Freeze–dried synthesized bifunctional biopolymer nanocomposite for efficient fluoride removal and antibacterial activity

Local fluoride contamination and bacterial infections in potable water have dangerous effects on the human body and are today a global concern. In this study, we have synthesized a pH-responsive bifunctional biopolymer nanocomposite (HAZ) of humic acid with incorporating aluminum zirconium bimetallic oxide by deep freeze–drying method. Fast nucleation and interconnection of nanoparticles form a highly porous network because of sublimation of frozen HAZ. This duo nanocomposite has efficiently worked for fluoride removal and showed potent antibacterial activity against the Escherichia coli Gram-negative and Staphylococcus aureus Gram-positive bacteria. The X-ray photoelectron spectroscopy (XPS) analysis demonstrates that the hydroxyl groups act as a pivot in the ion exchange process of adsorption, each element of bimetallic oxide primarily takes part in the adsorption mechanism. The maximum adsorption capacity of the adsorbent was 180.62 mg/g at pH seven. Thermodynamic parameters like Gibbs free energy change (ΔG⁰), entropy (ΔS⁰), and enthalpy (ΔH⁰) indicate that the process was endothermic, feasible, and taken place by a chemisorption mechanism. This is the first novel freeze–dried bifunctional biopolymer nanocomposite composed of humic acid natural polymer incorporated with Al–Zr metal oxide, and it exhibited three times higher adsorption efficacy with excellent antibacterial action at a concentration of 5 µg/mL of the nanocomposite.     

Ciprofloxacin adsorption from aqueous solution onto chemically prepared carbon from date palm leaflets

A chemically prepared carbon was synthesized from date palm leaflets via sulphuric acid carbonization at 160℃. Adsorption of ciprofloxacin (CIP) from aqueous solution was investigated in terms of time, pH, concentration, temperature and adsorbent status (wet and dry). The equilibrium time was found to be 48 hr. The adsorption rate was enhanced by raising the temperature for both adsorbents, with adsorption data fitting a pseudo second-order model well. The activation energy, E_a, was found to be 17 kJ/mol, indicating a diffusion-controlled, physical adsorption process. The maximum adsorption was found at initial pH 6. The wet adsorbent showed faster removal with higher uptake than the dry adsorbent, with increased performance as temperature increased (25-45℃). The equilibrium data were found to fit the Langmuir model better than the Freundlich model. The thermodynamic parameters showed that the adsorption process is spontaneous and endothermic. The adsorption mechanism is mainly related to cation exchange and hydrogen bonding.     

Antimony(V) removal from water by iron-zirconium bimetal oxide: Performance and mechanism

A Fe-Zr binary oxide adsorbent has been successfully synthesized using a co-precipitation method. It showed a better performance for antimonate (Sb(V)) removal than zirconium oxide or amorphous ferric oxide. The experimental results showed that the Fe-Zr adsorbent has a capacity of 51 mg/g at an initial Sb(V) concentration of 10 mg/L at pH 7.0. Sb(V) adsorption on the Fe-Zr bimetal oxide is normally an endothermic reaction. Most of the Sb(V) adsorption took place within 3 hr and followed a pseudo second-order rate law. Co-existing anions such as SO₄^2-, NO₃^- and Cl^- had no considerable effects on the Sb(V) removal; PO₃^4- had an inhibitory effect to some extent at high concentration; while CO_₃^2- and SiO₄^4- showed significant inhibitory effects when they existed in high concentrations. The mechanism of Sb(V) adsorption on the adsorbent was investigated using a combination of zeta potential measurements, XPS, Raman, FT-IR observations and SO₄^2- release determination. The ionic strength dependence and zeta potential measurements indicated that inner-sphere surface complexes were formed after Sb(V) adsorption. Raman and XPS observations demonstrated that both Fe-OH and Zr-OH sites at the surface of the Fe-Zr adsorbent play important roles in the Sb(V) adsorption. FT-IR characterization and SO₄^2- release determination further demonstrated that the exchange of SO₄^2- with Sb(V) also could promote the adsorption process. In conclusion, this adsorbent showed high potential for future application in Sb(V) removal from contaminated water.     

