Progress and challenges in molecularly imprinted polymers for adsorption of heavy metal ions from wastewater

Molecularly imprinted polymers (MIPs), prepared by the interaction forces such as forming covalent or non-covalent bonds by crosslinkers and initiators, are new types of specific recognition polymers with particular cavities. This is an ideal class of materials for wastewater treatment because of the particular holes left by the elution process. This review discusses the development process, classification, synthesis principles, systems, and polymerization methods of MIPs. At the same time, the adsorption mechanism of Copper (Cu), Mercury (Hg), Chromium (Cr), Silver (Ag), and Lead (Pb) in the MIPs technique are studied. Finally, some suggestions and prospects for the future development of MIPs are also put forward.     

Fast removal of heavy metal ions and phytic acids from water using new modified chelating fiber

The graft copolymerization of acrylic acid(AA) onto polyethylene glycol terephthalate(PET) fiber initialed by benzoy peroxide (BPO) was carried out in heterogeneous media.Moreover,modification of the grafted PET fiber(PET-AA) was done by changing the carboxyl group into acylamino group through the reaction with dimethylamine.The modified chelating fiber(NDWJN1) was characterized using elementary analysis,SEM and FT-IR spectroscopy.Adsorption kinetic curves indicated that NDWJNl could fast remove heavy metal ions and phytic acids from water effectively.Furthermore,batch kinetic studies indicated that heavy metal ions adsorbed to NDWJNl could be filted well by both pseudo-first-order and pseudo-second-order adsorption equations,but the intra-particle diffusion played a dominant role in the adsorption of phytic acids.     

Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review

The feasibility of using two important and common clay minerals, kaolinite and montmorillonite, as adsorbents for removal of toxic heavy metals has been reviewed. A good number of works have been reported where the modifications of these natural clays were done to carry the adsorption of metals from aqueous solutions. The modification was predominantly done by pillaring with various polyoxy cations of Zr4+, Al3+, Si4+, Ti4+, Fe3+, Cr3+or Ga3+, etc. Preparation of pillared clays with quaternary ammonium cations, namely, tetramethylammonium-, tetramethylphosphonium- and trimethyl-phenylammonium-, N'-didodecyl-N, N'-tetramethylethanediammonium, etc, are also common. Moreover, the acid treatment of clays often boosted their adsorption capacities. The adsorption of toxic metals, viz., As, Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, Zn, etc., have been studied predominantly. Montmorillonite and its modified forms have much higher metal adsorption capacity compared to that of kaolinite as well as modified-kaolinite.     

改良的橘皮果胶抑制半乳糖凝集素-3与肿瘤相关功能的研究进展

半乳糖凝集素-3(Gal-3)是半乳糖凝集素家族中唯一一种嵌合体结构蛋白,含有一个特定的糖基识别结构域(CRD),能够特异性识别并结合半乳糖,此结构域可介导细胞与细胞之间的黏附和识别,并且能够促进部分肿瘤细胞的增殖和转移等。改良的橘皮果胶(MCP)可通过特异性结合肿瘤相关蛋白Gal-3糖基识别结构域,抑制Gal-3与其相关肿瘤受体的结合,阻断肿瘤细胞之间相关信号的传导,从而表现出较强的抗肿瘤活性。本文综述了MCP在Gal-3介导肿瘤发生发展过程中相关作用的研究进展。     

Preparation of crosslinked polystyrene-supported ethylenediamine via a S-containing spacer and adsorption properties towards metal ions

Two novel chelating resins were prepared by anchoring ethylenediamine to crosslinked polystyrene via a spacer containing sulfide. Their structures were characterized by Fourier transform-infrared spectra (FTIR) and scanning electron microscopy (SEM). Porous structure parameters of the resins were measured by ASAP 2020 using BET and BJH methods. Their adsorption capacities for several heavy metal ions especially Hg²⁺ were investigated. The results showed that for the two resins, the more N contents did not mean the better adsorption capacity and the saturated adsorption capacity of poly(2-ethylenediamidomercaptomethylstyrene) (PSM-EDA) for Hg²⁺ could reach to 3.0 mmol/g at room temperature. Isothermal adsorptions of the resins for Hg²⁺ could be described by Langmuir formula. The adsorption mechanism of the resins for Hg²⁺, Cu²⁺ and Ag⁺ was confirmed by X-ray photoelectron spectroscopy (XPS) and FTIR.     

