Adsorption removal of o-nitrophenol and p-nitrophenol from wastewater by metal–organic framework Cr-BDC

In the present paper, a metal–organic framework Cr-BDC was prepared and used as adsorbent for adsorption of o-nitrophenol(ONP) and p-nitrophenol(PNP) from aqueous solutions. Cr-BDC was characterized by scanning electron microscopy, transmission electron microscope, X-ray diffraction and BET methods. The results indicate that Cr-BDC gets a very large specific surface area of 4128 m^2·g^(-1)and pore sizes are concentrated in 1 nm, which is a benefit for using for wastewater treatment. The influences of the adsorption conditions, such as temperature,solution concentration, adsorption time and reusability on adsorption performance were investigated. Cr-BDC exhibited an encouraging uptake capacity of 310.0 mg·g^(-1)for ONP, and adsorption capacity of Cr-BDC for ONP is significantly higher than that for PNP under suitable adsorption conditions. The characterizations of adsorption process were examined with the Lagergren pseudo-first-order, the pseudo-second-order kinetic model, and the intra-particular diffusion model. Kinetics experiments indicated that the pseudo-second-order model displayed the best correlation with adsorption kinetics data. Furthermore, our adsorption equilibrium data could be better described by the Freundlich equation. The results indicate that the as-prepared Cr-BDC is promising for use as an effective and economical adsorbent for ONP removal.

The Effect of Titania Structure on Ni/TiO_2 Catalysts for p-Nitrophenol Hydrogenation

The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma (ICP), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and temperature-programmed reduction (TPR). Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2(A) is higher than that of rutile titania supported nickel catalyst Ni/TiO2(R), possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2(A) is easier than that for Ni/TiO2(R) at similar reaction conditions.

Direct electrocatalytic reduction of p-nitrophenol at room temperature ionic liquid modified electrode

Direct electrochemical reduction ofp-nitrophenol （PNP） was investigated on a room temperature ionic liquid N-butylpyridinium hexafluorophosphate （BPPF6） modified carbon paste electrode （CILE）. The cathodic peak potential was positively shifted and the peak currents were increased compared to that obtained on traditional carbon paste electrode （CPE）. The results indicated that the presence of ionic liquid BPPF6 on the electrode surface showed excellent catalytic ability to the electrochemical reduction of PNP. The electrochemical behaviors of PNP on the CILE were investigated by cyclic voltammetry and the conditions such as the scan rate, the buffer pH, the substrate concentration were optimized. The electrochemical parameters were further calculated with the results of the electron transfer number （n）, the charge-transfer coefficient （α） and the surface concentration （Гr） as 1.76, 0.37 and 2.47 × 10^-9 mol/cm^2, respectively, for the selected reductive peak. The results indicated that PNP showed an irreversible adsorption-controlled electrode process on the CILE.

Synergetic Effects of UV/Fe^(3+) Combined with Electrocatalysis for p-Nitrophenol Degradation

Synergetic effects for p-nitrophenol degradation were observed in the combination of two-advanced oxidation processes, UV/Fe3+ and electrocatalysis. The enhancement of removal rate for p-nitrophenol and COD was around 123% and 278%, respectively. The possible contributions for the synergetic effects were the electrochemically regeneration of ferric ion and the role of the oxygen that formed on the anode.

Effect of Alumina Particle Size on Ni/Al2O3 Catalysts for p-Nitrophenol Hydrogenation

The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/Al2O3 catalyst on alumina support with different particle size. It is found that support particle size has significant influences on physiochemical properties and catalytic activity of the resulting Ni/Al2O3 catalyst, but little influence on the selec-tivity. At a comparable amount of Ni loading, the catalytic activity of Ni/Al2O3 prepared with alumina support of smaller particle size is lower. The reduction behavior of the catalyst is a key factor in determining the catalytic activity of Ni/Al2O3 catalyst. The supported nickel catalyst 10.3Ni/Al2O3-3 improves the life span of the membrane by reducing fouling on the membrane surface compared to nano-sized nickel.

