Aniline In Water Research Articles

Evidence for Superoxide-Initiated Oxidation of Aniline in Water by Pulsed, Atmospheric Pressure Plasma.

Plasma-driven solution electrochemistry (PDSE) uses plasma-generated reactive species to drive redox reactions in solution. Nonthermal, atmospheric pressure plasmas, when irradiating water, produce many redox species. While PDSE is a promising chemical tool, there is limited insight into the mechanisms of the reactions due to the variety of short-lived reagents produced. In this study, we use aniline as a model system for studying redox mechanisms of PDSE. We show that the plasma irradiation of aqueous aniline solutions drives the formation of polyaniline oligomer, which is suppressed under acidic starting conditions. The addition of (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO), a radical scavenger, decreases the formation of oligomer by 80%, and the addition of superoxide dismutase fully hinders oligomerization. These results lead us to conclude that the oligomerization of aniline by plasma irradiation is initiated by superoxide. This discovery provides novel insights into PDSE mechanisms and illustrates a potential method of harnessing superoxide for chemical reactions.

Theoretical Investigation of Regiodivergent Addition of Anilines and Phenolates to p-Benzoquinone Ring.

Two different products were obtained by the regiodivergent reaction of benzoquinone derivatives with phenolates and anilines: 3-aryloxybenzoquinone and 2-phenylamino-3-bromobenzoquinone. Calculated density functional theory free energies of reaction values corroborate the experimental observation of the formation of the substitution product in the reaction with phenolates in acetonitrile and the product of addition/oxidation for the reaction with aniline in water. Calculated charges and Fukui functions are similar for C2 and C3 atoms, indicating an equal possibility to suffer a nucleophilic attack. The calculated energy barriers for nucleophilic attack steps indicated that the first steps of the substitution with phenolates and addition/oxidation with anilines are faster, which justifies the formation of the respective products. The natural bond order analysis for the transition states revealed that there is a strong interaction between lone pairs of N and O atoms and the πC2C3 * for the O → C2 and N → C3 attacks and a weak interaction for the O → C3 and N → C2 attacks, which also agrees with experimental observations.

Film-based fluorescent sensor for visual monitoring and efficient removal of aniline in solutions and gas phase

Aniline has attracted much concern for its long degradation half-life and huge toxicity to the environment and human beings. Therefore, the development of a multi-functional device for visual detection and efficient removal of aniline was highly anticipated. In our work, the small-size Eu@UiO-66(COOH) was obtained by post-synthesis modification (PSM), and then the film-based fluorescent sensor was prepared by crosslinking reaction. The films not only showed incredible mechanical stability and potential for large-scale preparation, but also have excellent fluorescence response to aniline in solutions and gas phase. As the concentration of aniline increased, the fluorescence of films gradually increased at 350 nm, while the fluorescence gradually quenching at 620 nm, and the detection limits (LOD) of aniline in water and air were 0.27 ppb and 0.086 ppb, respectively. In addition, the adsorption performance of the film for aniline has also been confirmed and the maximum adsorption capacity was 32.6 mg/g, which is a strong guarantee for the realization of ultra-trace detection and toxicity reduction of aniline. In summary, the multi-functional film sensor has been designed for ultra-trace detection and efficient removal of aniline in solutions and gas phase, and have significant value for pollutant treatment, ecological restoration and early prevention.

Micellar Suzuki Cross-Coupling between Thiophene and Aniline in Water and under Air

The Suzuki–Miyaura cross-coupling reaction plays a fundamental role in modern synthetic organic chemistry, both in academia and industry. For this reason, scientists continue to search for new, more effective, cheaper and environmentally friendly procedures. Recently, micellar synthetic chemistry has been demonstrated to be an excellent strategy for achieving chemical transformations in a more efficient way, thanks to the creation of nanoreactors in aqueous environments using selected surfactants. In particular, the cheap and commercially available surfactant Kolliphor EL (a polyethoxylated castor oil derivative) has been used with success to achieve metal-catalyzed transformations in water with high yields and short reaction times, with the advantage of using air-sensitive catalysts without the need for inert atmosphere. In this work, the Kolliphor EL methodology was applied to the Suzuki cross-coupling reaction between thiophene and aniline, using the highly effective catalyst Pd(dtbpf)Cl2. The cross-coupling products were achieved at up to 98% yield, with reaction times of up to only 15 min, working at room temperature and without the need for inert atmosphere.

