Highly efficient and fast adsorption of Au(III) and Pd(II) by crosslinked polyethyleneimine-glutaraldehyde

An adsorbent (PEI-GA) is prepared by crosslinking polyethyleneimine with glutaraldehyde. PEI-GA shows outstanding adsorption performance towards Au(III) and Pd(II). PEI-GA presents large adsorption capacity towards Au(III) in a wide application pH range from 1 to 9. The adsorption capacities of PEI-GA for Au(III) and Pd(II) at 25°C reach 2575 and 497 mg/g, respectively. Au(III) and Pd(II) can be adsorbed completely within 10 min for 8.3 mg/L Au(III) and 20 min for 9.7 mg/L Pd(II). The adsorption equilibrium time required for 523.9 mg/L Au(III) and for 565.6 mg/L Pd(II) is 2 and 9 h, respectively. The Sips model is the most suitable to describe the adsorption isotherms which leads to more realistic adsorption capacities for both metals. PEI-GA also exhibits high selectivity and repeatability towards Au(III) and Pd(II). The adsorption mechanism involves redox, chelation coordination, and electrostatic interactions for Au(III), and coordination and electrostatic interactions for Pd(II).     

Removal of Copper (II) and Nickel (II) Ions from Aqueous Solutions by a Composite Chitosan Biosorbent

Abstract

A composite chitosan biosorbent (CCB) was prepared by coating chitosan on to ceramic alumina. The adsorption characteristics of the sorbent for copper and nickel ions were studied under batch equilibrium and dynamic flow conditions at pH 4.0. The equilibrium adsorption data were correlated with Langmuir, Freundlich, and Redlich‐Peterson models. The ultimate monolayer capacities, obtained from Langmuir isotherm, were 86.2 and 78.1 mg/g of chitosan for Cu(II) and Ni(II), respectively. In addition, dynamic column adsorption studies were conducted to obtain breakthrough curves. After the column was saturated with metal ions, it was regenerated with 0.1 M sodium hydroxide. The regenerated column was used for a second adsorption cycle.     

Separation and concentration processes of solutions of Co(II), Ni(II), Cr(III), Fe(III) and Mn(II) by extraction with toluene-dissolved rosin

The extraction and stripping of Co(II), Ni(II), Cr(III) and Fe(III) from aqueous solutions by rosin dissolved in toluene has been investigated. Results obtained show that rosin is better extractant than abietic or n-lauric acids under comparable conditions. From these results, and the data of Mn(II) solvent extraction studied previously under the same conditions, a separation and concentration process for these five cations in aqueous solutions has been designed. Saturated solutions of Fe(III), Cr(III), Mn(II) and finally Co(II) and Ni(II) have been obtained successively by extraction and stripping, by addition of ammonium hydroxide to obtain the appropriate pH value, and by modifying adequately the organic phase/aqueous phase volume ratio.     

Preparation of Poly(acrylamide-maleic Acid) Resin by Template Polymerization and Its Use for Adsorption of Co(II) and Ni(II)

Poly(acrylamide-maleic acid) resin P(AAm-MA) was prepared by template polymerization. Polyacrylamide PAAm was used as a template for the polymerization of MA in an aqueous solution using gamma rays as the initiator. The effects on the capacity of P(AAm-MA), such as concentration of maleic acid and amount of template polymer, were investigated. P(AAm-MA) has been utilized as an adsorbent for the removal of Co(II) and Ni(II) ions from an aqueous solution. The effects of time of equilibrium, pH, temperatures, and dosage of the adsorbent on the removal of Co(II) and Ni(II) ions have been studied. The equilibrium data were analyzed using the Langmuir and Freundlich isotherm models. The equilibrium process was described well by the Langmuir isotherm model.     