Ozonation with ultrasonic enhancement of p-nitrophenol wastewater

Synergetic effects for p-nitrophenol degradation were observed in the ozonation with ultrasonic enhancement. The enhancements of removal rate for p-nitrophenol and TOC were around 116% and 294% respectively in comparison with the individual ultrasound and ozonation systems. The synergetic phenomenon is attributed to two physicochemical mechanisms: (1) Ultrasound decomposes ozone causing augmentation of the activity of free radicals; (2) Ultrasonic wave increased the concen- tration of O3 in solution because of ultrasonic dispersion.

Frequency effect on p-nitrophenol degradation under conditions of strict acoustic and electric control

The process of decomposing p-nitrophenol （PNP） with power ultrasound requires strict control of acoustic and electric conditions. In this study, the conditions, including acoustic power and acoustic intensity, but not ultrasonic frequency, were controlled strictly at constant levels. The absorbency and the COD concentrations of the samples were measured in order to show the variation of the sample concentration. The results show significant differences in the trend of the solution degradation rate as acoustic power increases after the PNP solution （with a concentration of ll4 mg/L and a pH value of 5.4） is irradiated for 60 min with ultrasonic frequencies of 530.8 kHz, 610.6 kHz, 855.0 kHz, and 1130.0 kHz. The degradation rate of the solution increases with time and acoustic power （acoustic intensity）. On the other hand, the degradation rate of the solution is distinctly dependent on frequency when the acoustic power and intensity are strictly controlled and maintained at constant levels, The degradation rate of the PNP solution declines with ultrasonic frequencies of 530.8 kHz, 610.6 kHz, 855.0 kHz, and 1 130.0 kHz; the COD concentration, on the contrary, increase.

Activation of peroxydisulfate by gas-liquid pulsed discharge plasma to enhance the degradation of p-nitrophenol

Pulsed discharge in water and over water surfaces generates ultraviolet radiation,local high temperature,shock waves,and chemical reactive species,including hydroxyl radicals,hydrogen peroxide,and ozone.Pulsed discharge plasma（PDP） can oxidize and mineralize pollutants very efficiently,but high energy consumption restricts its application for industrial wastewater treatment.A novel method for improving the energy efficiency of wastewater treatment by PDP was proposed,in which peroxydisulfate（PDS） was added to wastewater and PDS was activated by PDP to produce more strong oxidizing radicals,including sulfate radicals and hydroxyl radicals,leading to a higher oxidation capacity for the PDP system.The experimental results show that the increase in solution conductivity slightly decreased the discharge power of the pulse discharge over the water surface.An increase in the discharge intensity improved the activation of PDS and therefore the degradation efficiency and energy efficiency of p-nitrophenol（PNP）.An increase in the addition dosage of PDS greatly facilitated the degradation of PNP at a molar ratio of PDS to PNP of lower than 80：1,but the performance enhancement was no longer obvious at a dosage of more than 80：1.Under an applied voltage of 20 kV and a gas discharge gap of 2 mm,the degradation efficiency and energy efficiency of the PNP reached 90.7%and45.0 mg kWh^（-1） for the plasma/PDS system,respectively,which was 34%and 18.0 mg kWh^（-1）higher than for the discharge plasma treatment alone.Analysis of the physical and chemical effects indicated that ozone and hydrogen peroxide were important for PNP degradation and UV irradiation and heat from the discharge plasma might be the main physical effects for the activation of PDS.

Synergetic effects for p-nitrophenol abatement using a combinedactivated carbon adsorption-electrooxidation process

A novel fluidized electrochemical reactor that integrated advanced electrochemical oxidation with activated carbon (AC) fluidization in a single cell was developed to model pollutant p-nitrophenol (PNP) abatement. AC fluidization could enhance COD removal by 22%-30%. In such a combined process, synergetic effects on PNP and COD removal was found, with their removal rate being enhanced by 137.8% and 97.8%, respectively. AC could be electrochemically regenerated and reused, indicating the combined process would be promising for treatment of biorefractory organic pollutants.

