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The increasing use of nanomaterials in consumer products is expected to lead to environmental contamination sometime soon. As water pollution is a pressing issue that threatens human survival and impedes the promotion of human health, the search for adsorbents for removing newly identified contaminants from water has become a topic of intensive research. The challenges in the recyclability of contaminated water continue to campaign the development of highly reusable catalysts. Although exfoliated 2D MXene sheets have demonstrated the capability towards water purification, a significant challenge for removing some toxic organic molecules remains a challenge due to a need for metal-based catalytic properties owing to their rapid response. In the present study, we demonstrate the formation of hybrid structure AuNPs@MXene (Mo2CTx) during the sensitive detection of Au nanoparticle through MXene sheets without any surface modification, and subsequently its applications as an efficient catalyst for the degradation of 4-nitrophenol (4-NP), methyl orange (MO), and methylene blue (MB). The hybrid structure (AuNPs@MXene) reveals remarkable reusability for up to eight consecutive cycles, with minimal reduction in catalytic efficiency and comparable apparent reaction rate constant (Kapp) values for 4-NP, MB, and MO, compared to other catalysts reported in the literature.

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4-Nitrophenol is a widely used emerging pollutant in various industries, including the production of agrochemicals, drugs, and synthetic dyes. Due to its potential environmental harmful effects, there is a need to study its reuse and removal from wastewater. This study used electrodialysis technology to separate 4-nitrophenol ions using a four-compartment stack. The effects of supporting electrolyte concentration, pH, voltages, and current density on the performance of electrodialysis for separating 4-nitrophenol were investigated. A high extraction percentage of 77% was achieved with low energy consumption (107 kWh kg-1) when high 4-nitrophenol flows and transport numbers were reached.

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The development of technologies capable of producing efficient and economically viable anodes is essential for the electrochemical treatment of water contaminated with complex organic pollutants. In this context, the use of ionic liquids as solvents to prepare mixed metal oxide (MMO) anodes has proven to be an up-and-coming alternative. Here, we analyze the influence of the temperature of calcination (300, 350, and 400 ºC) on the production of Ti(RuO2)0.8-(Sb2O4)0.2 anodes made using the thermal decomposition method using three ionic liquids (IL) as solvents: dipropyl ammonium acetate (DPA-Ac), dipropyl ammonium propionate (DPA-Pr), and dipropyl ammonium butyrate (DPA-Bu). The decomposition temperature for all IL, accessed by thermogravimetry, is below 200 ºC. Physical and electrochemical analyses demonstrate that the calcination temperature of the anodes is decisive for their durability and electrochemical properties. Anodes prepared with DPA-Bu at 350 ºC show higher stability (around 35 h) than those made with other ILs at temperatures of 300 and 400 ºC and improved results in terms of 4-NP mineralization, where 97% of TOC removal was achieved in 120 min. It could be verified that the calcination temperature and IL employed had a decisive influence on the characteristics of the presented anodes. Therefore, the anode prepared with DPA-Bu at 350 ºC is promising for application in the degradation of organic compounds.

RESUMO

Herein, we demonstrate a single-step synthesis of simple copper-doped borophosphate glasses and their unusual use for catalytic reduction of nitro groups from the aromatic nitro compounds. The copper-doped glasses were evaluated as an affordable heterogeneous catalytic glass-based material for the reduction of 4-nitrophenol by sodium borohydride. The glass matrix acts as a host and support material for in situ self-growth of zero-valent copper (Cu) nanoparticles (NPs) on the glass surface. Thus, zero-valent CuNPs are produced in situ on the glass surface that is accomplished by the interaction of copper ions with hydride ions. Using an intrinsic reaction kinetic constant, we find a catalytic activity of 0.144 L s-1 g-1 for a glass-based catalyst doped with a non-noble metal, which is an order of magnitude higher when compared to the values observed elsewhere. Furthermore, the reuse of glass catalyst after six successive cycles demonstrates an outstanding performance compared to that of the parent material. A mathematical model based on the Langmuir-Hinshelwood mechanism related to an empirical growth rate of the zero-valent CuNPs was proposed to describe the kinetic of the 4-nitrophenol catalytic hydrogenation.

