原子吸收光谱法研究巯基改性膨润土对Pb2+的吸附解吸

通过红外光谱(FTIR)法和扫描电镜(SEM)对钙基和巯基改性膨润土的官能团和表面结构进行了比较分析,以火焰原子吸收光谱法(FAAS)为检测手段,研究了巯基改性膨润土对Pb2+吸附的影响因素并优化了吸附条件,讨论了模拟酸雨解吸Pb2+的条件。比较了钙基和巯基改性膨润土作为吸附剂对水溶液中Pb2+的吸附、固定能力。研究表明：25 ℃下,吸附时间为60 min、离子强度为0.1 mol·L-1的KNO₃、pH 6.0时,5.0 g·L-1巯基改性膨润土对100 mg·L-1的Pb2+的吸附率达到98%以上,平衡吸附量达到67.27 mg·g-1,吸附能力明显优于钙基膨润土(9.667 mg·g-1),吸附过程符合Langmuir和Freundlich等温线方程。用pH 3.50的极限酸度模拟酸雨进行解吸,解吸率为0。表明该巯基改性膨润土对Pb2+具有很强的吸附、固定能力,适于重金属铅污染土壤中铅的吸附固定修复之用。     

Adsorption and solid phase extraction of 8-hydroxyquinoline from aqueous solutions by using natural bentonite

The nitrogen-heterocyclic compound 8-hydroxyquinoline (8HQ) is one of the components of coal tar and has a wide variety of uses in industry. Because of its toxicity for aquatic organisms and harmful effects for human health, the removal of 8HQ from aqueous solutions by adsorption onto natural bentonite was investigated in the present work. The experimental results show that the optimum pH value of 2.5 is favourable for the 8HQ adsorption. The experimental data were fitted well with the pseudo-second-order kinetic and Langmuir adsorption isotherm models at all studied temperatures. The maximum adsorption capacity obtained from the Langmuir isotherm model at 20 °C was 120.6 mg g⁻¹. The calculated thermodynamic results such as ΔG° (−24.3 kJ mol⁻¹) and ΔH° (−9.56 kJ mol⁻¹) indicate that the adsorption process is spontaneous and exothermic in nature. Solid phase extraction of 8HQ was also performed. The X-ray diffractometry (XRD), Fourier Transform Infrared (FTIR) and thermogravimetric (TG) analyses were carried out in order to confirm the 8HQ adsorption onto bentonite. According to the obtained results, natural bentonite can be a reusable and effective adsorbent for the removal of 8HQ.     

Synthesis of a Cationic Polymer-Bentonite Composite Utilizing a Simple and Green Process for the Adsorption of Acid Orange 7 from Aqueous Solution

A one-step, green process is reported for synthesis of poly([2-(methacryloyloxy)ethyl] trimethylammonium chloride) (PMETAC) modified bentonite (Bent-PMETAC). The Bent-PMETAC was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Zeta potential, scanning electron microscopy (SEM) and thermal gravimetric analysis (TGA). The results indicated that large amounts of PMETAC were successfully grafted on the surface and interlayers of bentonite, and changed the Zeta potential of the sample from negative to positive. Acid Orange 7 (AO 7), as adsorbate, was used to test the anionic dye adsorption of the samples. The batch adsorption results implied that this novel Bent-PMETAC adsorbent exhibited a much higher removal (95%) of AO 7 than bentonite (10%). In addition, the adsorption process was hardly influenced by pH, which is in good agreement with the results of the Zeta potential analysis. The equilibrium adsorption isotherms and the adsorption kinetics of AO 7 fitted well to the Langmuir model and pseudo-second-order kinetic model, respectively. The maximum adsorption capacity of AO 7 onto Bent-PMETAC was 208.6?mg·g^?1 at 298?K, which is much higher than for most other materials. Overall, the results indicated the Bent-PMETAC is a low-cost, simple synthesis and highly efficient adsorbent for anionic dye removal from aqueous solutions.     