硫氰酸锰及其相关衍生物的合成及化学表征

合成了金属有机配合物非线性光学晶体硫氰酸汞锰，及其相关衍生物，二二甲亚砜合硫氰酸汞锰，乙二醇一甲醚合硫氰酸汞锰，二水合二N，N－二甲基乙酰胺合硫氰酸汞锰，二水合二N－甲基－α－吡咯烷酮合硫氰酸汞锰。采用元素分析，红外光谱以及紫外－可见－近红外透央求我谱分析对其进行了化学表征。     

Epoxidation of Olefins Catalyzed by Mn(II) Salen Complex Anchored on PAMAM–SiO2 Dendrimer

New dendritic catalysts have been prepared by the immobilization of a Mn(II) salen complex on a polyamidoamine dendrimer propagated on the surface of silica. These have been applied in the catalytic epoxidation of olefins. Although the increase of the amount of Mn loading is found to be limited on high-generation dendrimers, the Mn(II) salen complex anchored on the fourth-generation dendrimer shows much higher catalytic activity toward the epoxidation of styrene than that anchored on lower generations. These results suggest that the length of the dendritic backbone chain plays an important role in increasing the accessibility between the catalytic active sites of the immobilized Mn(II) salen complex and the reactant molecules, resulting in the enhancement of the catalytic activity of the Mn(II) salen complex anchored on the fourth-generation dendrimer.     

含氮大分子吸附剂的制备及其对Cd(II)的吸附

利用三聚氯氰的温度梯度反应活性,在较低温度下,用多乙烯多胺与三聚氯氰进行亲核取代反应,合成出一种以三嗪环为连接点的不溶含氮大分子颗粒吸附剂(N-MGA),并将其用于去除水体中的Cd(Ⅱ).通过元素分析、FTIR和SEM对N-MGA进行表征,同时对Cd(Ⅱ)的吸附进行吸附动力学、等温吸附模型拟合和吸附机理进行研究,考察了溶液pH对Cd(Ⅱ)吸附性能的影响、吸附剂的吸附-解吸再生循环性能及结构稳定性.结果表明,该吸附剂对Cd(Ⅱ)的吸附机理是利用吸附剂氨基上氮的孤对电子与Cd(Ⅱ)的配位络合作用进行吸附,且吸附过程符合准二级动力学模型和Langmuir吸附等温线模型,最大吸附量可达539.1 mg/g,且对Cd(Ⅱ)的吸附较为容易,吸附能力较强;在Cd(Ⅱ)初始质量浓度为3636.5和70.0 mg/L时,对Cd(Ⅱ)的吸附率分别可达97.5％和99.9％,且10次吸附-解吸再生循环中吸附率维持在97.0％～98.2％,解吸率均在97.6％以上,吸附剂回收率均在92.0％以上.     

Recent studies in adsorption of Pb(II), Zn(II) and Co(II) using conventional and modified materials:a review

ABSTRACT

Heavy metal contamination and its detrimental effects on human health and environment have been a worldwide concern. Over the years, various technologies have been adapted to tackle this problem. Adsorption is still considered to be one of the most feasible and cost-effective methods for treating wastewater contaminated with heavy metals. Adsorbents such as activated carbon, clay, zeolites and silica have been studied extensively in the past. Modification of these conventional adsorbents and the synthesis of nonconventional adsorbents such as nanocomposites and metal organic frameworks (MOF’s) have been the main focus of study in recent times. This review article attempts to present a detailed account of various adsorbents and their removal efficiencies for the treatment of wastewater contaminated with lead(II), zinc(II) and cobalt(II) in the current decade. Influence of various parameters, adsorption isotherms and kinetics best described for their removal have also been reviewed in detail. It is observed that most of the adsorbents followed pseudo second order kinetics suggestive of a chemisorption process. After conducting a thorough review of more than 120 recently published papers, it can be inferred that nanomaterials and nanocomposites have shown excellent adsorption capacity for removal of these heavy metals.     

