Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use...Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.展开更多
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 elect...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.展开更多
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 ...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.展开更多
The kinetics and mechanisms of p-nitrophenol (PNP) biodegradation by Pseudomonas aeruginosa HS-D38 were investigated. PNP could be used by HS-D38 strain as the sole carbon, nitrogen and energy sources, and PNP was m...The kinetics and mechanisms of p-nitrophenol (PNP) biodegradation by Pseudomonas aeruginosa HS-D38 were investigated. PNP could be used by HS-D38 strain as the sole carbon, nitrogen and energy sources, and PNP was mineralized at the maximum concentration of 500 mg/L within 24 h in an mineral salt medium (MSM). The analytical results indicated that the biodegradation of PNP fit the first order kinetics model. The rate constant kpNp is 2.039 ×10^-2/h in MSM medium, KeNp+N is 3.603 × 10^-2/h with the addition of ammonium chloride and KPNP+c is 9.74 ×10^-3/h with additional glucose. The addition of ammonium chloride increased the degradation of PNP. On the contrary, the addition of glucose inhibited and delayed the biodegradation of PNP. Chemical analysis results by thin-layer chromatography (TLC), UV-Vis spectroscopy and gas chromatography (GC) techniques suggested that PNP was converted to hydroquinone (HQ) and further degraded via 1,2,4-benzenetriol (1 ,2,4-BT) pathway.展开更多
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 aroun...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.展开更多
A complex {[Cu(tib)2(H2O)2]·(NO3)2}n(1) has been synthesized under N,N-dimethylacetamide(DMA) and water conditions. The structure of complex 1 was characterized by single-crystal X-ray crystallography. ...A complex {[Cu(tib)2(H2O)2]·(NO3)2}n(1) has been synthesized under N,N-dimethylacetamide(DMA) and water conditions. The structure of complex 1 was characterized by single-crystal X-ray crystallography. It crystallizes in monoclinic, space group P21/n with a = 10.6273(7), b = 11.4184(7), c = 13.4215(8) A, β = 108.290(2)°, V = 1546.38(17)A3, Z = 2, F(000) = 798, Dc = 1.667 g/cm3 and m = 0.786 mm-1) Complex 1 exhibits a 3D network due to the existence of O–H…O interaction between coordinated water and nitrate anions. Furthermore, complex 1 has a good catalytic activity for the reduction of 4-nitrophenol in Na BH4 solution.展开更多
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 n...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.展开更多
Kinetic parameters of the decomposition of hazardous chemicals can be applied for the estimation of their thermal behavior under any temperature profile.Presented paper describes the application of the advanced kineti...Kinetic parameters of the decomposition of hazardous chemicals can be applied for the estimation of their thermal behavior under any temperature profile.Presented paper describes the application of the advanced kinetic approach for the determination of the thermal behavior also under adiabatic conditions occurring e.g.in batch reactors in case of cooling failure.The kinetics of the decomposition of different samples(different manufacturers and batches) of 3-methyl-4-nitrophenol were investigated by conventional DSC in non-isothermal(few heating rates varying from 0.25 to 8.0K/min) and isothermal(range of 200~260℃) modes.The kinetic parameters obtained with AKTS-Thermokinetics Software were applied for calculating reaction rate and progress under different heating rates and temperatures and verified by comparing simulated and experimental signals.After application of the heat balance to compare the amount of heat generated during reaction and its removal from the system,the knowledge of reaction rate at any temperature profiles allowed the determination of the temperature increase due to the self-heating in adiabatic and pseudo-adiabatic conditions.Applied advanced kinetic approach allowed simulation the course of the Heat-Wait-Search(HWS) mode of operation of adiabatic calorimeters.The thermal safety diagram depicting dependence of Time to Maximum Rate(TMR) on the initial temperature was calculated and compared with the results of HWS experiments carried out in the system with Ф-factor amounting to 3.2.The influence of the Ф-factor and reaction progress reached at the end of the HWS monitoring on the TMR is discussed.Presented calculations clearly indicate that even very minor reaction progress reduces the TMRad of 24h characteristic for a sample with initial reaction progress amounting to zero.Described estimation method can be verified by just one HWS-ARC,or by one correctly chosen ISO-ARC run of reasonable duration by knowing in advance the dependence of the TMR on the initial temperature for any Ф-factor.Proposed procedure results in significant shortening of the measuring time compared to a safety hazard approach based on series of ARC experiments carried out at the beginning of a process safety evaluation.展开更多
