Removal of the environmental pollutant carbamazepine using molecular imprinted adsorbents: Molecular simulation, adsorption properties, and mechanisms.

Carbamazepine (CBZ) is a typical pharmaceutical residue commonly found in aqueous environments, but its removal through activated carbon or advanced oxidation processes is often disrupted by co-existing organic matter. An imprinting system which consisted of the target pollutant CBZ (template molecule) and 10 different kinds of functional monomers was constructed via molecular simulation to screen for appropriate monomers, thereby addressing CBZ removal disruptions. An annealing method simulation was used to search for stable, low-energy conformations of the template-monomer interaction system to calculate the binding energy of these different monomers with CBZ. The order of binding affinity calculated was: 4-vinylbenzoic acid > itaconic acid > methacrylic acid, which was consistent with the experimental observations. The adsorption capacity of the molecular imprinted polymer (MIP) prepared using 4-vinylbenzoic acid reached 28.40 mg/g, and the imprinting factor reached 2.72. The simulation and measurement of the ultraviolet spectrum of the imprinting system showed that a new interaction system was formed between the template and monomers, and that multiple binding conformations between them took place when specific recognition occurred. Energy calculation and hydrogen bond analysis revealed that the van der Waals force, including the π-π conjugate and electrostatic forces including hydrogen bonding, played an important role during selective adsorption, which was confirmed by infrared spectroscopy analysis.

[Cathode Electric Field Enhanced Removal of Nitrobenzene from Aqueous Solution Based on Activated Carbon Fibers (ACF)-Ozone Technique].

Through the environmental factors impact experiments,such as current intensity,initial pH value of the reaction solution,and the type and concentration of the electrolyte,effect and mechanism of electrochemically enhanced removal of nitrobenzene from aqueous solution on activated carbon fibers (ACF)-ozone technique were studied.The result showed that compared with the ACF-O3 system,the removal efficiency of NB in electrochemically enhanced ACF-O3 system was significantly improved.The effect of current intensity on the NB removal efficiency in the electrochemically enhanced ACF-O3 system was not significant.O3 concentration had some effect on the NB removal efficiency.The pH value of the initial reaction solution had a great influence on the catalytic activity of ACF in ACF-O3 system.The presence of inorganic salts such as sodium sulfate,sodium nitrate and sodium chloride inhibited the catalytic ability of ACF in O3 system.In addition,ACF was destroyed by ozone and the promoting effect of ACF was reduced.When the cathode electric field was applied on the surface of ACF,the removal effect of the organic compounds by ACF-O3 was improved significantly and the structure of ACF was not destroyed by ozone.

Delta manganese dioxide nanosheets decorated magnesium wire for the degradation of methyl orange.

MnO2-decorated magnesium wire composite (MnO2-M) was fabricated via a simple hydrothermal reaction and accompanied by the calcination process (MnO2/Mn3O4-M). To clarify the optimized reaction condition of δ-MnO2 in the system, the effect of different pH, temperature and pollutant concentration of methyl orange (MO) for degradation process were investigated. Experimental results showed that MnO2-M achieves a high removal rate of 76% (2h, at 25°C) in the presence of H2O2 at pH 2.5, which is higher than that of MnO2/Mn3O4-M (54%). Moreover, reaction temperature and MO dye concentration have little effect on the degradation performance of MnO2-M. This implies the stability of the as-prepared samples and good potential in the application of wastewater treatment.

[Study on the Preparation of A New Composite Coagulant: Poly-Ferric-Titanium-Sulfate and Analysis of FTIR Spectrum and UV-Vis Spectrum].

