. The prepared Fe3O4-CHC was used for removal of Acid Red 17 (AR17) through ultrasound-assisted process. The decolorization efficiency decreased from 100 to 74% with the increase in initial dye concentration and from 100 to 91 and 85% in the presence of NaCl and Na2SO4, respectively. The synthesized Fe3O4-CHC exhibited good stability in the repeated adsorption-desorption cycles. The high correlation coefficient (R2=0.997) obtained from Langmuir model indicated that physical and monolayer adsorption of dye molecules occurred on the Fe3O4-CHC surface. Furthermore, the by-products generated through the degradation of AR17 was identified by gas chromatography-mass spectrometry analysis.

Green Chromatographic Separation of Coumarin and Vanillins Using Subcritical Water as the Mobile Phase.

Pure water was used as the eluent for separation of coumarin, vanillin and ethyl vanillin at temperatures ranging from 100 to 200°C using a homemade subcritical water chromatography (SBWC) system. Chromatographic separations were performed on five commercial columns including XTerra MS C18, XBridge C18, Zorbax RRHD Eclipse Plus, Zorbax SB-Phenyl and Zorbax SB-C18 columns. The retention time of all three solutes decreased with increasing water temperature. The shortest retention time among all acceptable separations, less than 4 min, was achieved on the Zorbax SB-C18 column at 200°C. While separations on the XTerra MS C18 column resulted in fronting peaks and a degradation peak from ethyl vanillin on the Zorbax RRHD Eclipse Plus column was observed, all three other columns yielded reasonable separations under SBWC conditions. In addition to separation of the standard test mixture, separation of coumarin contained in a skincare cream sample was also carried out using SBWC.

Degradation of Acid Red 274 using H2O2 in subcritical water: application of response surface methodology.

In this research, the degradation of Acid Red 274 (AR 274) was investigated under subcritical water conditions using H(2)O(2), which led to the oxidative degradation of Acid Red 274 up to its 80% of mineralization. The Box-Behnken design matrix and response surface methodology (RSM) were applied in designing the experiments for evaluating the interactive effects of the three most important operating variables. Thus, the interactive effects of temperature (100-250°C), oxidant (H(2)O(2)) concentration (50-250 mM), and time (30-60 min.) on the degradation of AR 274 were investigated. A total of 17 experiments were conducted in this research, and the analysis of variance (ANOVA) indicated that the proposed quadratic model could be used for navigating the design space. The proposed model was essentially in accordance with the experimental case with correlation coefficient R(2)=0.9930 and Adj-R(2)=0.9839, respectively. The results confirmed that RSM based on the Box-Behnken design was a compatible method for optimizing the operating conditions of AR 274 degradation.

Degradation of acid red 97 dye in aqueous medium using wet oxidation and electro-Fenton techniques.

Degradation of the acid red 97 dye using wet oxidation, by different oxidants, and electro-Fenton systems was investigated in this study. The oxidation effect of different oxidants such as molecular oxygen, periodate, persulfate, bromate, and hydrogen peroxide in wet oxidation system was compared. Mineralization of AR97 with periodate appeared more effective when compared with that of the other oxidants at equal initial concentration. When 5 mM of periodate was used, at the first minute of the oxidative treatment, the decolorization percentage of AR97 solution at 150 and 200 degrees C reached 88 and 98%, respectively. The total organic carbon removal efficiency at these temperatures also reached 60 and 80%. The degradation of AR97 was also studied by electro-Fenton process. The optimal current value and Fe(2+) concentration were found to be 300 mA and 0.2 mM, respectively. The results showed that electro-Fenton process can lead to 70 and 95% mineralization of the dye solution after 3 and 5h giving carboxylic acids and inorganic ions as final end-products before mineralization. The products obtained from degradation were identified by GC/MS as 1,2-naphthalenediol, 1,1'-biphenyl-4-amino-4-ol, 2-naphthalenol diazonium, 2-naphthalenol, 2,3-dihydroxy-1,4-naphthalenedion, phthalic anhydride, 1,2-benzenedicarboxylic acid, phthaldehyde, 3-hydroxy-1,2-benzenedicarboxylic acid, 4-amino-benzoic acid, and 2-formyl-benzoic acid.

Oxidative degradations of reactive blue 4 dye by different advanced oxidation methods.

The degradations of an anthraquinone dye, the reactive blue 4 (RB4), were studied by wet air oxidation (WAO), wet peroxide oxidation (WPO), photocatalytic oxidation, and electro-Fenton (EF) advanced oxidation. The RB4 oxidation was evaluated by the decrease in total organic carbon (TOC) content and concentration. The most efficient method for mineralization of RB4 was WPO, but in all methods TOC removal efficiency was above 75% after 60 min of treatment.

Terpene degradation and extraction from basil and oregano leaves using subcritical water.

In the first part of this study, the stability of five terpenes (alpha-pinene, limonene, camphor, citronellol, and carvacrol) under subcritical water conditions was investigated. The stability studies were carried out at four different temperatures (100, 150, 200, and 250 degrees C) with two different heating times (30 and 300 min). When water temperature was increased, the degradation of terpenes became more serious. Prolonged exposure time to each heating temperature also caused decreased terpene stability. The terpene recoveries were determined by conducting subcritical water extraction of sand spiked with terpenes. The recoveries are typically around 70 to 80% for extractions at 100 degrees C. Terpene recoveries were decreased with increasing water temperature due to poorer stability of terpenes. After the degradation and recovery studies, basil and oregano leaves were extracted using water at both 100 and 150 degrees C. The concentrations of each individual terpene in the water extract generally ranged from trace quantity to 65 microg terpene/g herb. However, the concentration of carvacrol in the oregano-water extract at 150 degrees C was found to be as high as 4270 microg carvacrol/g oregano.