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 dischar...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.展开更多
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 ozo...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.展开更多
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 concentrat...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%.展开更多
In the present study,a film consisting of TiO_2 doped with copper was prepared for efficiently decomposing 4-nitrophenol(4-NP) by photocatalysis.The preparing process of TiO_2 doped with copper includes two procedures...In the present study,a film consisting of TiO_2 doped with copper was prepared for efficiently decomposing 4-nitrophenol(4-NP) by photocatalysis.The preparing process of TiO_2 doped with copper includes two procedures:preparing Ti(OH)_4 doped with copper and synthesizing anatase and rutile TiO_2 doped with copper.Ti(OH)_4 doped with copper could be achieved by hydrolyzing TiCl_4in the mixed solution containing deionized water and copper oxalate.The Ti(OH)_4 doped with copper can be gained successfully by the following procedures:rinsing,drying and vacuum drying.The Ti(OH)_4 doped with copper could be converted into anatase TiO_2 doped with copper and rutile TiO_2 doped with copper by incineration for 4.5 h at 723 and 1 073 K,respectively.Characterizations of anatase TiO_2 doped with copper and rutile TiO_2 doped with copper were determined by X-ray diffraction(XRD) and energy dispersion of X-ray(EDX).Anatase and rutile TiO_2 doped with copper were dissolved in a mixed solution containing isopropanol and diethylamine.Stainless electrode was submerged into with the solutions,the film of TiO_2 was formed by drying the thin layer at a ramp rate of 3℃/min until 373 K,and this temperature was held for 1 h.The temperature of the oven was subsequently increased to a final temperature of 823 K at a ramp rate of 3℃/min,and was held at this value for 1 h.The stainless steel covered with modified TiO_2 film was utilized as the anode.The stainless steel mesh was used as the cathode.The cathode and anode were connected with the source and immersed into the solution with 100 mg/L 4-NP.The whole reaction on photocatalysis was perfectly carried out after ultraviolet radiation and aerator were run.The experimental results showed that:cracking ratio of 4-NP ring,the removal ratio of chemical oxygen demand(COD) and total organic carbon(TOC) were respectively more than 90%,80% and 80% within 2 h.Degradation of 4-NP implied its potential application in associated wastewater.展开更多
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 propert...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.展开更多
3-methyl-4-nitrophenol (MNP) is the main by-product of the organophosphate insecticide fenitrothion (FT), used in locust control. MNP is highly toxic because it is an endocrine disruptor and then may cause adverse in ...3-methyl-4-nitrophenol (MNP) is the main by-product of the organophosphate insecticide fenitrothion (FT), used in locust control. MNP is highly toxic because it is an endocrine disruptor and then may cause adverse in the biological systems. Then, it is necessary to develop analytical methods for determination of this pollutant in the environment. In this sense, we reported herein the development of an electrochemical sensor for the detection of 3-methyl-4-nitrophenol (MNP), one of the metabolites of fenitrothion (FT), by using naked and modified carbon fiber microelectrode (CFME) by nickel tetrasulfonated phthalocyanine polymer (CFME/p-NiTSPc). The voltammogram showed that MNP presents one irreversible anodic peak corresponding to the oxidation of the phenol group at 0.9 V vs Ag/AgCl. The effect of pH of the buffer on the peak current and SWV parameters such as frequency, scan increment and pulse amplitude were investigated in order to optimize the electrochemical response of the sensor. The obtained results lead to the following optimum value: pH = 6;frequency = 25 Hz, pulse amplitude = 50 mV, scan increment = 10 mV. With these optimum values, the calibration curves show that the peak current varied linearly upon MNP concentration leading to a limit of detection (LoD) for naked CFME close to 3 μg/L whereas for CFME modified by p-NiTSPc, it reaches 0.75 μg/L. This results prove that the presence of p-NiTSPc increasing the sensitivity of the sensor could be used to monitor 3-methyl-4-nitrophenol residue in real matrix.展开更多
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 plasm...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.展开更多
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 compari...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.展开更多
文摘Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.
基金Supported by the National Natural Science Foundation of China(No.21676133)the Natural Science Foundation of Fujian Province(2014J01051)
文摘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.