Preparation and characterization of a lipoid adsorption material and its atrazine removal performance

A novel adsorbent named lipoid adsorption material (LAM), with a hydrophobic nucleolus (triolein) and a hydrophilic membrane structure (polyamide), was synthesized to remove hydrophobic organic chemicals (HOCs) from solution. Triolein, a type of lipoid, was entrapped by the polyamide membrane through an interfacial polymerization reaction. The method of preparation and the structure of the LAM were investigated and subsequent experiments were conducted to determine the characteristics of atrazine (a type of HOC) removal from wastewater using LAM as the adsorbent. The results showed that LAM had a regular structure compared with the prepolymer, where compact particles were linked with each other and openings were present in the structure of the LAM in which the fat drops formed from triolein were entrapped. In contrast to the atrazine adsorption behavior of powdered activated carbon (PAC), LAM showed a persistent adsorption capacity for atrazine when initial concentrations of 0.57, 1.12, 8.31 and 19.01 mg/L were present, and the equilibrium time was 12 hr. Using an 8 mg/L initial concentration of atrazine as an indicator of HOCs in aqueous solution, experiments on the adsorption capacity of the LAM showed 69.3% removal within 6–12 hr contact time, which was close to the 75.5% removal of atrazine by PAC. Results indicated that LAM has two atrazine removal mechanisms, namely the bioaccumulation of atrazine by the nucleous material and physical adsorption to the LAM membrane. Bioaccumulation was the main removal mechanism.     

Preparation of Fe–Co based MOF-74 and its effective adsorption of arsenic from aqueous solution

To obtain a cost-effective adsorbent for the removal of arsenic in water,a novel nanostructured Fe–Co based metal organic framework(MOF-74)adsorbent was successfully prepared via a simple solvothermal method.The adsorption experiments showed that the optimal molar ratio of Fe/Co in the adsorbent was 2:1.The Fe_2Co_1MOF-74 was characterized by various techniques and the results showed that the nanoparticle diameter ranged from60 to 80 nm and the specific surface area was 147.82 m~2/g.The isotherm and kinetic parameters of arsenic removal on Fe_2Co_1MOF-74 were well-fitted by the Langmuir and pseudo-second-order models.The maximum adsorption capacities toward As(III)and As(V)were 266.52 and 292.29 mg/g,respectively.The presence of sulfate,carbonate and humic acid had no obvious effect on arsenic adsorption.However,coexisting phosphate significantly hindered the removal of arsenic,especially at high concentrations(10 mmol/L).Electrostatic interaction and hydroxyl and metal–oxygen groups played important roles in the adsorption of arsenic.Furthermore,the prepared adsorbent had stable adsorption ability after regeneration and when used in a real-water matrix.The excellent adsorption performance of Fe_2Co_1MOF-74 material makes it a potentially promising adsorbent for the removal of arsenic.     

Synthesis of malachite@clay nanocomposite for rapid scavenging of cationic and anionic dyes from synthetic wastewater

Synthesis of malachite@clay nanocomposite was successfully carried out for the removal of cationic (Methylene Blue, MB) and anionic dyes (Congo Red, CR) from synthetic wastewater. Nanocomposite was characterized by TEM, SEM, FT-IR, EDS analysis and zeta potential. TEM analysis indicated that the particle diameter of nanocomposite was in the range of 14 to 23 nm. Various important parameters viz. contact time, concentration of dyes, nanocomposite dosage, temperature and solution pH were optimized to achieve maximum adsorption capacity. In the case of MB, removal decreased from 99.82% to 93.67% while for CR, removal decreased from 88.55% to 75.69% on increasing dye concentration from 100 to 450 mg/L. pH study confirmed the higher removal of CR in acidic range while MB removal was higher in alkaline range. Kinetic study revealed the applicability of pseudo-second-order model for the adsorption of both dyes. Negative values of ΔG⁰ for both systems suggested the feasibility of dye removal and support for spontaneous adsorption of CR and MB on nanocomposite. Nanocomposite showed 277.77 and 238.09 mg/g Langmuir adsorption capacity for MB and CR respectively. Desorption of dyes from the dye loaded nanocomposite was easily carried out with acetone. The results indicate that the prepared malachite@clay nanocomposite is an efficient adsorbent with high adsorption capacity for the aforementioned dyes.     

