Synthesis of a new type of adsorbent containing carboxyl and amidoxime groups by preirradiation grafting and its absorption of metal ions

A new type of adsorbent containing amidoxime and carboxyl groups was synthesized by the preirradiation graft copolymerization of acrylonitrile (AN) and acrylic acid (AA) onto fibrous‐type poly(vinyl alcohol) followed by amidoximation with hydroxylamine. The radiation dose and ratio of AN and AA monomers influenced the degree of grafting, the content of the amidoxime group, and the adsorption capacity. The synthesis course, structure, and properties of the adsorbent were investigated with Fourier transform infrared, scanning electron microscopy, and thermogravimetry. The adsorption property of the adsorbent for palladium(II) ions was also studied systematically. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1986–1992, 2002     

Removal of concentrated heavy metal ions from aqueous solutions using polymers with enriched amidoxime groups

Particulate and fibrous adsorbents with enriched amidoxime groups were synthesized by using a novel monomer N,N′‐dipropionitrile acrylamide. The adsorption properties of amidoximated poly(N,N′‐dipropionitrile acrylamide) [poly(DPAAm)] particles and a nonwoven fabric grafted with the same for UO₂²⁺, Pb²⁺, Cu²⁺, and Co²⁺ at high concentrations were investigated by batch process. Metal ion adsorption studies were conducted from metal ion solutions with different initial concentrations (100–1500 ppm). It was shown that particulated amidoximated poly(DPAAm) has higher adsorption capacity than amidoximated nonwoven fabrics for all metal ions, especially for uranyl ions. The results of the adsorption studies showed that the interaction between UO₂²⁺ and amidoximated groups agree with the Langmuir‐type isotherm. From the Langmuir equation, the adsorption capacities were found as 400 mg UO₂²⁺/g dry amidoximated poly(DPAAm) and 250 mg UO₂²⁺/g dry amidoximated graft polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1705–1710, 2004     

Adsorption behavior of metal ions by amidoxime chelating resin

The adsorption properties of poly(acrylamidoxime) chelating resin for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), Cr(III), and U(VI) are investigated by the batch technique. Based on the research results of the binding capacity effect of the pH value on sorption kinetic experiments, it is shown that this resin has higher binding capacity to uranyl ions, fast kinetics, and very good selectivity from binary metal ion mixtures with Cu(II) and Pb(II). The uranyl ion sorption strongly depends on the pH value of the solution. The highest value of 99% is at pH 5, but at pH 1 there is no retention. The adsorbed UO can be eluted by sulfuric acid and sodium carbonate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1994–1999, 2000     

细菌纤维素对重金属离子的吸附机理研究

以细菌纤维素(BC)为吸附剂,对重金属离子Cu2+,Pb2+和Cd2+的吸附等温线和吸附动力学特性进行了研究,并采用红外光谱分析法探讨了吸附作用机理。结果表明:BC对Cu2+,Pb2+和Cd2+吸附更好地符合Langmuir吸附等温方程和准二级反应动力学模型,说明吸附过程为单分子层吸附,化学吸附作用为主。粒子内扩散拟合曲线均不经过原点,证明粒子内扩散并不是唯一速率控制步骤。FT-IR分析表明吸附金属离子后的BC中—OH最大吸收位发生不同程度的蓝移,说明BC中部分—OH参与吸附,即与重金属离子之间发生反应,从而使—OH的数量减少。     

Synthesis of new chelating ion exchange resin with hydroxamic and amidoxime groups and study of its metal binding property

The synthesis of a new chelating ion exchanger with hydroxamic and amidoxime groups was performed by an aminolysis reaction of an ethylacrylate/acrylonitrile/divinylbenzene copolymer with hydroxylamine in the presence of sodium ethoxylate. We studied the retention property of the new resin for Pb(II), Cd(II), Cu(II), Ni(II), Zn(II), Mn(II), and Fe(III) metal cations from aqueous solutions. The retention capacity depends on the contact time, the pH of the solution, and the types of counterions of the metal cations. Competitive adsorptions of Pb(NO₃)₂ + Fe₂(SO₄)₃, Pb(NO₃)₂ + MnSO₄, Pb(NO₃)₂ + Cd(NO₃)₂, and Pb(NO₃)₂ + CuCl₂ on the new chelating ion exchanger were performed. The results showed that the resin preferentially retained the Pb(II) ions from the binary aqueous mixtures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2956–2962, 2003     