RESUMO

The highly effective Au/Fe2O3-@Au/Fe2O3nanoreactors for the 4-nitrophenol (4-NP) reduction are successfully obtained by one-pot synthesis using the spray pyrolysis (SP) technique. The Au/Fe2O3-@Au/Fe2O3nanoreactors manifest superior catalytic activity in the reduction of 4-NP in the presence of sodium borohydride (NaBH4) compared to gold-iron oxide nanoreactors prepared via a colloidal approach. The negative effect of the reaction product accumulation, the 4-aminophenol (4-AP), on the catalytic reduction of 4-NP over Au/Fe2O3-@Au/Fe2O3is examined by a direct pre-injection of 4-AP to the reaction media. To the best of our knowledge, it is the first experimental evidence of gold active sites blocking by 4-AP. All obtained samples are characterized by the yolk-shell spherical hollow structure mainly consisted of two embedded hollow nanospheres. The reduction of iron oxide precursor concentration diminishes the diameter of final iron oxide nanospheres. According to STEM-EDS analysis and STEM, Au nano species are uniformly dispersed on both iron oxide nanospheres. The SP technique presently used to synthesize Au/Fe2O3-@Au/Fe2O3nanoreactors manifests high potential for the one-pot fabrication of a large variety of nanoreactors with various active materials applied as heterogeneous catalysts in numerous catalytic processes.

RESUMO

The nitroaromatic compounds, known as organic pollutants, have arising attention due to their carcinogenic character, highly dangerous to human health. In this work, the Ag@ZnO/MWCNT ternary nanocomposite synthesized via conjugation of sonochemical and solvothermal treatments manifests high performance in the reduction of 4-nitrophenol in the aqueous media (TOF value of 246 min-1µmol metal-1). The incorporation of MWCNT onto the nanocomposite structure favored the reusing of the catalysts even after eight consecutive catalytic runs without catalysts cleaning nor product removal. Obtained samples were characterized by XRD, TEM, UV-vis, Raman and FTIR spectroscopies. It was found that ultrasonic treatment at relatively moderate conditions leads to functionalization of MWCNT, the appearance of C=C and OH groups and change of electronic properties of Ag@ZnO/MWCNT composite which provide its stable material dispersion in aqueous solution and high catalytic performance in the 4-nitrophenol reduction. This technique may be effectively applied for the functionalization of carbon including materials for their usage in an aqueous media.

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V-doped TiO2 materials (0.01, 0.05, 0.10, and 1.00 nominal atomic %) were synthesized by the sol-gel method and characterized by X-ray diffraction, Raman spectroscopy, UV-visible diffuse reflectance spectroscopy, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and H2-temperature programmed reduction. Two vanadium precursors (vanadyl acetylacetonate and ammonium metavanadate) and three calcination temperatures (400, 500, and 600 °C, with and without air circulation) were assayed. The efficiency of the materials as photocatalysts was studied by the degradation of phenol with UV and visible lamps. The photocatalyst prepared from vanadium acetylacetonate, with a vanadium content of 0.01 nominal atomic %, calcination at 400 °C without air circulation (0.01VTi-400), showed the best performance, reaching 100% and 30% degradation of phenol (50 µM) by irradiation with UV lamps (3 h) and visible lamps (5 h), respectively. To evaluate the efficiency of this catalyst in the degradation of other structurally related compounds, two substituted phenols were selected: 4-chlorophenol and 4-nitrophenol. The 0.01VTi-400 photocatalyst showed to be applicable to the degradation of phenolic compounds when the substituent was an activating group or a weakly deactivating group (for electrophilic reactions). Additionally, the selectivity of 0.01VTi-400 for phenol degradation in the presence of Aldrich humic acid was tested: phenol degradation reached 68% (3 h, UV lamps). The performance of 0.01VTi-400 indicated that it is a promising material for further applications.

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RESUMO

The present work reports the degradation of 4-nitrophenol using BiVO4/CuO hybrid material synthesized by the precipitation of BiVO4 in the presence of CuO. Morphological and structural characterizations were performed using X-ray diffraction and scanning electronic microscopy coupled to energy dispersive X-ray spectroscopy. Through the calculation of the Kubelka-Munk function applied to diffuse reflectance spectrophotometry data, the hybrid material presented absorption edge of 1.85 eV. The formation of p-n heterojunction between BiVO4 and CuO renders the hybrid material suitable for the construction of a photoanode employed in hydroxyl radical generation. UV-vis spectrophotometry and high-performance liquid chromatography experiments were performed in order to monitor the degradation of 4-nitrophenol and the formation of secondary products. Additional information regarding the hybrid material was obtained through ion chromatography and total organic carbon analyses. The application of BiVO4/CuO-based photocatalyzer led to a 50.2% decrease in total organic carbon after the degradation of 4-nitrophenol. Based on the results obtained in the study, BiVO4/CuO has proved to be a promising material suitable for the removal of recalcitrant compounds in water treatment plants.