Simultaneous removal of Congo red and cadmium(II) from aqueous solutions using graphene oxide–silica composite as a multifunctional adsorbent

Graphene oxide is a very high capacity adsorbent due to its functional groups and π?π interactions with other compounds. Adsorption capacity of graphene oxide, however, can be further enhanced by having synergistic effects through the use of mixed-matrix composite. In this study, silica-decorated graphene oxide (SGO) was used as a high-efficiency adsorbent to remove Congo red (CR) and Cadmium (II) from aqueous solutions. The effects of solution initial concentration (20 to 120 mg/l), solution pH (pH 2 to 7), adsorption duration (0 to 140 min) and temperature (298 to 323 K) were measured in order to optimize the adsorption conditions using the SGO adsorbent. Morphological analysis indicated that the silica nanoparticles could be dispersed uniformly on the graphene oxide surfaces. The maximum capacities of adsorbent for effective removal of Cd (II) and CR were 43.45 and 333.33 mg/g based on Freundlich and Langmuir isotherms, respectively. Langmuir and Freundlich isotherms displayed the highest values of Q_max for CR and Cd (II) adsorption in this study, which indicated monolayer adsorption of CR and multilayer adsorption of Cd (II) onto the SGO, respectively. Thermodynamic study showed that the enthalpy (ΔH) and Gibbs free energy(ΔG) values of the adsorption process for both pollutants were negative, suggesting that the process was spontaneous and exothermic in nature. This study showed active sites of SGO (π-π, hydroxyl, carboxyl, ketone, silane-based functional groups) contributed to an enormous enhancement in simultaneous removal of CR and Cd (II) from an aqueous solution, Therefore, SGO can be considered as a promising adsorbent for future water pollution control and removal of hazardous materials from aqueous solutions.     

Synthesis of mesoporous Cu/Mg/Fe layered double hydroxide and its adsorption performance for arsenate in aqueous solutions

The mesoporous Cu/Mg/Fe layered double hydroxide(Cu/Mg/Fe-LDH) with carbonate intercalation was synthesized and used for the removal of arsenate from aqueous solutions.The Cu/Mg/Fe-LDH was characterized by Fourier transform infrared spectrometry,X-ray diffraction crystallography,scanning electron microscopy,X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller.Effects of various physico-chemical parameters such as pH,adsorbent dosage,contact time and initial arsenate concentration on the adsorption of arsenate onto Cu/Mg/Fe-LDH were investigated.Results showed that it was efficient for the removal of arsenate,and the removal efficiency of arsenate increased with the increment of the adsorbent dosage,while the arsenate adsorption capacity decreased with increase of initial pH from 3 to 11.The adsorption isotherms can be well described by the Langmuir model with R 2 > 0.99.Its adsorption kinetics followed the pseudo second-order kinetic model.Coexisting ions such as HPO42-,CO32-,SO42and NO3could compete with arsenate for adsorption sites on the Cu/Mg/Fe-LDH.The adsorption of arsenate on the adsorbent can be mainly attributed to the ion exchange process.It was found that the synthesized Cu/Mg/Fe-LDH can reduce the arsenate concentration down to a final level of < 10 μg/L under the experimental conditions,and makes it a potential material for the decontamination of arsenate polluted water.     