Mechanistic study of ozonation of p-nitrophenol in aqueous solution

Ozonlysis in the treatment of p-nitrophenol solution was studied in this paper. The results indicated that the decomposition of pnitrophenol was accelerated as the gas flow rate or pH value increased. When gaseous ozone concentration was 20.11 mg/L and pH was 3, after 24 m in reaction, the removal rate of p-nitrophenol reached 73.04%, 86. 11%, 91.71% and 95% at the gas flow rate of 32, 40, 48 and 56 ml/min respectively. And when pH was 3, 4, 5, 6, the decomposition rate was 66.38%, 82.09%, 90.46%, 97.50% after a 20 min reaction respectively. It was mainly O3 molecule that took part in the decomposition when pH was 3. The main intermediates during the decomposition include catechol, o-benzoquinone, hydroquinone, p-benzoquinone, phenol, fumaric acid, maleic acid, oxalic acid and formic acid. The decomposition mechanism of p-nitrophenol was also discussed.

Complex Formation between Heptakis(2,3,6-tri-O-butyl)-β-cyclodextrin with p-Nitrophenol in Heptane

Heptakis(2, 3, 6-tri-o-n-butyl)- β-cyclodextrin(TB- β-CD) has been found to form an inclusion compound with p-nitrophenol in heptane. The stability constent of the inclusion compound of p-nitrophenol with TB-β-CD in heptane is an order of magnitude greater than that in water.

Quality Control of Paracetamol Generic Tablets Marketed in Benin and Search of Its Two Impurities P-Aminophenol and P-Nitrophenol by HPLC-UV/Visible

In this work, we evaluated the quality of paracetamol generic tablets while seeking its two main impurities namely 4-para-aminophenol (4-AP) and 4-para-nitrophenol (4-NP) which have nephrotoxic and teratogenic properties. Ninety-four (94) samples were collected at various levels of the medicine supply chain and illegal markets in Benin for quality control tests such as visual inspection, pharmacotechnical tests as mass variation, disintegration test, dissolution test, followed by HPLC UV-Vis identification and assay of paracetamol, 4-AP and 4-NP. The analytes were separated on C18 Lichrocart column (250 mm × 4.0 mm i.d, 5 μm);the mobile phase was MeOH:10 mM ammonium acetate buffer pH 6.8 (35:65) pumped at a flow rate of 1 ml/min. The detection was done at 245 nm. Analysis of our results shows that 77.7% of the samples did not comply with the visual inspection test requirements, 2.1% did not pass the mass variation test, 24.3% of the sample batches didn’t comply with the disintegration test requirements. In addition none of these uncomply batches passed the dissolution test, even if the identification test indicated that all samples contained paracetamol. None contained 4-NP (acceptance limit < 0.05% m/m;BP), while 3 of 94 samples contained 4-AP but within acceptance limit (4-AP < 0.1% m/m;BP). As for the paracetamol assay, 80.9% complied with the specifications of the pharmacopoeias taken as reference (90% - 110%;USP). Further, broader studies should be conducted according to the same rules of good practice for a more comprehensive analysis of the situation. Generally the quality control of paracetamol in most African countries, particularly in Benin, is based on pharmacotechnical tests and paracetamol assay. This work, in addition to the usual tests, showed the importance to search for paracetamol and other drugs’ impurities during their routine quality control.

Adsorptive Removal of p-Nitrophenol from Aqueous Solution by Bone Char： Equilibrium and Kinetic Studies

Para-nitrophenol adsorbed on bone char synthesized from cow bones has been studied. The Langmuir Freundlich and Sips models were applied to the equilibrium data to describe the adsorption process. The Langmuir model best described the adsorption process with R^2 = 0.919; and maximum adsorption capacity, qmax of 365.76 mg/g. Batch kinetic studies conformed to pseudo-second-order indicating that several mechanisms may be involved in the process and gave a value of 2.5×10^4 g/mg/min for the rate constant for the sorption ofp-nitrophenol on bone char. The values of thermodynamic parameters, free energy ≈ -22.0 kJ/mol, enthalpy -20.2 kJ/mol and entropy 5.34 J/K mol for the adsorption of p-nitrophenol on bone char showed that the adsorption was spontaneous and exothermic.