Amorphous molybdenum sulfide mediated EDTA with multiple active sites to boost heavy metal ions removal

The rational design of strong affinity adsorbents for heavy metal ions removal remains a critical challenge for water treatment. In this study, amorphous molybdenum sulfide composites (EDTA-MoS_x (x = 2, 3)) were fabricated via a facile hydrothermal method mediated by EDTA, which was applied to heavy metal ions (Cu²⁺, Cd²⁺, Pb²⁺, Zn²⁺ and Ni²⁺) removal from aqueous solutions. A case study for Cu²⁺ ions showed that the adsorption capacity of EDTA-MoS_x (x = 2, 3) was superior to crystalline phase MoS₂ at pH 6.0 with an initial concentration of 200 mg/L. Adsorption mechanisms of different sulfide groups and COOH of EDTA-MoS_x (x = 2, 3) were verified systematically via a series of experiments, characterizations, and density functional theory (DFT) calculations. Both bridging S₂²⁻ and COOH covalently bonded with Cu²⁺ ions were ascribed to the critical factors for this enhanced removal efficiency on the surface of EDTA-MoS_x (x = 2, 3). This work offers a new method to enhance the adsorption performance of molybdenum sulfide-based materials by controlling crystallinity mediated with an organic complex small molecule.     

Recent developments in the adsorptive removal of heavy metal ions using metal-organic frameworks and graphene-based adsorbents

Clean and potable water is a growing concern around the globe. Among the different water pollutants, heavy metal ions pose a serious health concern to all living beings. The quest for new adsorbents to remove heavy metal ions received a boost with the development in the field of metal-organic framework (MOF). The advancement in synthetic strategies and designing of MOF enabled the researchers to tune the adsorption characteristics and tailor the material specific to a heavy metal ion. Similar to MOF, graphene-based two-dimensional and three-dimensional materials are also promising due to the diverse functionalization possibilities and cost-effectiveness. There had been growing interest in applying MOF and graphene-based materials for the removal of heavy metal ions in the past decade. This review summarizes these developments in detail.     

Surface modification of date palm activated carbonaceous materials for heavy metal removal and CO2 adsorption

In this study, high surface area activated carbon (AC) was prepared from a local palm tree (Phoenix Dactylifera) using a variety of metal carbonates activators and finally achieved an excellent S_BET of 2700 m²/g when Cs₂CO₃ was used as an activating agent at a temperature of 600 °C. Surface modification of AC was carried out using various nitrogen transporting agents, resulting in N-doped ACs with nitrogen content varying from 4.0 to 11.4 %, depending on the functionalizing agents and activators used. The bimodal (presence of micro- as well as meso-porosity) ACs with such excellent surface properties were studied for their CO₂ uptake capacity at two different temperatures (0 and 25 °C) by isotherms recorded at pressure 1 bar and showed a remarkable uptake ability of 3.52 mmol/g (at 25 °C) and 5.6 mmol/g (at 0 °C), respectively. Also, batch experiments with variable pH, contact time, adsorbate concentrations, adsorbent dose, and temperatures were evaluated to understand the mechanism of sorption phenomena of Cr(VI) and Pb(II) achieving > 99.9 % removal capacity by the prepared ACs. Depending on the heavy metal ions being investigated, it was revealed that the pH of the solution and the amount of adsorbent had a direct impact on the total adsorption ability. Nitrogen atoms doped into the carbon frameworks were found to enhance the adsorption in the case of Pb(II) while the removal of Cr(VI) appeared to be unaffected. Maximum adsorption for Cr(VI) was observed at pH 2 and was determined to follow Freundlich isotherm while that of Pb(II) was observed at pH 7 and follows Langmuir isotherm. Best adsorption was found at an adsorbate concentration of 10 ppm and an adsorbent dose of 10 g/L. Kinetic modeling parameters showed the applicability of pseudo-second-order model perfectly.     