Composite coagulants have drawn a widespread attention recently for its superior coagulation-flocculation performance. Fe and Ti based coagulants, as a kind of inorganic metal water treatment agent, h have received huge attention, but there is little study about the preparation and characterization of composite coagulate composite with Ti4+. In this paper we prepared a composite coagulant, in which the Ti (SO4)2 was introduced as coordination complexes, PO3-4 as stabilizer and complexant. Then, the FT-Infra Red spectrum (FT-IR) and ultraviolet/visible absorption spectrum (UV-Vis) were adopted to characterizse the changes of chemical group, species distribution of coagulants in case of varies Ti/Fe, P/Fe and OH/Fe molar ratio. The results shows other than simple mixture of the raw materials, the introduction of Ti4+ and ­PO4 group synthesized the chemical group bond as Ti­O, ­Fe­P­Fe­ and ­Ti­P­Ti­, which were beneficial to the degree of polymerization and increased the stability of the product. Furthermore, when the Ti/Fe molar ratio of 1∶8, P/Fe was in the range of 0.2~0.3, the optimal material is suitable for the generation of Fe­P­Ti­ chemistry bond and medium polymer as Fe6(OH)6+12，[Fex(OH)y]2H2PO(6x-2y-1)+4. Whereas, too much addition of Ti4+, PO3-4 and HCO-3 deteriorated the polymer structure, leading to the presentation of precipitate as TiO2, Ti3(PO4)4 and FePO4, which will decrease the coagulation performance.

[Study on the Catalytic Kinetic Spectrophotometric Determination of Trace Amounts of Iron(â ¢) and Its Reaction Mechanism].

A catalytic kinetic spectrophotometric method, which is based on the catalytic effect of Fe(Ⅲ) on the fading reaction between potassium persulfate(K2S2O8) and methyl red(MR) in the solution of 0.30 mol·L-1 hydrochloric acid, for the determination of trace amounts of Fe(Ⅲ) has been investigated. A novel detection system, Fe(Ⅲ)-HCl-K2S2O8-MR, has been developed. The optimum experimental conditions for the determination of trace amounts of Fe(Ⅲ) were found on the basis of orthogonal test. The kinetics parameters and equation of this fading reaction of MR were studied. Its reaction mechanism was discussed. The results show that there is a good linear relationship between the variation of MR absorbance at the maximum absorption wavelength of 518 nm and the concentration of Fe(Ⅲ) under the optimum experimental conditions: ln(A0/A)=1.334 1+0.001 0, the correlation coefficient is 0.999 1. The kinetic research shows that the reaction order with respect to Fe(Ⅲ) is 1 and the overall fading reaction is a pseudo-first order reaction. The apparent activation energy of the fading reaction of MR is 69.88 kJ·mol-1. Furthermore, the catalytic effects of Fe(Ⅲ) on this fading reaction is confirmed by its reaction mechanism. This novel method for the determination of trace Fe(Ⅲ) has never previously been published so far. Trace amounts of Fe(Ⅲ) can be selectively determined by this catalytic kinetic spectrophotometric method with high precision and accuracy. This method is simple and its reagents used are cheap and available. Its sensitivity is higher than that of conventional spectrophtometry with detection limit of 0.005 mg·L-1. This detection system is stable. This proposed method has been applied to the determination of trace amounts of Fe(Ⅲ) in food and water samples with satisfactory results. Relative standard deviation of the detection results is 1.18%～2.11%. Average recovery rate of the detection results is 98.0%～104.0%.

[The Preparation and Characterization of a New Solid Coagulant: Polymeric Ferric Silicate Sulfate].

As one of the most important water treatment agents, polysilicate coagulant, has been playing an important role in coagulation- flocculation, but it is prone to lose stability due to self-polymerization and the forming of silica gel. Therefore, research on the preparation of stable polysilicate coagulant has attract great attention. A new method to prepare a stable polysilicate coagulant (PSPF), was proposed in this paper. Its structure and morphology were characterized by using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) respectively. Fe species in PSPF was analyzed via Fe-Ferron complexation timed spectrophotometric method. The performance of PSPF was assessed by measuring micro-polluted water treatment efficiency. Primary chemicals, such as ferrous sulfate, sodium silicate, potassium dihydrogen phosphate, sodium carbonate, were used. The influence of those parameters affecting the preparation of PSPF, such as nSi/nFe, nP/nFe and nOH/nFe molar ratios were examined. The results showed that nSi/nFe of 1∶4, nP/nFe of 1∶6 and nOH/nFe of 1∶10 under 60 ℃ water bath for 30 min was the optimum condition for preparation. The FTIR spectrum indicated that PSPF was a kind of high molecular polymer, containing new groups (e.g., Si­O­Si and Fe­O­Si), which could increase the molecular weight，molecular chain and coagulation-flocculation efficiency. PSPF presented a cluster appearance similar to a network structure, which was conductive to adsorption-bridging capacity and precipitation sweeping. The increase of Fe(b) and Fe(c) as a result of Si increasing in PSPF improved the polymerization and solidification. The coagulation behaviors of PSPF that were largely affected by the coagulant dosage and pH, indicated that for pH and dosage at 6 and 8 mg·L-1, respectively, the residual turbidity and UV254 removal efficiency could achieve 0.33 NTU and 58.6%, respectively.