RESEARCH ON THE ESTIMATE OF SAFETY AND TOXICITY OF P-NITROPHENOL SODIUM WITHA PHYSIOLOGICALLY BASED PHARMACOKINETICS MODEL

The safety and toxicity of chemicals given first to animals and finally to humans are generally estimated with a method of safe coefficient, which is scientifically a way lack of grounds. To make a change of the old method, we designed a Physiologically Based Pharmacokinetics Medel for the estimate of safety and toxicity of chemicais. As an example,p-nitrophenol sodium (PNP-Na) is used in the research work. Studies of the PNP-Na pharmacokinetics in bodies of rat as well as humans are made, and possibilities of making use of the Model in the estimate of safety and toxicity of chemicals are discussed.

254/185 nm photolysis of p-nitrophenol

Degradation of low-concentration p-nitrophenol(p-NP)aqueous solution was carried out in 254/185 nm photolysis.The effects of Mn^(2+),pH value,O_2 and O_3 on the degradation efficiency have been investigated.It was observed that the singlet oxygen scavenger Mn^(2+)did not affect the degradation of p-NP.In acidic and alkaline solutions,the degradation efficiency was enhanced in comparison to that in neutral solution.The presence of O_2 dramatically promoted the degradation of p-NP,while that of O_3 impeded it.

Synthesis of p-nitrophenol under normal pressure with A-1 phase transfer catalysis

p nitrophenol is synthesized using p nitrochlorobenzene and sodium hydroxide with phase transfer catalyst. Several reaction factors, such as catalyst type, the amounts of catalysts and sodium hydroxide, the concentration of sodium hydroxide solution as well as reaction time, affect greatly the yield of p nitrophenol. The optimum reaction conditions are as follows: A 1 used as phase transfer catalyst whose consumption is 6% (mole fraction) of p nitrochlorobenzene; the molar ratio of sodium hydroxide to p nitrochlorobenzene is 3:1; the concentration of sodium hydroxide solution is 50% (mass fraction). Nitrobenzene, whose molar amount is 2.45 times as much as that of p nitrochlorobenzene; reaction time is 7 h at 140 ℃ under normal pressure. The final yield of p nitrophenol is 83.6%.

Degradation of p-nitrophenol(PNP) in aqueous solution by mFe/Cu-air-PS system

In this study,batch experiments were conducted to investigate the performance of microscale Fe/Cu bimetallic particles-air-persulfate system(mFe/Cu-air-PS)for p-nitrophenol(PNP)treatment in aqueous solution.First,the optimal operating parameters(i.e.,aeration rate of 1.0 L/min,theoretical Cu mass loading(TMLCu)of 0.110 g Cu/g Fe,mFe/Cu dosage of 15 g/L,PS total dosage of 15 mmol/L,feeding times of PS of 5,initial pH 5.4)were obtained successively by single-factor experiments.Under the optimal conditions,high COD and TOC removal efficiencies(71.0%,65.8%)were obtained after 60 min treatment.Afterword,compared with control experiments(i.e.,mFe/Cu,air,PS,mFe/Cu-air,mFe/Cu–PS,air-PS and mFe-air-PS),mFe/Cu-air-PS system exerted superior performance for pollutants removal due to the synergistic effect between mFe/Cu,air and PS.In addition,the results of control experiments and radical quenching experiments indicate this reinforcement by feeding of PS was greater than by aeration in m Fe/Cu-air-PS system.Furthermore,the degradation intermediates of PNP in mFe/Cu-air-PS process were identified and measured by HPLC.Based on the detected intermediates,the degradation pathways of PNP were proposed comprehensively,which revealed that toxic and refractory PNP in aqueous solution could be decomposed effectively and transformed into lower toxicity intermediates.As a result,m Fe/Cu-air-PS system with the performance of oxidation combined reduction can be also a potential technology for the treatment of toxic and refractory PNP contained wastewater.