Removal of heavy metal ions from aqueous solutions by alkaline-earth metal phosphates

The possibility of utilization of calcium or magnesium phosphates of various composition for heavy and non-ferrous metal extraction from aqueous solutions has been studied. The efficiency of the phosphates in removal of Pb(II), Cr(III) and Fe(III) ions has been shown to decrease in the following sequence: Mg₃(PO₄)₂>MgNH₄PO₄>Ca₃(PO₄)₂>CaHPO₄>Ca₁₀(PO₄)₆(OH)₂ which is inverse to their hydrolytic stability series. It has been established that phosphates of non-apatite structure are capable of binding up to 12 mmol g⁻¹ of the named heavy metals by a chemical interaction. Hydroxyapatite interacts with the polyvalent metal ions via either the above mentioned or ion-exchange mechanism, depending on preparation method used for the apatite and the nature of metal.     

Cysteine functionalized poly(hydroxyethyl methacrylate) monolith for heavy metal removal

The aim of this study was to investigate the performance of monoliths composed of hydroxyethyl methacrylate (HEMA) to which N-methacryloyl-(L)-cysteine methyl ester (MAC) was polymerized for removal of heavy metal ions. Poly(HEMA-MAC) monolith was produced by bulk polymerization. Poly(HEMA-MAC) monolith was characterized by FTIR and scanning electron microscopy (SEM). The poly(HEMA-MAC) monolith with a swelling ratio of 89%, and containing 69.4 μmol MAC/g were used in the adsorption studies. Adsorption capacity of the monolith for the metal ions, i.e., Cu²⁺, Cd²⁺, Zn²⁺, Hg²⁺, and Pb²⁺ were investigated in aqueous media containing different amounts of the ions (10–750 mg/L) and at different pH values (3.0–7.0). The maximum adsorption capacities of the poly(HEMA-MAC) monolith were 68.2 mg/g for Zn²⁺, 129.2 mg/g for Cu²⁺, 245.8 mg/g for Pb²⁺, 270.2 mg/g for Hg²⁺, and 284.0 mg/g for Cd²⁺. pH significantly affected the adsorption capacity of MAC incorporated monolith. The competitive adsorption capacities were 587 μmol/g for Zn²⁺, 1646 μmol/g for Cu²⁺, 687 μmol/g for Pb²⁺, 929 μmol/g for Hg²⁺, and 1993 μmol/g for Cd²⁺. The chelating monolith exhibited the following metal ion affinity sequence on molar basis: Cd²⁺ > Cu²⁺ > Hg²⁺ > Pb²⁺ > Zn²⁺. The formation constants of MAC–metal ion complexes have been investigated applying the method of Ruzic. The calculated values of stability constants were 5.28 × 10⁴ L/mol for Cd²⁺, 4.16 × 10⁴ L/mol for Cu²⁺, 2.27 × 10⁴ L/mol for Hg²⁺, 1.98 × 10⁴ L/mol for Pb²⁺, and 1.25 × 10⁴ L/mol for Zn²⁺. Stability constants were increased with increasing binding affinity. The chelating monoliths can be easily regenerated by 0.1 M HNO₃ with higher effectiveness. These features make poly(HEMA-MAC) monolith a potential adsorbent for heavy metal removal.     

The removal of heavy metal cations by natural zeolites

In this study, the adsorption behavior of natural (clinoptilolite) zeolites with respect to Co²⁺, Cu²⁺, Zn²⁺, and Mn²⁺ has been studied in order to consider its application to purity metal finishing wastewaters. The batch method has been employed, using metal concentrations in solution ranging from 100 to 400 mg/l. The percentage adsorption and distribution coefficients (K_d) were determined for the adsorption system as a function of sorbate concentration. In the ion exchange evaluation part of the study, it is determined that in every concentration range, adsorption ratios of clinoptilolite metal cations match to Langmuir, Freundlich, and Dubinin–Kaganer–Radushkevich (DKR) adsorption isotherm data, adding to that every cation exchange capacity metals has been calculated. It was found that the adsorption phenomena depend on charge density and hydrated ion diameter. According to the equilibrium studies, the selectivity sequence can be given as Co²⁺ > Cu²⁺ > Zn²⁺ > Mn²⁺. These results show that natural zeolites hold great potential to remove cationic heavy metal species from industrial wastewater.     