[Study on the Influence of Mineralizer on the Preparation of Calcium Aluminates Based on Infrared Spectroscopy].

In this study, effect of mineralizer on the structure and spectraproperties of calcium aluminates formation was extensively studied. Medium or low-grade bauxite and calcium carbonate were used as raw material and mineralizer CaF2 as additive. Calcium aluminates can be obtained after mixing fully, calcination and grinding. The prepared calcium aluminates can be directly used for the production of polyaluminiumchloride (PAC), polymeric aluminum sulfate, sodium aluminate and some other water treatment agents. The calcium aluminates preparation technology was optimized by investigating the mass ratio of raw materials (bauxiteand calcium carbonate) and mineralizer CaF2 dosage. The structure and spectra properties of bauxite and calcium aluminates were characterized by Fourier transform infrared(FTIR) spectroscopy analysis and the mineralization mechanism of the mineralizer was studied. FTIR spectra indicated that the addition of mineralizer promoted the decomposition and transformation of the diaspore, gibbsite and kaolinite, the decomposition of calcium carbonate, and more adequately reaction between bauxite and calcium carbonate. In addition, not only Ca in calcium carbonate and Si in bauxite were more readily reacted, but also Si-O, Si-O-Al and Al-Si bonds in the bauxite were more fractured which contributed to the release of Al in bauxite, and therefore, the dissolution rate of Al2O3 could be improved. The dissolution rate of Al2O3 can be promoted effectively when the mineralizer CaF2 was added in a mass ratio amount of 3%. And the mineralizer CaF2 cannot be fully functioned, when its dosage was in a mass percent of 1. 5%. Low-grade bauxite was easier to sinter for the preparation of calcium aluminates comparing with the highgrade one. The optimum material ratio for the preparation of calcium aluminates calcium at 1 250 °C was the mass ratio between bauxite and calcium carbonate of 1 : 0. 6 and mineralizer CaF2 mass ratio percent of 3%.

[Determination of trace amounts of nitrite and its chemical reaction kinetics].

A catalytic kinetic spectrophotometric method for the determination of nitrite, NO2(-)-S2O8(2-)-MR, was developed. It is based on the fading reaction of methyl red (MR) oxidized by potassium persulfate which can be catalyzed by NO2- in the medium of dilute HCl. The optimum experimental conditions were gained by combining single factor experiments with orthogonal experiments. Calibration curve, detection limit, precision, and anti-interference under the optimum experimental conditions were researched. Its kinetics principles and parameters were discussed. Its quantitative principle was investigated. The results show that the optimum experimental conditions of this method should be as follows: 1.0 mL 0.3 mol x L(-1) HCl, 1.0 mL 0.01 mol x L(-1) K2S2O8, 0.6 mL 0.2 g x L(-1) MR, reaction temperature 80 degrees C and reaction time 9 min. The principles for the quantitative determination of trace nitrite is that variation of MR concentration at the maximum absorption wavelength of 518 nm, ln(A0/A), shows a good linear relationship with the concentration of NO2- under the optimum experimental conditions. Its determination range is 0.01-0.80 mg x L(-1) and its detection limit is 0.007 mg x L(-1). The kinetic characteristics are that the reaction order in NO2- is 1 and the fading reaction is a pseudo first order reaction. Its apparent activation energy is 85.04 kJ x mol(-1). Its apparent rate constant is 0.021 4 min(-1), and the half-life is 32.39 min at 80 degrees C. The kinetic principle is that the variation of MR concentration is directly proportional to the concentration of NO2-, ln(A0/A) = kc(NO2-). This new method for the determination of trace nitrite has never previously been reported in the published literature so far. It is highly sensitive and selective. Most of the common ions don't interfere with the determination of nitrite. This method has the advantages of convenient operation and the regents used are cheap and nontoxic. It was applied to the determination of trace nitrite in food and water samples with satisfactory results.