Physical and chemical characteristics of polymer-based spherical activated carbon and its ability to adsorb organics

The characterization of a polymeric spherical activated carbon (PAC) was performed by comparing its adsorption, porosity, functional groups and some of the physical properties with a commercial spherical activated carbon (CAC). The PAC was about 4 times superior to the CAC with respect to the mechanical strength. The micropore volume of the PAC was about 5% smaller than that of the CAC. The maximum methylene blue adsorption values of the PAC and the CAC were 32 and 14 mg g⁻¹, respectively, which indicated low mesopore volumes as consistent with the values of BJH volume. This resulted in the low butane working capacity values for both activated carbons. Adsorption parameters for the Langmuir and the Freundlich isotherm models were determined for all organic substances tested. Both isotherms were suitable models to analyze the equilibrium data for the removal of all organics. However, the Langmuir model fitted better than the Freundlich model and the adsorption capacities of the PAC were somewhat higher than those of the CAC. The chemical properties of the activated carbons, the pH of solutions and the substituents on absorbates have an effect on adsorption of the organics tested.     

Formation of thermosensitive copolymer beads having phosphinic acid groups and adsorption ability for metal ions

Hydrophilic thermosensitive copolymer beads having phosphinic acid groups were prepared by suspension copolymerization of acryloyloxypropyl n‐octylphosphinic acid (APPO), N‐isopropyl acrylamide (NIPAAm), and tetraethyleneglycol dimethacrylate (4G). The thermosensitivity and the adsorption ability of the copolymer beads for metal ions beads were studied. The APPO‐NIPAAm‐4G copolymer beads were obtained in a good yield by suspension copolymerization of monomers (APPO, NIPAAm, and 4G) dissolved in chloroform, in a saturated Na₂SO₄ aqueous solution in the presence of surfactant and MgCO₃. The APPO‐NIPAAm‐4G copolymer beads had higher adsorption ability for lanthanide metal ions (Eu³⁺, Sm³⁺, Nd³⁺, or La³⁺) than for main transition metal ions (Cu²⁺, Ni²⁺, or Co²⁺). Furthermore, it was also found that the APPO‐NIPAAm‐4G copolymer beads had selective adsorption ability between lanthanide metal ions, and the order of adsorption ability for lanthanide metal ions was as follows: Eu³⁺ > Sm³⁺ > Nd³⁺ > La³⁺. The selective adsorption for these metal ions from their mixed solutions was performed by both a batch method and a column method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 449–460, 2006     

聚酰胺接枝纤维素的合成及对金属离子的吸附性能

以葡萄秸秆为原料提取纤维素,以环氧树脂为交联剂,将聚酰胺交联到纤维素上制得聚酰胺-葡萄纤维素吸附剂。测定聚酰胺-葡萄纤维素吸附剂对Co2+和Fe2+的吸附性能,并研究环氧树脂用量、反应温度和吸附平衡时间对吸附性能的影响。结果表明,当反应温度25℃、吸附平衡时间60 min和m(聚酰胺)∶m(葡萄纤维素)∶m(环氧树脂)=2∶1∶1.5时,制备的聚酰胺-葡萄纤维素吸附剂的吸附性能最好。聚酰胺-葡萄纤维素吸附剂对Co2+和Fe2+的吸附均在60 min后达到平衡,Fe2+和Co2+的最大吸附容量分别为22.40 mg·g-1和16.82 mg·g-1。     

Water‐insoluble polymers with ability to remove metal ions

Crosslinked poly[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide‐co‐2‐acrylamido glycolic acid [P(MAAPDSA‐co‐AGCO)] was synthesized by radical polymerization and tested as an adsorbent under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) by batch and column equilibrium procedures. The resin–metal ion equilibrium was achieved before 1 h. The resin showed a maximum retention capacity value for Hg(II) at pH 2 of 1.084 meq/g. The recovery of the resin was investigated at 20°C under different concentrations of HNO₃ and HClO₄. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3679–3685, 2004     