壳聚糖/膨润土复合材料的制备及对甲基橙的吸附性能

利用壳聚糖和膨润土,合成了具有良好吸附效果的天然高分子絮凝吸附材料。用傅里叶变换红外光谱仪表征了原料和产物的结构,通过改变吸附时间、温度、pH值和甲基橙溶液质量浓度等条件,考察了合成材料对甲基橙的吸附性能。结果表明,吸附剂用量为10g/L,温度20℃,溶液pH为4.70,吸附平衡30min后,甲基橙去除率达90%以上,其吸附过程符合Langmuir吸附模型,是放热过程。     

LDH of NiZnFe and its composites with carbon nanotubes and data-palm biochar with efficient adsorption capacity for RB5 dye from aqueous solutions: Isotherm,kinetic, and thermodynamics studies

In the study, the layered double hydroxide (LDH) of NiZnFe and its composites with date-palm biochar (LDH-DPb) and carbon nanotubes (LDH-cnt) were synthesized for adsorbing reactive black 5 (RB5) dye from aqueous solutions. In the first 5 min, rapid adsorption was followed by a gradual increase in both dye uptake and removal efficiency of up to 60 min of starting time. In the investigated pH range (3.0–8.0), the removal efficiency linearly decreased while the sorption capacity linearly increased for all three adsorbents as their doses increased to 0.3 or 0.4 g following a decreasing trend up to 0.6 g. By increasing the initial RB5 concentration from 10 to 100 mg L⁻¹, the removal efficiency linearly decreased. A nearly perfect fitting of the pseudo-second-order kinetic model to the adsorption data was observed; however, the Elovich kinetic model showed the heterogeneous surface of adsorbents with chemisorption. At the solid–liquid interface, from a thermodynamics point of view, we obtained the nonspontaneous nature of the adsorption of RB5 dye of the studied adsorbents with an increased disorder, which supported the endothermic nature onto the studied adsorption process. Furthermore, a nearly perfect fitting of the Langmuir model was obtained to the adsorption data, thereby suggesting the monolayer adsorption of RB5 dye onto the studied adsorbents. In the Dubinin–Radushkevich model, a good agreement of the calculated adsorption capacities to the experimental values were observed and the chemical adsorption of RB5 dye on to the studied adsorbents was proposed based on E (8 – 16 kJ mol⁻¹).     

An optimization study using response surface methods on the decolorization of Reactive Blue 19 from aqueous solution by ultrasound

The decolorization of reactive dye C.I. Reactive Blue 19 from aqueous solution was studied by using ultrasound, activated carbon and combined ultrasound/activated carbon. The combined effects of independent variables, such as ultrasound power, temperature, time, activated carbon concentration, dye concentration and initial pH were investigated on the decolorization by using the central composite design. The decolorization of RB 19 was modelled statistically and optimized by means of the Matlab computer software. The decolorization were accomplished at optimum conditions by using ultrasound, activated carbon and combined ultrasound/activated carbon as 36%, 91% and 99.9%, respectively. The application of ultrasonic irradiation was found to be beneficial for decolorization of RB 19 from aqueous solution by adsorption.     

改性膨润土吸附染料废水的研究进展

综述了近几年来国内利用改性膨润土吸附处理染料废水的某些进展,探讨了改性方法、pH值、温度、吸附时间、膨润土投加量和共存离子等因素对膨润土吸附染料的影响。展望了改性膨润土吸附染料的发展趋势。     

Synergistic effects of combining ultrasound with the Fenton process in the degradation of Reactive Blue 19

The decoloration of reactive dye C.I. Reactive Blue 19 (RB 19) using combined ultrasound with the Fenton process has been investigated. The effect of varying the concentrations of hydrogen peroxide and iron sulfate, initial pH, ultrasonic power, initial dye concentration and dissolved gas on the decoloration and degradation efficiencies was measured. Calibration of the ultrasound systems was performed using calorimetric measurements and oxidative species monitoring using the Fricke dosimeter and degradations were carried out with a 20 kHz probe type transducer at 2, 4, 6 and 8 W cm⁻² of acoustic intensity at 15, 25, 50 and 75 mg L⁻¹ initial dye concentrations. First order rate kinetics was observed. It was found that while the degradation rate due to ultrasound alone was slow, sonication significantly accelerated the Fenton reaction. While the results were similar to those reported for other dyes, the effects occurred at lower concentrations. The rate and extent of decoloration of RB 19 increased with rising hydrogen peroxide concentration, ultrasonic powers and iron sulfate concentration but decreased with increasing dye concentration. An optimum pH value of pH = 3.5 was found. The rate of decoloration was higher when dissolved oxygen was present as compared with nitrogen and argon confirming the solution phase mechanism of the degradation.     

Adsorptive removal of congo red dye from aqueous solution using bael shell carbon

This study investigates the potential use of bael shell carbon (BSC) as an adsorbent for the removal of congo red (CR) dye from aqueous solution. The effect of various operational parameters such as contact time, temperature, pH, and dye concentration were studied. The adsorption kinetics was modeled by first-order reversible kinetics, pseudo-first-order kinetics, and pseudo-second-order kinetics. The dye uptake process obeyed the pseudo-second-order kinetic expression at pH 5.7, 7 and 8 whereas the pseudo-first-order kinetic model was fitted well at pH 9. Langmuir, Freundlich and Temkin adsorption models were applied to fit adsorption equilibrium data. The best-fitted data was obtained with the Freundlich model. Thermodynamic study showed that adsorption of CR onto BSC was endothermic in nature and favorable with the positive ΔH° value of 13.613 kJ/mol.     