Arsenic adsorption using copper (II) oxide nanoparticles

Arsenic poisoning is a major problem in today's life. To reduce its concentration in drinking water, different metal based compounds were explored as arsenic adsorbents. In the present study, copper (II) oxide nanoparticles were prepared by thermal refluxing technique and used as an adsorbent for arsenic removal from water. Characterization of the adsorbent using TEM, BET, XRD and FTIR implied that the prepared adsorbent was in nano size and had excellent adsorption behavior with surface area of 52.11 m²/g. Systematic adsorption experiments were carried out with different process parameters such as contact time, adsorbent mass, pH, temperature and stirring speed and found that copper (II) oxide had very good efficiency towards arsenic adsorption. Thermodynamic parameters and adsorption kinetics were studied in detailed to know the nature and mechanism of adsorption. Results showed that the adsorption process followed pseudo second order kinetic and endothermic behavior. Adsorption equilibrium was studied with Langmuir and Freundlich isotherm models. The adsorption process followed Langmuir isotherm with an adsorption capacity of 1086.2 μg/g. A regeneration study was proposed in order to reuse the adsorbent for better economy of the process. Finally, a process design calculation is reported to know the amount of adsorbent required for efficient removal of arsenic from aqueous medium.     

Adsorption of Pb(II) ions from aqueous solutions by carbon nanotubes oxidized different methods

This study investigated the heavy metal adsorption of the carbon nanotubes (CNTs) oxidized different methods. Besides the conventional ultrasonication method, the UV-light used as an oxidation agent. The two oxidation methods compared with each other by Pb(II) adsorption. The characterizations of oxidized CNTs were analyzed by FTIR, XRD, DTG, SEM and total acidity capacity analysis. The adsorption capacities of carbon nanotubes were compared with using Langmuir and Freundlich isotherms. Two different kinetic theories were applied to experimental data. These theories are pseudo-second order and intra-particle diffusion models. The adsorption results can be compared using non-linear Langmuir isotherm parameters. For single wall carbon nanotubes (SWCNTs), theoretical adsorption capacity value (Q_m) of UV-light method is 511.99 mg/g and ultrasonication method is 342.36 mg/g. The UV-light increased the surface acidity of the carbon nanotubes more than ultrasonication. After the adsorption experiments, it is apparently seen that the UV-light oxidation method is a useful method for heavy metal adsorption.     

Investigation of Pb(II) adsorption onto natural and synthetic polymers

Adsorption of toxic metal ion Pb(II) onto two different insoluble humic acids (IHAs) obtained from Beysehir (BIHA) and Ermenek (EIHA) low grade lignites and two synthesized terpolymers: styrene-divinylbenzene-methacrylic acid (SDBM) and styrene-divinylbenzene allylmethacrylate (SDBAM) were investigated and compared with commercial activated carbon (AC). The synthesized polymers were characterized by FTIR. Effects of pH (in neutral and acidic range), time, and initial metal concentration on the effectiveness of IHAs and terpolymers were determined. All synthesized adsorbents could adsorb Pb(II) with much higher capacity at half of the retention of AC in acidic medium. The adsorption capacities varied in the range of 51–76 mg g⁻¹. The affinity order of polymers in acidic medium for Pb(II) ions was observed as: SDBAM>SDBM>BIHA≈EIHA>AC. IHAs fit Freundlich model while SDB polymers were fitting Langmuir isotherm. The maximum adsorption capacities in neutral medium were 48 mg g⁻¹ for SDBM and 15 mg g⁻¹ for BIHA. Desorption studies for the polymer of highest performance indicated that about 90% desorption was achieved at 5 h by using EDTA regenerant solution. The polymer can be used repeatedly in Pb(II) adsorption with close capacities to initial use. The higher selectivity of SDBAM to Pb(II) ions in multimetal solution was also indicated in the study. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Separation of Co(II) and Mn(II) from sulphate media via a HFSLM: Reaction flux model and experimental verification

Separation of Co(II) and Mn(II) from sulphate media through triple HFSLM in series using D2EHPA was explored. Mn(II) was extracted preferentially over Co(II) at the pH value of 5, 100 ppm of Co(II) and Mn(II), 5% (v/v) of D2EHPA, 0.2 M HCl. The highest extraction percentage of Mn(II) was 98.14%, and Co(II) remained at 94.05% in the raffinate stream. The reaction order (n) and the reaction rate constant (k_f) were found to be 1.00 and 0.0180 min⁻¹, respectively. Furthermore, the reaction flux model proved to be in good agreement with the experimental data at an average deviation of 2.24%.     