基金the National Natural Science Foundation of China(Nos.20405008,20635020)
文摘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.
基金supported by the National Natural Science Foundation of China(No.30771429)the Specialized Research Fund for the Doctoral Program of Higher Education(No.20060511002)the Construction Fund for"211" Project of the Ministry of Education of China and the Excellent Middle-aged and Younger Talents Foundation of Hubei Province of China(No.Q200727005)
文摘The kinetics and mechanisms of p-nitrophenol (PNP) biodegradation by Pseudomonas aeruginosa HS-D38 were investigated. PNP could be used by HS-D38 strain as the sole carbon, nitrogen and energy sources, and PNP was mineralized at the maximum concentration of 500 mg/L within 24 h in an mineral salt medium (MSM). The analytical results indicated that the biodegradation of PNP fit the first order kinetics model. The rate constant kpNp is 2.039 ×10^-2/h in MSM medium, KeNp+N is 3.603 × 10^-2/h with the addition of ammonium chloride and KPNP+c is 9.74 ×10^-3/h with additional glucose. The addition of ammonium chloride increased the degradation of PNP. On the contrary, the addition of glucose inhibited and delayed the biodegradation of PNP. Chemical analysis results by thin-layer chromatography (TLC), UV-Vis spectroscopy and gas chromatography (GC) techniques suggested that PNP was converted to hydroquinone (HQ) and further degraded via 1,2,4-benzenetriol (1 ,2,4-BT) pathway.
文摘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.
基金Supported by the National Natural Science foundation of China(21301005,21671004,51404006)Natural Science Foundation of Anhui Province(1408085QB31)the open fund of Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control(KFK201508)
文摘A complex {[Cu(tib)2(H2O)2]·(NO3)2}n(1) has been synthesized under N,N-dimethylacetamide(DMA) and water conditions. The structure of complex 1 was characterized by single-crystal X-ray crystallography. It crystallizes in monoclinic, space group P21/n with a = 10.6273(7), b = 11.4184(7), c = 13.4215(8) A, β = 108.290(2)°, V = 1546.38(17)A3, Z = 2, F(000) = 798, Dc = 1.667 g/cm3 and m = 0.786 mm-1) Complex 1 exhibits a 3D network due to the existence of O–H…O interaction between coordinated water and nitrate anions. Furthermore, complex 1 has a good catalytic activity for the reduction of 4-nitrophenol in Na BH4 solution.
基金supported by the National Natural Science Foundation of China (Grant No. 10974044)the Foundation of State Key Laboratory of Hydrology-Water Resources and Hydraulic Engineering (Grant No. 2010490911)the Fundamental Research Funds for the Central Universities (Grant No. 2009B31514)
文摘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.
文摘Kinetic parameters of the decomposition of hazardous chemicals can be applied for the estimation of their thermal behavior under any temperature profile.Presented paper describes the application of the advanced kinetic approach for the determination of the thermal behavior also under adiabatic conditions occurring e.g.in batch reactors in case of cooling failure.The kinetics of the decomposition of different samples(different manufacturers and batches) of 3-methyl-4-nitrophenol were investigated by conventional DSC in non-isothermal(few heating rates varying from 0.25 to 8.0K/min) and isothermal(range of 200~260℃) modes.The kinetic parameters obtained with AKTS-Thermokinetics Software were applied for calculating reaction rate and progress under different heating rates and temperatures and verified by comparing simulated and experimental signals.After application of the heat balance to compare the amount of heat generated during reaction and its removal from the system,the knowledge of reaction rate at any temperature profiles allowed the determination of the temperature increase due to the self-heating in adiabatic and pseudo-adiabatic conditions.Applied advanced kinetic approach allowed simulation the course of the Heat-Wait-Search(HWS) mode of operation of adiabatic calorimeters.The thermal safety diagram depicting dependence of Time to Maximum Rate(TMR) on the initial temperature was calculated and compared with the results of HWS experiments carried out in the system with Ф-factor amounting to 3.2.The influence of the Ф-factor and reaction progress reached at the end of the HWS monitoring on the TMR is discussed.Presented calculations clearly indicate that even very minor reaction progress reduces the TMRad of 24h characteristic for a sample with initial reaction progress amounting to zero.Described estimation method can be verified by just one HWS-ARC,or by one correctly chosen ISO-ARC run of reasonable duration by knowing in advance the dependence of the TMR on the initial temperature for any Ф-factor.Proposed procedure results in significant shortening of the measuring time compared to a safety hazard approach based on series of ARC experiments carried out at the beginning of a process safety evaluation.