Removal of phosphate by Fe-coordinated amino-functionalized 3D mesoporous silicates hybrid materials

Phosphate removal from aqueous waste streams is an important approach to control the eutrophication downstream bodies of water. A Fe(III) coordinated amino-functionalized silicate adsorbent for phosphate adsorption was synthesized by a post-grafting and metal cation incorporation process. The surface structure of the adsorbent was characterized by X-ray di raction, N2 adsoropion/desoprotion technique, and Fourier transform infrared spectroscopy. The experimental results showed that the adsorption equilibrium data were well fitted to the Langmuir equation. The maximum adsorption capacity of the modified silicate material was 51.8 mg/g. The kinetic data from the adsorption of phosphate were fitted to pseudo second-order model. The phosphate adsorption was highly pH dependent and the relatively high removal of phosphate fell within the pH range 3.0–6.0. The coexistence of other anions in solutions has an adverse e ect on phosphate adsorption; a decrease in adsorption capacity followed the order of exogenous anions: F?? > SO2?? 4 > NO??3 > Cl??. In addition, the adsorbed phosphate could be desorbed by NaOH solutions. This silicate adsorbent with a large adsorption capacity and relatively high selectivity could be utilized for the removal of phosphate from aqueous waste streams or in aquatic environment.     

Synthesis of a novel illite@carbon nanocomposite adsorbent for removal of Cr(Ⅵ) from wastewater

A novel illite@carbon(I@C) nanocomposite adsorbent has been synthesized via a facile hydrothermal carbonization process(HTC) using glucose as carbonaceous source and illite as the carrier.The morphology,microstructure and surface properties of the prepared nanocomposite adsorbent were analyzed by FESEM,TGA,XRD,FT-IR and Zeta potential measurements.Batch experiments were carried out on the adsorption of Cr(Ⅵ) to determine the adsorption properties of the composite.The adsorption of Cr(Ⅵ) onto the I@C nanocomposite was well described by the pseudo-second-order kinetic model and Langmuir isotherm.Compared with the illite and carbon material(SC) separately,the prepared I@C nanocomposite adsorbent exhibited enhanced adsorption performance for Cr(Ⅵ) with a maximum adsorption capacity of 149.25 mg/g,which was higher than that of most reported adsorbents.In addition,the adsorption process was spontaneous and endothermic based on the adsorption thermodynamics study.The adsorption of Cr(Ⅵ) by I@C was highly p H-dependent and the optimum adsorption occurred at p H 2.0.The Zeta potential analysis results indicated that the electrostatic interactions between anionic Cr(Ⅵ) and the positively charged surface of the adsorbent might be critical to the adsorption mechanism.This study demonstrated that the I@C nanocomposite should be a promising candidate for a low-cost,environmental friendly and highly efficient adsorbent for the removal of toxic Cr(Ⅵ) from wastewater.     

Dye removal from wastewater using the adsorbent developed from sewage sludge

Introduction Adsorptionisrelevantinenvironmentalpollutionandprotectionwithreferencetowaterandwastewatertreatment(Bowen,1992).Toxicmaterials,hazardousionsanddyes fromindustrialeffluentsbythewayofadsorptionareofgreatsignificantinconnectionwithenvironmentala…     

Modification of a magnetic carbon composite for ciprofloxacin adsorption

A magnetic carbon composite, Fe₃O₄/C composite, was fabricated by one-step hydrothermal synthesis, modified by heat treatment under an inert atmosphere (N₂), and then used as an adsorbent for ciprofloxacin (CIP) removal. Conditions for the modification were optimized according to the rate of CIP removal. The adsorbent was characterized by Fourier transform infrared spectroscopy, X-ray diffraction measurements, vibrating-sample magnetometry, scanning electron microscopy, transmission electron microscopy, and N₂ adsorption/desorption isotherm measurements. The results indicate that the modified adsorbent has substantial magnetism and has a large specific area, which favor CIP adsorption. The effects of solution pH, adsorbent dose, contact time, initial CIP concentration, ion strength, humic acid and solution temperature on CIP removal were also studied. Our results show that all of the above factors influence CIP removal. The Langmuir adsorption isotherm fits the adsorption process well, with the pseudo second-order model describing the adsorption kinetics accurately. The thermodynamic parameters indicate that adsorption is mainly physical adsorption. Recycling experiments revealed that the behavior of adsorbent is maintained after recycling for five times. Overall, the modified magnetic carbon composite is an efficient adsorbent for wastewater treatment.     