[Study on infrared spectroscopy of cationic polyacrylamide initiated by ultraviolet].

Cationic Polyacrylamide P(AM-DAC-BA) was synthesized by UV initiation, with acrylamide (AM), acryloyloxyethyl trimethyl ammonium chloride (DAC), butyl acrylate (BA) as the monomers. P(AM-DAC-BA). UV spectroscopy and infrared spectroscopy were employed to study the structural characteristics. Attributions of typical infrared vibrational frequencies in AM/DAC/BA/P(AM-DAC-BA) were analysed. By comparing with infrared spectroscopy of the monomers, symmetrical characteristic of P(AM-DAC-BA) increasesd, and the infrared spectroscopy of polymerization product was simpler. The intrinsic viscosity increased with the increase in light intensity, BA content, photoinitiator concentration and illumination time. The groups of -CONH2, -COOCH2(C=O), -COOCH2--(C-O-C), -CH2--N(CH3 )3 group in AM, DAC, BA were selected as characteristic absorption peaks for studying. With the increase in light intensity and BA content, the characteristic peak areas increased. With the increase in photoinitiator concentration, the characteristic peak areas decreased. The characteristic peak areas decreased firstly and then increased with increasing the illumination time. But the corresponding characteristic IR absorption peaks of P(AM-DAC-BA) were similar, and the positions of characteristic peaks were basically the same.

[Determination of cationic degree in PDA with near infrared reflectance spectroscopy].

Cationic degree has been investigated as an important factor in polyacrylamide materials. Diallyl dimethyl ammonium chloride and acrylamide (PDA) was grafted by free radical polymerisation of acrylamide monomer (AM) onto the cationic monomer dimethyl diallyl ammonium chloride (DMDAAC). In the present study, near infrared reflectance spectroscopy (NIRS) was used as a rapid and accurate method to determine the cationic degree in the PDA. In this experiment, the near infrared spectra of 37 PDA samples that were self-prepared in the laboratory from 900.00 to 1 700.00 were collected. The characteristic peaks and the entire spectrum segment as the input layer neurons in radical basis function (RBF) were investigated for establishing the mathematical conversion NIRS calibration mode. For reduction of the NIR spectrum noise, the wavelet analysis was used as pretreatment process. The measured value was determined by using precipitation titration and a comparison between the simulated value and measured value was made. It was found that the external validation determination coefficient was more than 0.9, and the simulation value is in good agreement with the measured value. The statistics analysis showed that there was no significant difference between simulated value and measured value. Therefore, the calibration model (RBF neural network) established in this paper exhibited a remarkable feasibility for predicting the cationic degree of PDA based on the near infrared spectroscopy.

[Ultraviolet-initiated synthesis and characterization of anionic polyacrylamide].

APAM was prepared under the action of composite initiator and UV irradiation, using acryl amide (AM), 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and acrylic acid (AA) as raw materials. The paper studied the effect of proportion between monomers, monomer ratio, initiator concentration and other factors on intrinsic viscosity of the polymer, and optimized preparation conditions. The chemical structure and thermal stability of APAM were characterized by UV, FTIR, SEM and DTA-TGA respectively. The results showed that the APAM with the intrinsic viscosity 1.6 x 10(3) mL x g(-1) can prepared when the proportion between monomers was 70 : 10 : 10, the monomer ratio was 40%, initiator concentration was 0.20%, pH was 9 and the illumination time was 60 min.

[Spectroscopy study on the selectively distinguishing cefalexin with the molecular imprinted polymer].

Molecular imprinted polymers of cefalexin (CFL) were prepared by non-covalent molecular imprinting technique in the present paper. Using CFL as template molecule, acrylamide (AM) or methacrylic acid (MAA) as functional monomer, ethylene dimethacrylate (EGDMA) as cross-linker, AIBN as initiator and methanol as porogen agent, different molecularly imprinted polymers (MIPs) of CFL were synthesized by bulk or suspension polymerization as synthetic method. The intermolecular action between AM and CFL was investigated by UV and IR spectrophotometric analysis, and the results indicated that polymerizing functional monomer AM could bond effectively with template molecule CFL. By using UV spectrophotometric analysis method, it was found that the MIP prepared with AM-EGDMA by bulk polymerization showed the highest binding capacity for CFL. Test of selective adsorption made clear that the MIP represented more excellent identification property to CFL than to cefadroxol and ampicillin. The MIPs were used as solid-phase extraction sorbent for extraction and enrichment of CFL in actual samples. And the recoveries for CFL extraction were found to be 99.3%-99.7% (n=3), demonstrating the feasibility of the prepared MIPs for CFL extraction.