Calcined tetrabutylammonium kaolinite and montmorillonite and adsorption of Fe(II), Co(II) and Ni(II) from solution

Kaolinite and montmorillonite were modified with tetrabutylammonium (TBA) bromide, followed by calcination. The structural changes were monitored with XRD, FTIR, surface area and cation exchange capacity measurements. The modified clay minerals were used for adsorption of Fe(III), Co(II) and Ni(II) ions from aqueous solution under different conditions of pH, time and temperature. The uptake of the metal ions took place by a second order kinetics. The modified montmorillonite had a higher adsorption capacity than the corresponding kaolinite. The Langmuir monolayer capacities for the modified kaolinite and montmorillonite were Fe(III): 9.3 mg g^− 1 and 22.6 mg g^− 1; Co(II): 9.0 mg g^− 1 and 22.3 mg g^− 1; and Ni(II): 8.4 mg g^− 1 and 19.7 mg g^− 1. The modified kaolinite interacted with Co(II) in an endothermic manner, but all the other interactions were exothermic. The decrease of the Gibbs energy in all the cases indicated spontaneous adsorption.     

Adsorption of Cu(II) from aqueous solutions by tannins immobilized on collagen

Novel adsorbents were prepared by immobilizing tannins on collagen fibre matrices. Their adsorption properties, including adsorption equilibrium, adsorption kinetics, and column adsorption kinetics to Cu(II) were investigated. Immobilized Myrica rubra tannin and black wattle tannin exhibited significantly higher adsorption capacity than larch tannin and the adsorption isotherms of these three immobilized tannins can be described by the Freundlich model. Detailed adsorption studies of immobilized black wattle tannin to Cu(II) indicated that temperature had little effect on the adsorption isotherms whereas the effect of pH was significant. Adsorption rate data fitted well to a pseudo‐second‐order rate model, and the adsorption capacity calculated by this model was consistent with the result of actual measurement at relatively higher adsorption temperatures. Immobilized black wattle tannin also had excellent column adsorption kinetic properties and high binding capacity. The adsorptivity of the column was stable even after repeated adsorption–desorption cycles. Copyright © 2004 Society of Chemical Industry     

Efficient removal of Cr(VI) and Pb(II) from aqueous solution by magnetic nitrogen-doped carbon

The magnetic nitrogen-doped carbon (MNC) was prepared from polypyrrole by a simple high temperature calcination process in this paper. The structure and properties of MNC were analyzed by scanning electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction, Brunner-Emmet-Teller, vibrating sample magnetometer, and X-ray photoelectron spectroscopy. The capacity of MNC to adsorb Cr(VI) and Pb(II) was evaluated. The effects of the initial pH, dosage, concentration and temperature on the adsorption capacity of MNC were measured. MNC had a large specific surface area and a special porous structure. Its nitrogen and carbon sources were rich, and the ratio of carbon to nitrogen was fixed. The maximum Cr(VI)-adsorption capacity and maximum Pb(II) adsorption capacity of MNC could reach 456.63 and 507.13 mg∙g⁻¹ at 318 K, respectively. The pseudo-second-order model was used to describe the adsorption kinetics of MNC, and the Freundlich model was employed to discuss its isotherms. The adsorption process was affected by the electrostatic force, the reducing reaction, pores and chelation. The results of this study suggest that MNC is a material with superior performance, and is very easily regenerated, reused, and separated in the adsorption process.     