基金supported by National Natural Science Foundation of China(Grant No.21577011)the Fundamental Research Funds for the Central Universities(Grant No. DUT15QY23)
文摘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.
文摘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.
文摘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%.
基金Environmental Protection Department of Jiangsu Province,China(No.2013023)Jiangsu Key Laboratory of Industrial Water-Conservation & Emission Reduction,China(No.IWCER201202)
文摘In the present study,a film consisting of TiO_2 doped with copper was prepared for efficiently decomposing 4-nitrophenol(4-NP) by photocatalysis.The preparing process of TiO_2 doped with copper includes two procedures:preparing Ti(OH)_4 doped with copper and synthesizing anatase and rutile TiO_2 doped with copper.Ti(OH)_4 doped with copper could be achieved by hydrolyzing TiCl_4in the mixed solution containing deionized water and copper oxalate.The Ti(OH)_4 doped with copper can be gained successfully by the following procedures:rinsing,drying and vacuum drying.The Ti(OH)_4 doped with copper could be converted into anatase TiO_2 doped with copper and rutile TiO_2 doped with copper by incineration for 4.5 h at 723 and 1 073 K,respectively.Characterizations of anatase TiO_2 doped with copper and rutile TiO_2 doped with copper were determined by X-ray diffraction(XRD) and energy dispersion of X-ray(EDX).Anatase and rutile TiO_2 doped with copper were dissolved in a mixed solution containing isopropanol and diethylamine.Stainless electrode was submerged into with the solutions,the film of TiO_2 was formed by drying the thin layer at a ramp rate of 3℃/min until 373 K,and this temperature was held for 1 h.The temperature of the oven was subsequently increased to a final temperature of 823 K at a ramp rate of 3℃/min,and was held at this value for 1 h.The stainless steel covered with modified TiO_2 film was utilized as the anode.The stainless steel mesh was used as the cathode.The cathode and anode were connected with the source and immersed into the solution with 100 mg/L 4-NP.The whole reaction on photocatalysis was perfectly carried out after ultraviolet radiation and aerator were run.The experimental results showed that:cracking ratio of 4-NP ring,the removal ratio of chemical oxygen demand(COD) and total organic carbon(TOC) were respectively more than 90%,80% and 80% within 2 h.Degradation of 4-NP implied its potential application in associated wastewater.
文摘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.
文摘3-methyl-4-nitrophenol (MNP) is the main by-product of the organophosphate insecticide fenitrothion (FT), used in locust control. MNP is highly toxic because it is an endocrine disruptor and then may cause adverse in the biological systems. Then, it is necessary to develop analytical methods for determination of this pollutant in the environment. In this sense, we reported herein the development of an electrochemical sensor for the detection of 3-methyl-4-nitrophenol (MNP), one of the metabolites of fenitrothion (FT), by using naked and modified carbon fiber microelectrode (CFME) by nickel tetrasulfonated phthalocyanine polymer (CFME/p-NiTSPc). The voltammogram showed that MNP presents one irreversible anodic peak corresponding to the oxidation of the phenol group at 0.9 V vs Ag/AgCl. The effect of pH of the buffer on the peak current and SWV parameters such as frequency, scan increment and pulse amplitude were investigated in order to optimize the electrochemical response of the sensor. The obtained results lead to the following optimum value: pH = 6;frequency = 25 Hz, pulse amplitude = 50 mV, scan increment = 10 mV. With these optimum values, the calibration curves show that the peak current varied linearly upon MNP concentration leading to a limit of detection (LoD) for naked CFME close to 3 μg/L whereas for CFME modified by p-NiTSPc, it reaches 0.75 μg/L. This results prove that the presence of p-NiTSPc increasing the sensitivity of the sensor could be used to monitor 3-methyl-4-nitrophenol residue in real matrix.
基金Supported by the National Basic Research Program (No.2003CB615702) and the National Natural Science Foundation of Chin(No.20436030).
文摘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.
文摘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.
基金Supported by the Special Funds for Major State Basic Research Program of China (No.2003CB615702), the National Natural Science Foundation of China (No.20636020) and the Natural Science Foundation of Jiangsu Province (No.BK2006722).