Preparation and adsorption performance of cellulose nanofibrils/polyvinyl alcohol composite gel spheres with millimeter size

Wastewater treatment is a huge problem facing human beings. The development of recyclable and efficient adsorption materials is of great benefit to solve the problem. Based on the biodegradable cellulose nanofibers (CNFs) derived from biomass resources, the large sized CNFs/PVA composite hydrogel spheres (CV-HSs, 1–3 mm) were successfully prepared by the inverse suspension pellet-forming technology using the polymers as raw materials, and another hydrophobic CNFs/PVA composite aerogel spheres (HCV-ASs) were also obtained by lyophilization and followed silylation of as-prepared CV-HSs. The CV-HSs showed excellent adsorption properties for simulated pollutants, including Cu2+, phenol and aniline in water. The maximum absorption capacity of CV-HSs was 17.22 mmol/g for Cu2+, 176.72 mg/g for phenol and 341.93 mg/g for aniline respectively. The HCV-ASs exhibited good absorption properties for weak polar organic solvents, such as petroleum ether, ethyl acetate and toluene. In summary, two kinds of large-sized CNFs/PVA composite gel spheres were successfully fabricated, and exhibited good adsorption properties for organic pollutants and heavy metal ions, indicating their potential for wastewater treatment.

Degradation of aniline in water with gaseous streamer corona plasma.

This paper demonstrated the effects and influencing factors in degrading aniline by gaseous streamer corona plasma along water surface under different discharging gas atmospheres. For aniline with an initial concentration of 100 mg l−1, the degradation was fastest when the reactor was not ventilated, and the degradation rate is 98.5% under 7.5 min treatment. While the degradation was slowest when Ar was ventilated, the degradation rate is 98.6% after treatment for 60 min. Some active particles were detected using a multi-channel fibre-optic spectrometer during the discharge, such as Ar, OH, N2, and N. In particular, NO was detected during air discharge. The NO and could produce ; then generated nitric acid would affect the pH value of the solution. The intermediate product by N2 discharge is nitrophenol, and nitrophenol would be converted to p-benzoquinone. The O2 discharge could produce an intermediate product of aminophenol. The intermediate products in Ar discharge were in small amounts and the final mineralization effect was the best.

Supported Pt-Cu bimetallic catalysts: preparation and synergic effects in their catalytic oxidative degradation of aniline.

Catalytic Fenton oxidation is an effective way to remove organic pollutants in water, and the performance of the catalyst is a key issue for the competiveness of this method. In this work, various supported bimetallic Pt–Cu catalysts were prepared by different impregnation methods and their performances for catalytic Fenton oxidation of aniline in water were investigated. In the different impregnation methods employed, factors including the reduction method of the metal precursor, type of catalytic support, and loading of metal were investigated. The effect of different reduction methods on actual loadings of the active components on the supported Pt–Cu catalysts showed the order of (i) H2 reduction > (ii) liquid phase methanal reduction. Meanwhile, compared with the monometallic catalysts, the Pt–Cu alloy phase (mainly in the form of PtCu3) was generated and the specific surface area was significantly reduced for the bimetallic catalysts. In the process of Fenton catalytic oxidation of aniline, it was found that most of the prepared catalysts had a certain catalytic activity for H2O2 accompanied with aniline degradation. It was found that Pt0.5Cu1.5/AC (where AC denotes activated carbon) exhibited superb catalytic activity compared with all other prepared catalysts. In particular, aniline was almost completely mineralized in a neutral solution (500 mg L−1 aniline, 0.098 mol L−1 H2O2) after 60 min at 50 °C using Pt–Cu/AC (Pt: 0.5%, Cu: 1.5%). The characterization results showed that the Pt and Cu components were rather evenly distributed on the AC support for this catalyst. More importantly, there was an obvious synergic effect on the supported bimetallic catalyst between the Pt and Cu components for the catalytic oxidation of aniline.