Competitive removal of heavy metal ions by cellulose graft copolymers

The effect of composition of graft chains of four types cellulose graft copolymers on the competitive removal of Pb²⁺, Cu²⁺, and Cd²⁺ ions from aqueous solution was investigated. The copolymers used were (1) cellulose‐g‐polyacrylic acid (cellulose‐g‐pAA) with grafting percentages of 7, 18, and 30%; (2) cellulose‐g‐p(AA–NMBA) prepared by grafting of AA onto cellulose in the presence of crosslinking agent of N,N′‐methylene bisacrylamide (NMBA); (3) cellulose‐g‐p(AA–AASO₃H) prepared by grafting of a monomer mixture of acrylic acid (AA) and 2‐acrylamido‐2‐methyl propane sulphonic acid (AASO₃H) containing 10% (in mole) AASO₃H; and (4) cellulose‐g‐pAASO₃H obtained by grafting of AASO₃H onto cellulose. The concentrations of ions which were kept constant at 4 mmol/L in an aqueous solution of pH 4.5 were equal. Metal ion removal capacities and removal percentages of the copolymers was determined. Metal ion removal capacity of cellulose‐g‐pAA did not change with the increase in grafting percentages of the copolymer and determined to be 0.27 mmol metal ion/g_copolymer. Although the metal removal rate of cellulose‐g‐p(AA–NMBA) copolymer was lower than that of cellulose‐g‐pAA, removal capacities of both copolymers were the same which was equal to 0.24 mmol metal ion/g_copolymer. Cellulose did not remove any ion under the same conditions. In addition, cellulose‐g‐pAASO₃H removed practically no ion from the aqueous solution (0.02 mmol metal ion/g_copolymer). The presence of AASO₃H in the graft chains of cellulose‐g‐p(AA–AASO₃H) created a synergistic effect with respect to metal removal and led to a slight increase in metal ion adsorption capability in comparison to that of cellulose‐g‐pAA. All types of cellulose copolymers were found to be selective for the removal of Pb²⁺ over Cu²⁺ and Cd²⁺. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2034–2039, 2003     

Adsorption behavior of heavy metal ions on cellulose graft copolymers

The adsorption behavior of cadmium, copper and lead ions on holocellulosic materials containing various levels of polyacrylonitrile and poly(acrylic acid) grafts was examined. The amount of metal ions adsorbed per gram of the modified cellulosic substrate depended on the metal ion type, the nature and level of the incorporated graft polymer. In all cases grafting increased the metal ion-binding capacity of the cellulosic materials (by up to 50% for Cu (II) ions). The influence of temperature and initial metal ions concentration on the sorption behavior of the metal ions on the composite materials was investigated.     

Decomposition of peroxide on carboxymethyl cellulose and its ability to initiate graft copolymerization

The decomposition of the peroxide group on fibrous carboxymethyl cellulose (CMC) and its ability to initiate graft copolymerization were investigated. The peroxide on CMC liberated hydrogen peroxide when the sample was heated in an aqueous medium. The decomposition of the peroxide was markedly increased by the use of ferrous salt and the irradiation with light of λ > 300 nm. The grafting of methyl methacrylate on CMC peroxide was initiated by heating or irradiating with light, where the rate of grafting and the reciprocal of the average molecular weight of grafts in general were proportional to the square root of the peroxide content of the sample. The peroxide content of the sample was related closely to the number of grafts in initiation. The number was estimated as 17 times for thermal initiation and 6 times for photoinitiation at the maximum values. The CMC peroxide showed a marked activity toward photografting of acrylamide, acrylic acid, acrylonitrile, and vinyl acetate on the substrate.     