利用新型稀土铈铁复合吸附剂去除水体腐殖质的研究

研究了稀土铈铁复合材料(CFA)对水体中黄腐酸(FA)的去除效能和作用机制.结果表明:CFA在平衡pH3.0～6.5的范围内对FA的去除效果较好,吸附速度快,120min即达到平衡.水体中FA与砷酸根在CFA上有很强的竞争作用,当FA加入量为5mg/L～10mg/L时,砷的饱和吸附量Q_o即丧失40%～50%,表明两者作用于材料相同的活性位点.吸附前后的红外谱图(FTIR)揭示了CFA表面羟基在FA去除中起着重要作用.通过Zeta电位的测定得出材料的等电点为5.6,因而pH偏酸性的条件有利于FA的去除.     

天然菱铁矿改性及强化除砷研究

我国高砷地下水分布广泛,经济、高效地饮用水除砷技术受到广泛关注.静态批实验采用资源丰富、价格便宜的天然菱铁矿为主要原材料,考虑灼烧温度、时间及添加黏合剂等因素确定最优改性条件使除砷效果达到最佳.结果表明,在加铝量为10 mg.g-1、350℃下恒温灼烧90 min后造粒达到强度要求并除砷效果较优.25℃、固液比为0.5 g∶50 mL、As(Ⅲ)和As(Ⅴ)初始浓度为5 mg.L-1时,吸附后溶液中残留As浓度均<10μg.L-1.静态吸附批实验结果表明,25℃时,接触反应时间为12 h可达到吸附平衡,吸附过程较好地符合Lagergren假二级吸附速率方程;最优改性天然菱铁矿对砷的吸附规律可用Langmuir和Freundlich等温吸附模型很好地描述,As(Ⅲ)、As(Ⅴ)饱和吸附容量分别可以达到1 039、1 026μg.g-1.结合XRD、SEM等研究方法和比表面及孔结构分析初步探讨天然菱铁矿改性以及除砷的主要机制.分析表明,改性后天然菱铁矿比表面积大幅度增大,孔径减小,且在表面活化生成一层圆球状的含Fe(Ⅱ)和Fe(Ⅲ)的化合物.改性天然菱铁矿是一种值得进一步研究并实际应用的除砷材料.     

Removal of ammonium ion from water by Na-rich birnessite: Performance and mechanisms

Na-rich birnessite (NRB) was synthesized by a simple synthesis method and used as a high-efficiency adsorbent for the removal of ammonium ion (NH₄⁺) from aqueous solution. In order to demonstrate the adsorption performance of the synthesized material, the effects of contact time, pH, initial ammonium ion concentration, and temperature were investigated. Adsorption kinetics showed that the adsorption behavior followed the pseudo second-order kinetic model. The equilibrium adsorption data were fitted to Langmuir and Freundlich adsorption models and the model parameters were evaluated. The monolayer adsorption capacity of the adsorbent, as obtained from the Langmuir isotherm, was 22.61 mg NH₄⁺-N/g at 283 K. Thermodynamic analyses showed that the adsorption was spontaneous and that it was also a physisorption process. Our data revealed that the higher NH₄⁺ adsorption capacity could be primarily attributed to the water absorption process and electrostatic interaction. Particularly, the high surface hydroxyl-content of NRB enables strong interactions with ammonium ion. The results obtained in this study illustrate that the NRB is expected to be an effective and economically viable adsorbent for ammonium ion removal from aqueous system.     