Application of superparamagnetic microspheres for affinity adsorption and purification of glutathione

The superparamagnetic poly-(MA–DVB) microspheres with micron size were synthesized by the modified suspension polymerization method. Adsorption of glutathione by magnetic poly-(MA–DVB) microspheres with IDA-copper was investigated. The effect of solution pH value, affinity adsorption and desorption of glutathione was studied. The results showed that the optimum pH value for glutathione adsorption was found at pH=3.5, the maximum capacity for glutathione of magnetic poly-(MA–DVB) microspheres was estimated at 42.4 mg/g by fitting the experimental data to the Langmuir equation. The adsorption equilibrium of glutathione was obtained in about 10 min and the adsorbed glutathione was desorbed from the magnetic microspheres in about 30 min using NaCl buffer solution. The magnetic microspheres could be repeatedly utilized for the affinity adsorption of glutathione.     

Solar photocatalytic degradation of RB5 by ferrite bismuth nanoparticles synthesized via ultrasound

In this paper, the photocatalytic degradation of Reactive Black 5 (RB5) was investigated with ferrite bismuth synthesized via ultrasound under direct sunlight irradiation. The intensity of absorption peaks of RB5 gradually decreased by increasing the irradiation time and finally vanished in 50 min in acidic medium. The formation of new intermediate was observed in basic medium. The relative concentration of RB5 in solution and on the surface of ferrite bismuth (BiFeO₃) nanoparticles was considered during the experiment in acidic and basic media. The effects of various parameters such as amount of catalyst, concentration of dye, and pH of the solution have been studied on the dye degradation. The adsorption isotherm and the kinetic of photocatalytic degradation of RB5 were investigated. The adsorption constants in the dark and in the presence of sunlight irradiation were compared. The photocatalytic degradation mechanism of RB5 has been evaluated through the addition of some scavengers to the solution. In addition, the stability and reusability of the catalyst were examined in this work.     

巯基化、钠化和酸化膨润土对Cu2+，Pb2+和Zn2+的吸附性能研究

基于改性膨润土可能存在的优异吸附能力,利用傅里叶变换红外光谱仪和场发射扫描电镜研究分析了巯基化、钠化及酸化三种改性膨润土对Cu2+,Pb2+和Zn2+的等温吸附与竞争吸附实验结果。研究结果表明,在单一重金属离子的等温吸附环境下,巯基化膨润土对Cu2+,Pb2+和Zn2+的吸附能力明显优于其他两种材料,且对Pb2+具有一定的吸附选择性,吸附率达到近100%;在竞争吸附环境下,三种改性膨润土对Cu2+,Pb2+和Zn2+的吸附率都有所下降,但巯基化膨润土仍旧能够保持较好的吸附能力,较其他膨润土的吸附率大约高出10%～40%;三种重金属离子的吸附量均表现为Cu2+＞Pb2+＞Zn2+,这与三种重金属离子的竞争能力、化学亲和力等大小有关;膨润土的巯基改性,步骤简单且吸附重金属的效果好,对膨润土改性及其应用具有重要意义。     

Ultrasound-assisted synthesis of nanocomposites based on aromatic polyamide and modified ZnO nanoparticle for removal of toxic Cr(VI) from water

In this study, novel nanocomposites (NCs) of aromatic polyamide (PA) and surface modified ZnO nanoparticle with s-triazine heterocyclic ring was introduced for efficient removal of toxic hexavalent chromium (VI) from aqueous solution. The surface of ZnO nanoparticle was modified by s-triazine core silane coupling agent (ZnO-TSC) and PA/ZnO-TSC NCs with different amount of ZnO-TSC nanoparticles (0, 5, 10 and 15 wt%) were prepared by ultrasonic irradiation. The synthesized PA/ZnO-TSC NCs were characterized by FT-IR, XRD, FE-SEM, TEM and TGA methods. TEM images showed that ZnO nanoparticles were dispersed homogeneously in the polymer matrix. The adsorption experiments were carried out in batch mode to optimize various parameters like contact time, pH and concentration of metal ion that influence the adsorption rate. The maximum uptakes of Cr(VI) at pH 4.0 was 72%, 81%, 89% and 91% for pure PA, NC5%, NC10% and NC15%, respectively. The kinetic of adsorption was investigated and the pseudo second-order model is an appropriate model for interpretation of adsorption mechanism of Cr(VI) ions.     