Effects of metal cations on sorption-desorption of p-nitrophenol onto wheat ash

The mutual effects of metal cations （Cu2＋, Pb2＋, Zn2＋, and Cd2＋） and p-nitrophenol （NP） on their adsorption desorption behavior onto wheat ash were studied. Results suggested that Cu2＋, Pb2＋, and Zn2＋ diminished the adsorption and increased the desorption of NP remarkably, while Cd2＋ had no such effect. In contrast, NP diminished the adsorption of Cu2＋, Pb2＋, and Zn2＋ onto ash, however, this suppression effect depended on the initial concentrations of metal cations. NP had no effect on Cd〉 adsorption on ash. Fourier transform infrared （FT-IR） and X-ray absorption spectroscopic （XAS） studies suggested the following mechanisms responsible for the metal suppression effect on NP adsorption： （1） large hydrated Cu2＋, Pb2＋, and Zn〉 shells occupied the surface of ash and prevent nonspecific adsorption of NP onto ash surface; （2） Cu2＋, Pb2＋, and Zn2＋ may block the micropores of ash, resulting in decreased adsorption of NP; （3） cornplexation of Cu2＋, Pb2＋, and Zn2＋ was likely via carboxyl, hydroxylic and phenolic groups of wheat ash and these same groups may also react with NP during adsorption. As a ＂soft acid＂, Cd2＋ is less efficient in the complexation of oxygencontaining acid groups than Cu2＋, Pb2＋, and Zn2＋. Thus, Cd2＋ had no effect on the adsorption of NP on wheat ash.

Facile synthesis of Au embedded CuOx-CeO2 core/shell nanospheres as highly reactive and sinter-resistant catalysts for catalytic hydrogenation of p-nitrophenol

Exploring cost-effective catalysts with high catalytic performance and long-term stability has always been a general concern for environment protection and energy conversion.Here,Au nanoparticles(NPs)embedded CuOx-CeO2 core/shell nanospheres(Au@CuOx-CeO2 CSNs)have been successfully prepared through a versatile one-pot method at ambient conditions.The spontaneous auto-redox reaction between HAuCl4 and Ce(OH)3 in aqueous solution triggered the self-assembly growth of micro-/nanostructural Au@CuOx-CeO2 CSNs.Meanwhile,the CuOx clusters in Au@CuOx-CeO2 CSNs are capable of improving the anti-sintering ability of Au NPs and providing synergistic catalysis benefits.As a result,the confined Au NPs exhibited extraordinary thermal stability even at a harsh thermal condition up to 700℃.In addition,before and after the severe calcination process,Au@CuOx-CeO2 CSNs can exhibit enhanced catalytic activity and excellent recyclability towards the hydrogenation of p-nitrophenol compared to previously reported nanocatalysts.The synergistic catalysis path between Au/CuOx/CeO2 triphasic interfaces was revealed by density functional theory(DFT)calculations.The CuOx clusters around the embedded Au NPs can provide moderate adsorption strength of p-nitrophenol,while the adjacent CeO2-supported Au NPs can facilitate the hydrogen dissociation to form H*species,which contributes to achieve the efficient reduction of p-nitrophenol.This study opens up new possibilities for developing high-efficient and sintering-resistant micro-/nanostructural nanocatalysts by exploiting multiphasic systems.

Flow synthesis of a novel zirconium-based UiO-66 nanofiltration membrane and its performance in the removal of p-nitrophenol from water

In this work,a thin zirconium-based UiO-66 membrane was successfully prepared on an alumina hollow fiber tube by flow synthesis,and was used in an attempt to remove p-nitrophenol from water through a nanofiltration process.Two main factors,including flow rate and synthesis time,were investigated to optimize the conditions for membrane growth.Under optimal synthesis conditions,a thin UiO-66 membrane of approximately 2 um in thickness was fabricated at a flow rate of4 mL.h for 30 h.The p-nitrophenol rejection rate for the as-prepared UiO-66 membrane applied in the removal of p-nitrophenol from water was only 78.1%due to the existence of membrane defects caused by coordinative defects during membrane formation.Post-synthetic modification of the UiO-66 membrane was carried out using organic linkers with the same flow approach to further improve the nanofiltration performance.The result showed that the p-nitrophenol rejection for the post-modified membrane was greatly improved and reached over 95%.Moreover,the post-modified UiO-66 membrane exhibited remarkable long-term operational stability,which is vital for practical application.