水合氧化镧吸附除磷的试验研究

以开发新型高效除磷吸附剂材料为目的,以金属水合氧化物MeH(metal hydrate)为试验对象,对所选材料进行了吸附除磷性能评价.通过对多种水合金属氧化物吸附除磷性能的比较研究,发现水合氧化镧LaH(lan-thanum hydrate)具有优异的除磷吸附容量,其吸附容量大约为参照物粉末活性氧化铝的十几倍.该吸附剂的吸附容量随pH值变化显著,在pH=3附近达最大值;吸附等温线较符合Langmuir方程;进行了抗无机阴离子干扰能力测试,给出了干扰离子的影响顺序;该吸附剂对正磷酸根的去除性能优越,但对聚磷酸根的去除效果不理想.试验结果表明,水合氧化镧在平衡吸附容量、pH适应范围等方面与参照物活性氧化铝相比较,具有优异的性能.     

醋酸纤维素吸附剂的制备及其性能表征

研究开发了1种球形醋酸纤维素吸附剂,对其制备方法、形态结构及其对水中4种有机氯农药的吸附性能进行了研究.扫描电镜结果表明,所制备醋酸纤维素吸附剂的外表面是一层致密的醋酸纤维素膜,内部为网状结构;对水中狄氏剂、艾氏剂、异狄氏剂、七氯4种有机氯农药有较强的吸附能力,12h后去除率均达到85%以上;并且对正辛醇-水分配系数(lgK_ow)较大的有机物具有更快的吸附速度,对七氯、艾氏剂的去除率在0·5h后可达99%.说明该吸附剂对水中亲脂性的有机物具有较高的吸附效能.     

Evaluation of zeolites synthesized from fly ash as potential adsorbents for wastewater containing heavy metals

Both pure-form zeolites (zeolites A and X) were synthesized by applying a two-stage method during hydrothermal treatment of fly ash prepared initial gel. The difference of adsorption capacity of both fly ash-synthesized zeolits was assessed under the same adsorption conditions. Copper and zinc were chosen as target heavy metal ions. It was found that adsorption capacity of zeolite A showed much higher value than that of zeolite X. Thus, attention was focused on investigating the removal performance of heavy metal ions in aqueous solution on the synthetic pure-form zeolite A from fly ash, zeolite HS (hydroxyl-solidate) prepared from the residual fly ash (after synthesis of pure-form zeolite A from fly ash) and a commercial grade zeolite A. Batch method was employed to study the influential parameters such as initial pH value, adsorbents dosage and adsorption temperature on the adsorption process. The equilibrium data were well fitted by the Langmuir model and showed the affinity: Cu2+ > Zn2+ (adsorbent FA-ZA). The removal mechanism of metal ions followed adsorption and ion exchange processes. Attempts were also made to recover heavy metal ions and regenerate adsorbents (adsorbent FA-ZA).     

活性氧化铝对六价铬的吸附研究

为了应对水体中六价铬的污染问题,文章研究了活性氧化铝(AA)对六价铬的吸附效果。实验考察了吸附过程中的影响因素pH、六价铬初始浓度、投加量和吸附时间对吸附效果的影响。研究结果表明:活性氧化铝对六价铬的吸附效果受pH的影响较大,六价铬的去除率随着pH值的升高先升高然后降低,最佳pH为3,去除率为84.04%。六价铬的去除率随着活性氧化铝的投加量和吸附时间的增加逐渐升高然后趋于稳定,最佳的投加量和吸附时间分别为10 g/L和90 min,去除率分别为87.34%和84.04%。随着初始浓度的不断上升,六价铬的去除率逐渐下降。在原水条件下的吸附速度和吸附容量都比在纯水条件下低。平衡吸附数据符合Freundlich和Langmuir吸附等温线模型。活性氧化铝对六价铬吸附效果非常好,可以作为去除水中六价铬的吸附剂。