[Preparation and structural analysis of diatomite-supported SPFS flocculant].

In the presetn study, polymerized ferric sulphate (PFS) flocculant was prepared and tested. In the preparation of PFS flocculant, industrial by-product ferrous sulfate heptahydrate (FeSO4.7H2O) was reused as the main material. By composition with diatomite and drying up at certain temperature in vacuum drying oven, solid PFS flocculant was produced. Structural characteristics of the new flocculant product were examined through infrared spectroscopy and scanning electron microscopy (SEM), which showed that by compositing with diatomite, new group bridging emerged in the structure of PFS, which made the bond of groups stronger. In addition, part of the metalic contents in diatomite was polymerized with PFS, the product of which was polymerized ferric complex. Furthermore, the absorbing and agglomerating capacity of the diatomite carrier was significant. Considering the factors listed above, the new solid polymerized ferric sulphate (SPFS) flocculant was characterized with a larger molecule structure and enhanced absorbing, bridging and rolling sweep capacities. Through orthogonal experiment, optimum conditions of synthesis were as follows: the ratio of FeSO4.7H2O/diatomite in weight was 43/1, the reaction time is 1 h and the reaction temperature is 55 degrees C. By wastewater treatment experiment, it was found that the synthetic products showed good flocculation performance in the treatment of domestic sewage, the removal of COD was 80.00% and the removal of turbidity was 99.98%.

[Topography structure and flocculation mechanism of polymeric phosphate ferric sulfate (PPFS)].

Characteristics of polymeric phosphate ferric sulfate (PPFS) were investigated using FTIR (Fourier transform infrared spectrometer), XRD (X-ray diffraction) and SEM (scanning electron microscope) in the present study. The formed PPFS structure and morphology were stereo meshwork, which was clustered and close to coral reef, synthesis of high charge density, bioactive polyhydroxy and mixed polynuclear complex PPFS. The results showed that charge neutralization of PPFS had not played a decisive role in the coagulation beaker test and the zeta potential proved that PPFS was largely affected by bridging and netting sweep. Therefore, the coagulation mechanisms of PPFS were mainly composed of charge neutralization, adsorption bridging and netting sweep mechanisms.

[Study of ferric species distribution in polymeric phosphate ferric sulfate (PPFs)].

Based on the strong polymeric role of phosphate (PO4-) on the PFS, PO4(3-) was introduced in the ferric sulfate (PFS), and a new type of composite flocculant polymeric phosphate ferric sulfate (PPFS) was developed. The study includes the preparation of PPFS, and erric species distribution in PFSS was investigated by ultraviolet-visible spectrum method, infrared spectrum method and Fe-ferron complexation timed spectrophotometry method. The ultraviolet-visible spectrum showed that the change in the spectral curve of the different pH polymer ferric sulfate flocculants is corresponding to the flocculation morphology. Infrared spectra showed that the -P-O or -P=O vibration exists in the PPFS, certificated the ferric ion in PFS and phosphate caused the reaction, and produced the phosphate ferric polymer; and Fe-ferron complexation timed spectrophotometry showed that the amount of Fe(c) in polymeric phosphate ferric sulfate (PPFS) flocculants was the most in the three species, while the amount of Fe(a) and Fe(b) was small, that is PPFS mainly exists in the form of phosphate ferric polymer.

[Determination of acrylamide in PDA with near infrared reflectance spectroscopy].