Trace analysis of heavy metal ions by ion chromatography

Summary An ion chromatographic separation technique for heavy metal ions is described. Using pressure-stable, silica-based, ion-exchange supports and standard HPLC equipment with post-column reaction detector high resolution is achieved as well as extremely high sensitivity in the parts per trillion (ppt)-range.     

Supported carbon dots decorated with metallothionein for selective cadmium adsorption and removal

Carbon dots are prepared and immobilized onto spherical SiO_2 through a one-step thermal oxidation and then decorated with metallothionein(MT), a protein with high affinity towards thiophilic metals. The MT-carbon dots composites are characterized by means of FT-IR, SEM and TGA, giving rise to a MT loading amount of 823 μg g~(-1). The adsorption of cadmium by the composites is a fast process and follows Langmuir model. In comparison with native SiO_2, a 2- and 2.4-folds improvement on the static and dynamic adsorption capacity of the composites for cadmium are obtained, respectively. Moreover,the adsorption efficiency is not affected by the presence of other metals. Finally, the composites are successfully applied for the removal of cadmium in a series of environmental water samples.     

络合吸附伏安法同时测定多种重金属离子

在络合剂亚硝基苯胲 乙醇 乙酸铵体系中,Cr(Ⅵ)、Cd2 、Cu2 、Pb2 、Ni2 等离子都能在汞电极上产生灵敏的阴极络合吸附波,其二次导数伏安峰电流均与离子质量浓度有良好的线性关系,可用于这些离子的定量检测,测定线性范围为Cr(Ⅵ)0.0017～0.67μg mL、Cd2 0.0017～0.117μg mL、Cu2 0.0083～5 8μg mL、Pb2 0.083～1.25μg mL、Ni2 0.17～150μg mL,RSD分别为5.7%、1 3%、1.4%、2 5%和1.6%。方法为工业废水、地表水及生活用水等样品中重金属离子的同时测定提供了可靠、灵敏的检测方法。     

Novel nanostructured dendrimer based on 1,3-bis(4,6-dichloro-1,3,5-triazine-2-yl)urea as an excellent adsorbent for Pb2+, Ni2+, Co2+ and Zn2+ metal ions

Human health is seriously harmed by the consumption of poor-quality water. Due to high toxicity and water solubility, heavy metals are present in wastewater discharged from numerous industries. In the environmental realm, metal-containing water must be treated before being released. A dendrimer is a superior adsorbent for the removal of heavy metal ions due to its nanostructure and hydrophilic end group. In this work, a novel triazine-based hydroxy-terminated dendrimer up to generation three is designed employing a carbamide core. The dendrimer's structure was explored using FT-IR and ¹H NMR studies. Full generation dendrimers UG1.0, UG2.0, and UG3.0 were utilized as an adsorbent for Pb²⁺, Ni²⁺, Co²⁺ and Zn²⁺ metal ion removal from water in a series of tests. The ability of dendrimers to uptake Pb²⁺, Ni²⁺, Co²⁺ and Zn²⁺ metal ions was investigated under various pH, time interval and dendrimer generation parameters. The presence of metal in the dendrimer was confirmed by FT-IR studies of dendrimer-metal complexes. The overall results show that Pb²⁺, Ni²⁺, Co²⁺ and Zn²⁺ metal ions uptake increases with the generation, time, and pH.     

Myoglobin modified electrodes as anchors for d metal cationic complexes

The capability of adsorption of different electroactive cationic Re(V)-amine complexes onto myoglobin-containing electrodes has been investigated. The goal of this work was the development of an Au/thiol/myo electrode and, after incubation of such ensemble in the presence of three different Re(V)-amine complexes, the evaluation of the extent of surface coverage by the complexes (as a way to evaluate the interaction complex-protein) using electrochemical techniques. Our results showed that a protein-containing electrode could therefore be used for the detection of the interaction of small electroactive cationic complexes and the biomolecule. The extent of the coverage of the myoglobin electrode by the complex depends on the number of free tails from the ligands and the total charge of the complex.     