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In this work, we report a facile strategy for 4-nitrophenol (4-NP) sensing using highly luminescent nitrogen-doped oxidized carbon dots. The quenching of fluorescence (turn OFF), with the addition of trace amounts of organic pollutant (4-NP) in NOCDs, has been attributed to the complete reduction of nitrogen-doped oxidized carbon dots (NOCDs) to reduced nitrogen-doped oxidized carbon dots (rNOCDs) and its formation was confirmed by infrared, X-ray diffraction and X-ray photoelectron spectroscopy measurements. The chemical changes in oxygen-containing functional groups of NOCDs, in the presence of 4-NP, are elucidated and corresponding characterization through XPS reveals the changes in the peak intensities of CC (284.5 eV) and OCO (288.6 eV), indicating a decrement in hydroxyl groups that hinder its complete reduction to NOCDs. The sensitivity of NOCDs towards 4-NP has been tested in spiked tap water in the concentration range 2 µM to 2 mM with the minimum detection limit of 2 µM (linear detection range from 2 to 100 µM with regression coefficient R2 =0.99). The proposed simple sensing platform can be used to reduce NOCDs and simultaneously sense low concentrations of 4-NP. Finally, an effective treatment to improve the reduction of nitrogen-doped graphene oxide is proposed.

RESUMO

Geobacter sulfurreducens and anthraquinone-2-sulfonate (AQS) were used suspended and immobilized in barium alginate during the biotransformation of 4-nitrophenol (4-NP). The assays were conducted at different concentrations of 4-NP (50-400 mg/L) and AQS, either in suspended (0-400 µM) or immobilized form (0 or 760 µM), and under different pH values (5-9). G. sulfurreducens showed low capacity to reduce 4-NP in absence of AQS, especially at the highest concentrations of the contaminant. AQS improved the reduction rates from 0.0086 h-1, without AQS, to 0.149 h-1 at 400 µM AQS, which represent an increment of 17.3-fold. The co-immobilization of AQS and G. sulfurreducens in barium alginate beads (AQSi-Gi) increased the reduction rates up to 4.8- and 7.2-fold, compared to incubations with G. sulfurreducens in suspended and immobilized form, but in absence of AQS. AQSi-Gi provides to G. sulfurreducens a barrier against the possibly inhibiting effects of 4-NP.

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Resumen Se evaluó la aminación de un carbón activado preoxidado con ácido nítrico en la adsorción de 4-nitrofenol. Se aplicó el modelo de Sips a la adsorción desde solución acuosa, utilizando Sigmoidal Logistic 3 Parameter del programa SigmaPlot 12. Los parámetros obtenidos se compararon con los calculados con el programa Statistica 7 para los modelos de Sips y Langmuir. Se encontró que la modificación realizada sobre el carbón activado incrementó la adsorción de 4-nitrofenol de 2,16 a 2,19 mmolg-1, aumentando, a su vez, la afinidad adsorbente-adsorbato. El parámetro para la energía característica del sistema determinado con el modelo de Langmuir toma un valor de 377,47 L mmol-1 al no considerar la heterogeneidad energética, mientras que a partir del modelo de Sips se presenta un valor de 8,32 (Lmmol-1)1/n. Adicionalmente, se encontró que en la ecuación matemática Sigmoidal Logistic 3 Parameter del programa SigmaPlot el valor de 1/x0 corresponde a la constante KLF del modelo Langmuir-Freundlich, mientras que el valor del parámetro Ks del modelo de Sips es igual a (1/x0)-b. Se concluye que la adsorción de 4-nitrofenol sobre el carbón activado se favorece por el incremento de grupos nitrogenados sobre su superficie.