In the present study, near infrared reflectance spectroscopy(NIRS) was used as a rapid and accurate method to determine the residual of acrylamide monomer in the product of diallyl dimethyl ammonium chloride and acrylamide. In this experiment 38 products were used which were self-prepared in the laboratory, then near infrared spectra of the product were scanned, seven bands were selected, the characteristic peaks of each band were used as the independent variables, and the absorption peak was used as the dependent variable, using partial least squares (PLS) method to establish the mathematical conversion near infrared reflectance spectroscopy (NIRS) calibration model. In the analysis of the spectrum, using wavelet analysis as the method of reducing the noise of spectrum, and with comparison of the simulated value and measured value, the measured value was determined by using UV spectrum, the external validation determination coefficient was found to be 0.99, and the distribution trend forecast was good. Statistics showed that there was no significant difference between simulated value and measured value. The results show that using the calibration model established by the data of near infrared spectroscopy to predict the residual AM monomer in PDA is of high feasibility.

[A new method for the preparation of potassium ferrate and spectroscopic characterization].

Calcium hypochlorite was used as the raw material for preparation of the high purity potassium ferrate. The study includes the effects of reaction temperature, recrystallization temperature, reaction time, Ca(ClO)2 dosage, and the amount of calcium hypochlorite on the yield. It was determined that when the reaction temperature was 25 degrees C, recrystallization temperature 0 degree C and reaction time 40 min, the yield was more than 75%. The purity was detected by direct spectrophotometric method to be more than 92%. The product was characterized by infrated spectrum(IR), X-ray diffraction (XRD) and ultraviolet spectrum (UV) methods and proved to be potassium ferrate that was prepared by calcium hypochlorite as the raw material.

[Decoloration and degradation of direct pink 12B by microwave-promoted heterogeneous Fenton-like reaction].

Microwave-promoted heterogeneous Fenton-like reaction, the combination of Fenton-like reagent with microwave, is an efficient method for waste water treatment. In the present paper, the degradation of direct pink 12B (a kind of organic dye) was studied using this method was studied. Through numerous experiments, the influences of various parameters including the initial pH value, dosage of Fe-Ni-Mn/AlO3, dosage of H2O2 and microwave were investigated intensively. The characteristic curve of direct pink12B, the concentration-absorbency curve of direct pink12B, the orthogonal optimization tests and comparative tests were given. In this paper, the mechanisms of this reaction were also been probed. It is concluded from the experiments that the microwave can accelerate the process of degradation effectively. Under optimal conditions, the overall color removal was more than 99.0% within 10 min. In the study, all the characterization was carried out using UV-Vis spectral-analysis.

[Transport kinetics of Pb(II) through bulk liquid membrane using PC-88A as carrier].

The effects of stirring speed, carrier concentration and reaction temperature on the transport of Pb(II) ion through bulk liquid membrane were studied with chloroform as membrane solvent and 2-ethylhexyl phosphonic acid-mono-2-ethylhexylester as carrier. The Pb(II) ions concentrations of feed phase and stripping phase were assayed by atomic absorption spectroscopy. The kinetic parameters, including apparent rate constants of Pb(II) ion extraction and re-extraction reactions, the maximum concentration of Pb(II) ion in the liquid membrane, the time of the maximum value of maximum concentration of Pb(II) ion in the liquid membrane and the maximum entry and exit fluxes of Pb(II) ion through the liquid membrane of the extraction and stripping reactions, were evaluated. The apparent activation energy value is 31.65 kJ x mol(-1) for extraction and 23.11 kJ mol(-1) for stripping. The results indicate that good agreement between experimental data and theoretical predictions could be achieved and the kinetics of Pb(II) transport could be evaluated by two consecutive irreversible pseudo-first order reactions. In this condition the chemical reaction is a procedure of controlled reaction rates.

[Decoloration and degradation of rhodamine B by microwave-promoted Fenton-like reaction].

Microwave-promoted Fenton-like reaction, the combination of Fenton-like reagent with microwave, is an efficient method for waste water treatment. In the present paper, the degradation of rhodamine B (a kind of organic dye) using this method was studied. Through numerous experiments, the influences of various parameters including the initial pH value, reaction time, dosage of K2Cr2O7, dosage of H2O2 and microwave were investigated intensively. The characteristic curve of rhodamine B, the concentration-absorbency curve of rhodamine B, the orthogonal optimization tests and comparative tests were given. The mechanism of this reaction was also probed. It is concluded from the experiments that the microwave can accelerate the process of degradation effectively. Under optimal conditions, the overall color removal was more than 99.9% within 9 min. In the study, the method for characterization was entirely UV-Vis spectral analysis.