Study of an organically modified clay: selective adsorption of heavy metal ions and voltammetric determination of mercury(II)

In this work, a hydrophilic clay, Na-montmorillonite from Wyoming, USA, was rendered organophilic by exchanging the inorganic interlayer cations for hexadecyltrimethylammonium ions (HDTA), with the formulae of [(CH₃)₃N(C₁₆H₃₃)]⁺ ion. Based on fact that organo-clay has high affinities for non-ionic organic molecules, 1,3,4-thiadiazole-2,5-dithiol was loaded on the HDTA-montmorillonite surface, resulting in the 1,3,4-thiadiazole-2,5-dithiol-HDTA-montmorillonite complex (TDD-organo-clay).The following properties of TDD-organo-clay are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II).The main point of this paper is the construction of a selective sensor, a carbon paste electrode modified with TDD-organo-clay, its properties and its application to the determination of mercury(II) ions, as this element belongs to the most toxic metals. The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination.     

石墨烯基复合材料去除和检测重金属离子的研究进展

石墨烯具有超大的比表面积、较快的载流子迁移速率和优异的电催化活性,广泛用于环境保护与检测领域。过去几年,基于石墨烯的大批高效吸附剂和传感器均被开发并应用于重金属离子的污染治理。本文详细阐述了石墨烯基复合材料在重金属离子去除和检测方面的研究进展,同时比较了不同方法的优缺点,最后对后续研究方向进行了展望。     

Surface adsorption behaviour of milk whey protein and pectin mixtures under conditions of air-water interface saturation

Milk whey proteins (MWP) and pectins (Ps) are biopolymer ingredients commonly used in the manufacture of colloidal food products. Therefore, knowledge of the interfacial characteristics of these biopolymers and their mixtures is very important for the design of food dispersion formulations (foams and/or emulsions). In this paper, we examine the adsorption and surface dilatational behaviour of MWP/Ps systems under conditions in which biopolymers can saturate the air-water interface on their own. Experiments were performed at constant temperature (20 °C), pH 7 and ionic strength 0.05 M. Two MWP samples, β-lactoglobulin (β-LG) and whey protein concentrate (WPC), and two Ps samples, low-methoxyl pectin (LMP) and high-methoxyl pectin (HMP) were evaluated. The contribution of biopolymers (MWP and Ps) to the interfacial properties of mixed systems was evaluated on the basis of their individual surface molecular characteristics. Biopolymer bulk concentration capable of saturating the air-water interface was estimated from surface pressure isotherms. Under conditions of interfacial saturation, dynamic adsorption behaviour (surface pressure and dilatational rheological characteristics) of MWP/Ps systems was discussed from a kinetic point of view, in terms of molecular diffusion, penetration and configurational rearrangement at the air-water interface. The main adsorption mechanism in MWP/LMP mixtures might be the MWP interfacial segregation due to the thermodynamic incompatibility between MWP and LMP (synergistic mechanism); while the interfacial adsorption in MWP/HMP mixtures could be characterized by a competitive mechanism between MWP and HMP at the air-water interface (antagonistic mechanism). The magnitude of these phenomena could be closely related to differences in molecular composition and/or aggregation state of MWP (β-LG and WPC).     

Removal of heavy metal ions from water by using poly(ethyleneglycol dimethacrylate-co-acrylamide) beads

Poly(ethyleneglycol dimethacrylate-co-acrylamide) (poly(EDGMA-co-AAm)) copolymer beads have been prepared for use in the separation Pb(II), Hg(II), and Cd(II), metal ions in aqueous solution by a batch equilibration technique. Adsorption capacity were increased with pH for Pb(II), Cd(II) and Hg(II) and then reached almost plateau value around 6.0. The high initial rate of metal ions uptake (<10 min) suggests that the adsorption occurs mainly at the bead surface. The metal uptake results show that poly(EGDMA-co-AAm) can be used for the adsorption of the following metals in the indicated order: Pb(II) > Cd(II) > Hg(II) expressed on a molar basis. However, when the uptake was expressed in terms of the amount of metal removed from solution was as follows: Pb(II) > Hg(II) > Cd(II). The beads still showed preference toward Pb(II) when this metal was in a mixture with Hg(II) and Cd(II). A linearized form of the Freundlich and the Langmuir isotherm model fits the experimental equilibrium concentration data of Hg(II) and Cd(II) better than isotherm type model of Pb(II). The recovery of the metal ions after adsorption and the regeneration of the adsorbent can be carried out by treatment of the loaded beads with either 0.5 M NaCl, or 1 M HNO₃.