Formation of peroxide on aldehyde cellulose and its ability to initiate graft copolymerization

Cellulose peroxide formed by the treatment of aldehyde cellulose with hydrogen peroxide (H₂O₂) was investigated with respect to formation and decomposition conditions and with respect to graft initiation. Periodic acid-oxidized cellulose was proved to produce the peroxide group on the substrate by subsequent treatment with H₂O₂, whereas no peroxide was produced with unoxidized cellulose. Since the peroxide content of oxidized cellulose increased with increasing carbonyl content of the sample, the peroxide was presumed to be introduced at the site of the aldehyde group of the sample. The peroxide groups formed were proved to revert to aldehyde groups by decomposition upon heating with water to nearly the same level as the original. The structure of the peroxide group was believed therefore to be an α-hydroxy hydroperoxide type. The cellulose peroxide was found to initiate graft copolymerization of methyl methacrylate very easily in thermal initiation and photoinitiation systems.     

Hydrogel beads based on carboxymethyl cellulose for removal heavy metal ions

Environment‐friendly carboxymethyl cellulose (CMC) hydrogel beads were successfully prepared using epichlorohydrin (ECH) as a crosslinking agent in the suspension of fluid wax. There was an ether linkage formed between ECH and CMC, which was identified from bands in FTIR spectra of the prepared hydrogel. The prepared hydrogel beads with diameters about 4 mm were apparently spherical and fully transparent. The X‐ray diffraction (XRD) spectra indicated that the adsorption of metal ion onto the oxygen atom of carboxyl group led to change in crystallinity patterns of hydrogels. The scanning electron microscope (SEM) images clearly showed that the hydrogels had an internal porous structure. The adsorption capacity increased as initial concentrations of metal ions and the pH value of metal ion solution increased. Freundlich and Langmuir isotherm models were employed to analyze the data from batch adsorption experiments. There are vey good correlation coefficients of linearized equations for Langmuir model, which indicated that the sorption isotherm of the hydrogel beads for metal ions can be fitted to the Langmuir model. The maximum adsorption amount of hydrogel beads for metal ions is 6.49, 4.06, and 5.15 mmol/g for Cu(II), Ni(II), and Pb(II), respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

壳聚糖共混膜的制备及其对Cu2+的吸附

采用流延法将不同比例的壳聚糖、聚乙烯醇、甘油复合制膜,对水中Cu~(2+)进行吸附,考察了吸附时间、吸附温度、pH值对吸附性能的影响,结果表明,当pH=8、吸附温度为25℃、吸附时间为1 h,吸附率可达93%。     

Interaction of metal ions with carboxylic and carboxamide groups in protein structures

An analysis of the geometry of metal binding by carboxylic andcarboxamide groups in proteins is presented. Most of the ligandsare from aspartic and glutamic acid side chains. Water moleculesbound to carboxylate anions are known to interact with oxygenlone-pairs. However, metal ions are also found to approach thecarboxylate group along the C - O direction. More metal ionsare found to be along the syn than the anti lone-pair direction.This seems to be the result of the stability of the five-memberedring that is formed by the carboxylate anion hydrogen bondedto a ligand water molecule and the metal ion in the syn position.Ligand residues are usually from the helix, turn or regionswith no regular secondary structure. Because of the steric interactionsassociated with bringing all the ligands around a metal center,a calcium ion can bind only near the ends of a helix; a metal,like zinc, with a low coordination number, can bind anywherein the helix. Based on the analysis of the positions of watermolecules in the metal coordination sphere, the sequence ofthe EF hand (a calcium-binding structure) is discussed.     

基于金属盐溶液的纤维素溶解及其应用研究进展

纤维素是自然界储量最丰富的可再生生物质资源，其绿色高值化利用在实现“双碳”和“循环经济”目标中起到重要作用。纤维素的绿色高效溶解是实现其高值化利用重要途径之一。众多纤维素溶剂体系存在价格昂贵、毒性和环境威胁、溶解工艺复杂、溶解效率低、溶剂回收困难和能耗高等问题。金属盐溶液体系具有稳定性高、价格便宜，同时溶解纤维素速度快、溶解工艺简单等特点，是更具应用前景的低成本绿色溶剂。该文综述了不同金属盐溶液溶解纤维素的溶解机理，总结了影响溶解性能的关键因素，并进一步介绍了基于不同金属盐溶液溶解纤维素在薄膜材料、凝胶材料以及复合材料等领域的应用研究进展，总结并展望了金属盐溶液在纤维素溶解及功能化应用方面的优势、不足及发展方向。