Sorption of Pb(II), Cd(II) and Zn(II) by iminodiacetate chelating resins in non-competitive and competitive conditions

Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.     

Heterocyclic modification of chitosan for the adsorption of Cu (II) and Cr (VI) ions

A heterocyclic modification of chitosan has been attempted for development of an effective adsorbent material for removal of metal ions. The modified polymer was characterized using infrared (IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) techniques. The adsorption capacity exhibited for Cu (II) and Cr (VI) were 83.75 and 85.0 mgg^?1, respectively, which is a significant improvement over chitosan. The adsorption on the modified polymer was a second-order kinetic process and followed Langmuir isotherm model. The thermodynamic analysis indicated exothermic and spontaneous nature of adsorption. About 80% of the adsorbed metal ions were desorbed in appropriate stripping solutions indicating reusability.     

Carbon Metabolism of a Soilborne Mn(II)-Oxidizing Escherichia coli Isolate Implicated as a Pronounced Modulator of Bacterial Mn Oxidation

Mn(II)-oxidizing microorganisms are generally considered the primary driving forces in the biological formation of Mn oxides. However, the mechanistic elucidation of the actuation and regulation of Mn oxidation in soilborne bacteria remains elusive. Here, we performed joint multiple gene-knockout analyses and comparative morphological and physiological determinations to characterize the influence of carbon metabolism on the Mn oxide deposit amount (MnODA) and the Mn oxide formation of a soilborne bacterium, Escherichia coli MB266. Different carbon source substances exhibited significantly varied effects on the MnODA of MB266. A total of 16 carbon metabolism-related genes with significant variant expression levels under Mn supplementation conditions were knocked out in the MB266 genome accordingly, but only little effect on the MnODA of each mutant strain was accounted for. However, a simultaneous four-gene-knockout mutant (namely, MB801) showed an overall remarkable MnODA reduction and an initially delayed Mn oxide formation compared with the wild-type MB266. The assays using scanning/transmission electron microscopy verified that MB801 exhibited not only a delayed Mn-oxide aggregate processing, but also relatively smaller microspherical agglomerations, and presented flocculent deposit Mn oxides compared with normal fibrous and crystalline Mn oxides formed by MB266. Moreover, the Mn oxide aggregate formation was highly related to the intracellular ROS level. Thus, this study demonstrates that carbon metabolism acts as a pronounced modulator of MnODA in MB266, which will provide new insights into the occurrence of Mn oxidation and Mn oxide formation by soilborne bacteria in habitats where Mn(II) naturally occurs.     

A Halomanganates(II) with P,P’-Diprotonated Bis(2-Diphenylphosphinophenyl)ether: Wavelength-Excitation Dependence of the Quantum Yield and Role of the Non-Covalent Interactions

A [H₂DPEphos][MnX₄] [X = Br, Cl] tetrahalomanganates(II) with P,P’-diprotonated bis[2-(diphenylphosphino)phenyl]ether cation has been designed and investigated in photophysics and EPR terms. The complexes exhibit a green luminescence resulted from the Mn(II) d–d transitions (⁴T₁→⁶A₁) with the wavelength-excitation dependence of the quantum yield. The solid [H₂DPEphos][MnBr₄] complex exhibits a bright green phosphorescence (λ_max = 515 nm) with the high luminescence quantum yield depending on the excitation energy whereas the solid [H₂DPEphos][MnCl₄] complex exhibits a very weak phosphorescence (λ_max = 523 nm). The unexpected shorter luminescence lifetime for the [H₂DPEphos][MnCl₄] than for the [H₂DPEphos][MnBr₄] at 300 K can be a result of the higher non-radiative relaxation contribution. On the one hand, the non-covalent PH…X(Mn) interactions quench the manganese(II) luminescence. On the other hand, the PH…X(Mn) interactions are a pathway of the excitation transfer from [H₂DPEphos]²⁺ to [MnX₄]²⁻.