Scale-up of vortex based hydrodynamic cavitation devices: A case of degradation of di-chloro aniline in water

Hydrodynamic cavitation (HC) is being increasingly used in a wide range of applications. Unlike ultrasonic cavitation, HC is scalable and has been used at large scale industrial applications. However, no information about influence of scale on performance of HC is available in the open literature. In this work, we present for the first time, experimental data on use of HC for degradation of complex organic pollutants in water on four different scales (~200 times scale-up in terms of capacity). Vortex based HC devices offer various advantages like early inception, high cavitational yield and significantly lower propensity to clogging and erosion. We have used vortex based HC devices in this work. 2,4 dichloroaniline (DCA) – an aromatic compound with multiple functional groups was considered as a model pollutant. Degradation of DCA in water was performed using vortex-based HC devices with characteristic throat dimension, dt as 3, 6, 12 and 38 mm with scale-up of almost 200 time based on the flow rates (1.3 to 247 LPM). Considering the experimental constraints on operating the largest scale HC device, the experimental data is presented here at only one value of pressure drop across HC device (280 kPa). A previously used per-pass degradation model was extended to describe the experimental data for the pollutant used in this study and a generalised form is presented. The degradation performance was found to decrease with increase in the scale and then plateaus. Appropriate correlation was developed based on the experimental data. The developed approach and presented results provide a sound basis and a data set for further development of comprehensive multi-scale modelling of HC devices.

Microporous Hydrogen-Bonded Organic Framework for Highly Efficient Turn-Up Fluorescent Sensing of Aniline.

A microporous three-dimensional (3D) hydrogen-bonded organic framework (HOF-20) has been constructed from an aromatic-rich tetratopic carboxylic acid, 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid (H4BCPIA). The activated HOF-20a has a moderately high Brunauer-Emmett-Teller (BET) surface area of 1323 m2 g-1 and excellent stability in water and HCl aqueous solution. HOF-20 exhibits highly efficient turn-up fluorescent sensing of aniline in water with a detection limit of 2.24 μM and is selective toward aniline in the presence of aromatic interferents, owing to the hydrogen bonding and edge-to-face π-π stacking interactions between the HOF-20 host and the guest aniline molecules, as demonstrated in the single-crystal X-ray structure of HOF-20⊃aniline. Density functional theory (DFT) calculations further demonstrate that the recognition of aniline molecules by HOF-20 could restrict the rotation of the aromatic rings in H4BCPIA linkers, reducing the nonradiative decay pathways upon photoexcitation and subsequently enhancing the fluorescence intensity.

UiO-66-supported Fe catalyst: a vapour deposition preparation method and its superior catalytic performance for removal of organic pollutants in water.

A vapour deposition (VD) method was established for preparation of the UiO-66-supported Fe (Fe/UiO-66) catalyst, which provided the first case of the metal-organic framework (MOF)-supported Fe catalyst prepared by using the vapour-based method. The Fe loading was around 7.0–8.5 wt% under the present preparation conditions. The crystal structure of UiO-66 was not obviously influenced by the Fe loading, while the surface area significantly decreased, implicating most of the Fe components resided in the pores on UiO-66. The results for the methyl orange (MO) removal tests showed that MO in aqueous solution can be removed by UiO-66 by adsorption, and in contrast, it can be oxidized by H2O2 with the catalysis of Fe/UiO-66. Further catalytic tests showed that Fe/UiO-66 was rather effective to catalyse the oxidation of benzene derivatives like aniline in water in terms of chemical oxygen demand (COD) removal efficiency. The catalytic test results for Fe/UiO-66 were compared to those of Fe/Al2O3 with the same Fe loading and to the catalysts reported in the literature. This paper provides a general strategy for VD preparation of MOF-supported Fe catalyst on the one hand, and new catalysts for removing organic pollutants from water, on the other hand.