Sorption and diffusion behaviours of strontium in sodium-type bentonite bed

Sorption and diffusion of Sr were examined using a typical Japanese bentonite. The experimental results showed that Sr sorption on the bentonite had linear relationship between the equilibrium Sr concentration and Sr sorption amount, i.e., Henry’s type of sorption, in wide initial Sr concentration from 1.1×10⁻⁹ to 1.1×10⁻⁴ mol L⁻¹ at pH 10. The Sr sorption also indicated pH dependence in pH range between 2 and 12. Sorption modelling calculation indicated that cation-exchange reactions contributed to Sr sorption in the pH range studied and a surface complexation reaction was predominant above pH 8. Diffusion of Sr in loosely compacted bentonite bed was described by pore and surface diffusion and surface complexation of Sr. Chemical-transport calculations reproduce the diffusion data at pH 5 using the cation-exchange parameters obtained in the analysis of the batch sorption experiment.     

Thermodynamic and kinetic parameters of ciprofloxacin adsorption onto modified coal fly ash from aqueous solution

Batch adsorption experiments were carried out for the removal of ciprofloxacin from aqueous solution using modified coal fly ash as adsorbent. The effects of various parameters such as contact time, initial solution concentration and temperature on the adsorption system were investigated. The optimum contact time was found to be 100 min. The isotherm adsorption data fit well with the Langmuir model, and the kinetic data fit well with the pseudo-second order and the intra-particle diffusion model. Intra-particle diffusion analysis demonstrates that ciprofloxacin diffuses quickly among the particles at the beginning of the adsorption process, and then the diffusion slows down and stabilizes. Thermodynamic parameters such as ΔG, ΔH and ΔS were also calculated. The negative Gibbs free energy change and the positive enthalpy change indicated the spontaneous and endothermic nature of the adsorption, and the positive entropy change indicated that the adsorption process was aided by increased randomness.     

Heterogeneous sono-Fenton process using pyrite nanorods prepared by non-thermal plasma for degradation of an anthraquinone dye

Natural pyrite (NP) was treated using oxygen and nitrogen non-thermal plasmas to form modified catalysts. Cleaning effect of the O₂ plasma by chemical etching leads to removal of impurities from catalyst surface and sputtering effect of the N₂ plasma results in formation of pyrite nanorods. The mentioned plasmas were applied separately or in the order of first O₂ and then N₂, respectively. The catalytic performance of the plasma-modified pyrites (PMPs) is better than the NP for treatment of Reactive Blue 69 (RB69) in heterogeneous sono-Fenton process (US/H₂O₂/PMP). The NP and the most effective modified pyrite (PMP₄) samples were characterized by XRD, FT-IR, SEM, EDX, XPS and BET analyses. The desired amounts were chosen for operational parameters including initial pH (5), H₂O₂ concentration (1 mM), PMP₄ dosage (0.6 g/L), dye concentration (20 mg/L), and ultrasonic power (300 W). Moreover, the effects of peroxydisulfate and inorganic salts on the degradation efficiency were investigated. Gas chromatography–mass spectrometry (GC–MS) method was applied to identify the generated intermediates and a plausible pathway was proposed for RB69 degradation. Environmentally-friendly modification of the NP, low amount of leached iron and repeated reusability at milder pH are the significant privileges of the PMP₄. The phytotoxicity test using Spirodela polyrrhiza verified the remarkable toxicity removal of the RB69 solution after the treatment process.     

Application of bifunctional Saccharomyces cerevisiae to remove lead(II) and cadmium(II) in aqueous solution

A magnetic adsorbent, EDTAD-functionalized Saccharomyces cerevisiae, has been synthesized to behave as an adsorbent for heavy metal ions by adjusting the pH value of the aqueous solution to make carboxyl and amino groups protonic or non-protonic. The bifunctional Saccharomyces cerevisiae (EMS) were used to remove lead(II) and cadmium(II) in solution in a batch system. The results showed that the adsorption capacity of the EMS for the heavy metal ions increased with increasing solution pH, and the maximum adsorption capacity (88.16 mg/g for Pb²⁺, 40.72 mg/g for Cd²⁺) at 10 °C was found to occur at pH 5.5 and 6.0, respectively. The adsorption process followed the Langmuir isotherm model. The regeneration experiments revealed that the EMS could be successfully reused.     