Abstract The amination of a nitric acid pre oxidized activated carbon in the adsorption of 4-nitrophenol was evaluated. The Sips model application to the aqueous solution adsorption data, using Sigmoidal Logistic 3 Parameter formula, in the SigmaPlot 12 program was applied. The obtained parameters were compared with those calculated with Statistica 7 program for Sips and Langmuir models. It was found that the activated carbon increases the adsorption from 2.16 to 2.19 mmol g-1, showing good adsorbent-adsorbate affinity. The system's characteristic energy parameter calculated with the Langmuir model was 377.47 L mmol-1, when not considering energy heterogeneity, while from the Sips model was 8.32 (L.mmol-1)1/n. Additionally, it was found that in the mathematical equation Sigmoidal Logistic 3 Parameter of the SigmaPlot program, the 1/x0 value corresponds to the Langmuir-Freundlich model constant KLF, while the parameter value KS in the Sips model is equal to (1/x0)-b in this program. It was concluded that the 4-nitrophenol adsorption on activated carbon is favored by the presence of nitrogen groups on their activated carbon surface.

Resumo Foi avaliada a aminação de um carvão ativado preoxidado com ácido nítrico na adsorção do 4-nitrofenol. Foi aplicado o modelo de Sips à adsorção desde solução aquosa usando Logística Sigmoidal 3 do programa Sigmaplot 12. Os parâmetros obtidos foram comparados com os calculados com o programa Statistica 7, para os modelos de Sips e Langmuir. Foi encontrado que a modificação do carvão ativado incrementou a adsorção de 4-nitrofenol de 2,16 até 2,19 mmolg-1, acrescentando a afinidade adsorvente-adsorvato. O parâmetro para a energia característica do sistema calculado com o modelo Langmuir teve um valor de 377,47 Lmmol-1 porque não considerou a heterogeneidade energética, enquanto que no modelo de Sips este parâmetro teve um valor de 8,32 (Lmmol-1)1/n. Além disso, foi encontrado que na equação matemática Sigmoidal Logistic 3 Parameter do programa Sigmaplot 3 o valor de 1/x0 corresponde à constante KLF do modelo Langmuir-Freundlich, enquanto o valor do parâmetro KS do modelo de Sips é igual a (1/x0)-b. Conclui-se que a adsorção do 4-nitrofenol sobre carvão ativado é favorecida pela presença de grupos nitrogenado na superfície destes.

RESUMO

Abstract Activity of hepatic metabolic enzymes of glucuronidation and sulfation of 4-nitrophenol (PNP) and biliary excretion of its glucuronide (PNP-G) and sulfate (PNP-S) conjugates have been investigated in control and streptozotocin (STZ)-induced diabetic rats. 500 µM PNP solution was luminally perfused in a cannulated jejunal loop for 90 minutes. It was found that biliary excretion of PNP-G was significantly decreased in the diabetic rats. This effect of STZ could be completely reversed by administration of rapid-acting insulin. Activity of hepatic UDP-glucuronyltransferase and ß-glucuronidase was also depressed by the STZ pretreatment. Administration of insulin antagonized the inhibitory action of STZ on UDP-glucuronyltransferase, but the reduced activity of ß-glucuronidase was not reversed. Biliary excretion of PNP-S was also depressed in the diabetic rats. Whereas, different effects of insulin administration were observed. Namely, the lower biliary excretion rate of PNP-S was not changed after administration of insulin. Activity of the sulfotransferase and the arylsulfatase enzymes was not altered either by STZ pretreatment or by insulin administration. Biliary excretion of PNP was also significantly depressed by STZ and this depression was not changed after insulin administration. The results call attention to hepatobiliary circulation of low molecular weight xenobiotics and their glucuronide and sulfate conjugates

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This work describes the removal of chromium ions from industrial effluent using a hybrid magnetic adsorbent, CoFe2O4/NOM, synthesized using water rich in natural organic matter. The hybrid obtained at ambient temperature (HbAmb) was calcined at 200, 400, and 800°C for 2h, and formation of the cobalt ferrite phase was confirmed by XRD, which indicated the presence of NOM in the structure of the material. Removal tests showed that HbAmb provided efficient removal of chromium at the natural pH of the effluent, while the other materials were effective at pH 6. Evaluation of the kinetics showed excellent performance of the process, with 70-87% removal in 20min, which provided a high degree of flexibility. The hybrid showed high removal during five reuse cycles, ranging from 96% in the first cycle to 82% in the final. The matrices containing the saturated adsorbent (HbAmb_Sat) and recovered chromium ions (CrD) showed high performance in the catalytic reduction of 4-nitrophenol, with conversion rates of 99.9% in short periods of time, as well as excellent potential for reuse in three cycles. The results demonstrated that the production of a technological material and its use for remediation could be achieved in an ecologically sustainable manner.