Activation of sodium percarbonate by vanadium for the degradation of aniline in water: Mechanism and identification of reactive species

Sodium percarbonate (SPC)-based advanced oxidation process has been applied to the wastewater treatment in recent years. In the present study, a novel catalyst utilization of vanadium(V) was investigated for the activation of SPC for aniline degradation. The mechanism of SPC activation by V(IV) was demonstrated, and the major free radicals were identified through scavenging tests and electron paramagnetic resonance (EPR) analysis. The performance of aniline degradation was evaluated in the V(IV)/H2O2 and V(IV)/H2O2/Na2CO3 systems and compared with that of the V(IV)/SPC system. The influences of initial pH and effects of inorganic anions were also studied. The results show that aniline could be decomposed efficiently by SPC activated with V(IV) and the degradation efficiency increased with the increase in V(IV) and SPC dosage. O2−, CO3−, and OH were found to participate in aniline degradation, and O2− and CO3− were confirmed to be the predominant species. The decomposition of aniline was enhanced when equal amount of H2O2 was utilized instead of SPC under acidic condition while a comparative behavior was achieved in the V(IV)/H2O2/Na2CO3 system. Furthermore, aniline degradation was not impacted significantly by the initial pH and addition of Cl−, SO42− and NO3−, while HCO3− led to a betterment of aniline removal. These results indicate that the V(IV)/SPC system is an effective and promising approach for the removal of aniline from water for its feasibility and stability, which achieves eliminating contaminants by another waste.

Solvation thermodynamics of benzene, nitrobenzene, and aniline in water–acetonitrile mixtures

The enthalpies of dissolution of benzene, nitrobenzene, and aniline in water–acetonitrile mixtures are determined via calorimetry. The concentration dependences of the standard enthalpies of solvation of solutes are calculated. It is found that the concentration dependences of the standard enthalpies of solvation pass through maxima. The height of the observed maxima is shown to depend largely on the nature of the substituent. In the presence of a hydrophilic amino group capable of forming strong hydrogen bonds with water molecules, the value of a maximum falls; in the presence of a nitro group, it rises. The enthalpy parameters of pair interaction between molecules of water and benzene and its derivatives are calculated.

A Copper(II)-Paddlewheel Metal-Organic Framework with Exceptional Hydrolytic Stability and Selective Adsorption and Detection Ability of Aniline in Water.

Copper(II)-paddlewheel-based metal-organic frameworks (CP-MOFs) represent a unique subclass of MOFs with highly predictable porous structures, facile syntheses, and functional open metal sites. However, the lack of high hydrolytic stability is an obstacle for CP-MOFs in many practical applications. In this work, we report a new CP-MOF, [Cu4(tdhb)] (BUT-155), which is constructed from a judiciously designed carboxylate ligand with high coordination connectivity (octatopic), abundant hydrophobic substituents (six methyl groups), and substituent constrained geometry (tetrahedral backbone), tdhb8- [H8tdhb = 3,3',5,5'-tetrakis(3,5-dicarboxyphenyl)-2,2',4,4',6,6'-hexamethylbiphenyl)]. BUT-155 shows high porosity with a Brunauer-Emmett-Teller surface area of 2070 m2/g. Quite interestingly, this CP-MOF retains its structural integrity after being treated in water for 10 days at room temperature or in boiling water for 24 h. To the best of our knowledge, BUT-155 represents the first CP-MOF that is demonstrated to retain its structural integrity in boiling water. The high hydrolytic stability of BUT-155 allowed us to carry out adsorption studies of water vapor and aqueous organic pollutants on it. Water-vapor adsorption reveals a sigmoidal isotherm and a high uptake (46.7 wt %), which is highly reversible and regenerable. In addition, because of the availability of soft-acid-type open Cu(II) sites, BUT-155 shows a high performance for selective adsorption of soft-base-type aniline over water or phenol, and a naked-eye detectable color change for the MOF sample accompanies this. The adsorption selectivity and high adsorption capacity of aniline in BUT-155 are also well-interpreted by single-crystal structures of the water- and aniline-included phases of BUT-155.