Facile synthesis of additive-assisted nano goethite powder and its application for fluoride remediation

The present article describes a novel synthesis route for nano-sized goethite (α-FeOOH) using hydrazine sulphate as an additive. The X-ray diffraction (XRD) peaks of synthesized powder matched well with those of α-FeOOH. Transmission electron microscopy (TEM) showed the particles of irregular shape in the range of 1–10 nm. Batch adsorption experiments for fluoride uptake were performed to study the influence of various experimental parameters such as contact time (10 min to 7 h), initial fluoride concentration (10–150 mg L⁻¹), pH (2–11.6) and the presence of competing anions. The time data fitted well to pseudo-second-order kinetic model. The fluoride removal passed through broad maxima in pH ranges of 6–8. High adsorption capacity of 59 mg g⁻¹ goethite was obtained. The isothermic data fitted well to Freundlich model. The presence of other ions namely chloride and sulphate adversely affected fluoride removal. Fluoride from contaminated water sample could be successfully brought down from 10.25 to 0.5 mg L⁻¹.     

Screening and optimization of highly effective ultrasound-assisted simultaneous adsorption of cationic dyes onto Mn-doped Fe3O4-nanoparticle-loaded activated carbon

The ultrasound-assisted simultaneous adsorption of brilliant green (BG) and malachite green (MG) onto Mn-doped Fe₃O₄ nanoparticle-loaded activated carbon (Mn-Fe₃O₄-NP-AC) as a novel adsorbent was investigated and analyzed using first derivative spectrophotometry. The adsorbent was characterized using FT-IR, FE-SEM, EDX and XRD. Plackett–Burman design was applied to reduce the total number of experiments and to optimize the ultrasound-assisted simultaneous adsorption procedure, where pH, adsorbent mass and sonication time (among six tested variables) were identified as the most significant factors. The effects of significant variables were further evaluated by a central composite design under response surface methodology. The significance of independent variables and their interactions was investigated by means of the analysis of variance (ANOVA) within 95% confidence level together with Pareto chart. Using this statistical tool, the optimized ultrasound-assisted simultaneous removal of basic dyes was obtained at 7.0, 0.02 g, 3 min for pH, adsorbent mass, and ultrasonication time, respectively. The maximum values of BG and MG uptake under these experimental conditions were found to be 99.50 and 99.00%, respectively. The adsorption process was found to be followed by the Langmuir isotherm and pseudo-second order model using equilibrium and kinetic studies, respectively. According to Langmuir isotherm model, the maximum adsorption capacities of the adsorbent were obtained to be 101.215 and 87.566 mg g⁻¹ for MG and BG, respectively. The value of apparent energy of adsorption obtained from non-linear Dubinin–Radushkevich model (4.348 and 4.337 kJ mol⁻¹ for MG and BG, respectively) suggested the physical adsorption of the dyes. The studies on the well regenerability of the adsorbent in addition to its high adsorption capacity make it promising for such adsorption applications.     

Adsorption of hexavalent chromium onto montmorillonite modified with hydroxyaluminum and cetyltrimethylammonium bromide

Aluminum hydroxypolycation and cetyltrimethylammonium bromide (CTMAB) were chosen to synthesize inorganic-organic pillared montmorillonite. Three different methods were employed for the intercalation. The characteristics of natural and modified montmorillonite were determined with X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), X-ray photoelectron spectrum (XPS), and zeta potential. It was found that aluminum hydroxypolycation and CTMAB had either entered the interlayer or sorbed on the external surface of the clay. Different intercalation orders can result in different structures. Batch adsorption of hexavalent chromium (Cr⁶⁺) onto modified montmorillonite was also investigated. The experimental data revealed that if aluminum hydroxypolycation was intercalated before CTMAB, the adsorption capacity was better than that of intercalated simultaneously or CTMAB pre-intercalated. The pH of the solution and environmental temperature had significant influences on the adsorption of Cr⁶⁺. The optimal pH for the removal was about 4, and the temperature of 298 K was best suitable. All adsorption processes were rapid during the first 5 min and reached equilibrium in 20 min. The adsorption kinetics can be described quite well by pseudo-second-order model. The adsorption rates of ACM, CAM and ACCOM were 3.814, 0.915, and 3.143 mg/g/min, respectively. The adsorption capacities of Cr⁶⁺ at 298 K on ACM, CAM, and ACCOM inferred from the Langmuir model were 11.970, 6.541, and 9.090 mg/g, respectively. The adsorption of Cr⁶⁺ on modified montmorillonite was mainly induced by the surface charge and the complexation reaction between CTMA⁺ and hexavalent chromium species at the edge of the clay particle.