Magnetic M x O y @N-C as heterogeneous catalysts for the catalytic oxidation of aniline solution with sulfate radicals

Metal nanoparticles have been combined with magnet metal–organic frameworks (MOFs) to afford new materials that demonstrate an efficient catalytic degradation, high stability, and excellent reusability in areas of catalysis because of their exceptionally high surface areas and structural diversity. Magnetic M x O y @N-C (M = Fe, Co, Mn) nanocrystals were formed on nitrogen-doped carbon surface by using 8-hydroxyquinoline as a C/N precursor. The Co@N-C, MnO@N-C, and Fe/Fe2O3@N-C catalysts were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), N2 adsorption/desorption, and X-ray photoelectron spectroscopy (XPS). The catalytic performances of catalysts were thoroughly investigated in the oxidation of aniline solution based on sulfate radicals (SO4 −.) toward Fenton-like reaction. Magnetic M x O y @N-C exhibits an unexpectedly high catalytic activity in the degradation of aniline in water. A high magnetic M x O y @N-C catalytic activity was observed after the evaluation by aniline degradation in water. Aniline degradation was found to follow the first-order kinetics, and as a result, various metals significantly affected the structures and performances of the catalysts, and their catalytic activity followed the order of Co > Mn > Fe. The nanoparticles displayed good magnetic separation under the magnetic field.

Cobalt super-microparticles anchored on nitrogen-doped graphene for aniline oxidation based on sulfate radicals

Cobalt super-microparticles anchored on nitrogen-doped graphene (Co–NG) were prepared using an inexpensive method and were tested for heterogeneous oxidation of aniline with peroxymonosulfate (PMS) in aqueous solutions. The crystal structure, morphology, and textural properties of Co–NG hybrids were investigated by various characterization techniques, such as X-ray diffraction, Raman spectroscopy, dark-field scanning transmission electron microscopy and X-ray photoelectron spectroscopy. Electron paramagnetic resonance and classical quenching tests were conducted to investigate the mechanism of PMS activation and aniline oxidation. The catalyst Co–NG exhibits an unexpectedly high catalytic activity in the degradation of aniline in water by advanced oxidation technology based on sulfate radicals (SO4−), and 100% decomposition can be achieved in 10min. This paper offers new insights on heterogeneous catalysis.

Fabrication of nanoporous gold thin films on glass substrates for amperometric sensing of aniline

Nanoporous gold (NP-Au) thin films were fabricated on glass substrates by dealloying an Au–Si alloy produced by co-deposition of Au and Si. Si was selectively removed from the Au–Si alloy with potassium hydroxide solution, which is a very simple and safe dealloying method. We investigated the optimum conditions for sputtering and dealloying to obtain stable and durable nanoporous films. The NP-Au films were used as a working electrode for amperometric sensing of aniline in water and exhibited a wider sensing range and lower detection limit than NP-Au electrodes fabricated on Si substrates with HF etchant. The larger surface roughness factor of the NP-Au sensor is responsible for the enhanced sensing performance.

Photocatalytic degradation of aniline in water using CuO nanoparticles

The removal of aniline as a carcinogen from aqueous environments is highly significant. In the present study, the feasibility of photocatalytic degradation of aniline by CuO nanoparticles was evaluated. A batch reactor with an internal UV lamp was used and the effects of the parameters of pH (3–11), dosage of catalyst (0.01–0.1 g/L), initial concentration of aniline (50–250 mg/L), and duration of reaction (15–90 min) were investigated. The remaining concentration of aniline was determined by spectrophotometer at the wavelength of 198 nm. The Langmuir–Hinshelwood model was used for examining the kinetics of the reaction. The results showed that the degradation of aniline is maximum at pH 7. Also, the removal efficiency of 90.16% after 90 minutes of reaction in the case of initial concentration of 50 mg/L was obtained. The aniline degradation was elevated from 40 to 82% by increasing CuO nanoparticles’ dosage from 0.01 to 0.1 g/L. In addition, the obtained data properly fit with the Langmuir–Hinshelwood kinetic model and showed that the K app decreased from 0.029 to 0.016 min −1 by increasing of the initial concentration of aniline. Considering the obtained results, the UV/CuO process can be an effective method for removing aniline from aqueous solution.

Photodegradation of aniline in water in the presence of chemically activated halloysite

Photocatalytic degradation of aniline was investigated in aqueous solutions containing halloysite (Hal) nanotubes, chemically activated halloysite (AHal), and photocatalysts: TiO2 (anatase) and commercial titania P25, under UV illumination. Powder X-ray diffraction (XRD), UV–Vis/DR spectra and nitrogen adsorption isotherms were carried out to characterize the activated halloysite. The effects of the AHal and titania photocatalyst amount as well as aniline concentration were examined. It is observed that the photodegradation of aniline has a similar course in the presence of AHal and in the presence of P25 and TiO2, both with respect to the decomposition of aniline and in decreasing the amounts of photoproducts being formed during the irradiation of aniline. The photodegradation of aniline is clearly slower in presence of Hal nanotubes than for AHal and P25. The disappearance of aniline follows approximately according to the Langmuir–Hinshelwood kinetics. The values of rate photodegradation constant are decreasing in the following order: P25>TiO2>AHal>Hal nanotubes. These results have indicated that halloysite containing titanium dioxide could be employed during photocatalytic removal of aniline from the aqueous solution, similarly to commercial titania photocatalysts.

Effects of solid poly (ethylene glycols) addition to the solutions of aniline or N,N-dimethylaniline with water: Experimental measurements and modeling

In this work, the liquid - liquid and solid - liquid phase behaviour of ten aqueous pseudo-binary and three binary systems containing polyethylene glycol 2050, polyethylene glycol 35000, aniline, N,N-dimethylaniline and water, in the temperature range T = (298.15 to 350.15) K and at ambient pressure of 0.1 MPa, was studied. The obtained temperature-composition phase diagrams showed that the only functional co-solvent was PEG2050 for aniline in water, while PEG35000 even showed a clear anti-solvent effect in the N,N-dimethylaniline aqueous system. The experimental SLE data have been correlated by the Non-Random Two-Liquid (NRTL) model, and the correlation results are in accordance with the experimental results.

Cloud Point Phenomena in the (Aniline or N,N-Dimethylaniline + Water) Solutions, and Cosolvent Effects of Liquid Poly(ethylene glycol) Addition: Experimental Measurements and Modeling

In this work, liquid phase behavior (cloud point phenomena) was studied for two binary and four aqueous pseudobinary systems containing aniline or N,N-dimethylaniline and poly(ethylene glycol) 200 or poly(ethylene glycol) 400, (PEG200 and PEG400, respectively) in the temperature range T = (290.15 to 351.15) K and an ambient pressure of 0.1 MPa. Experimental data (cloud-points) were obtained by the visual cloud point method. The studied systems exhibit an upper critical solution temperature (UCST) type of phase behavior and the immiscibility increases with increasing the average molar mass of poly(ethylene glycols). PEG200/PEG400 showed as a good cosolvent for aniline in water. The experimental data were correlated using non-random two-liquid model (NRTL) with one form of temperature dependent parameters.