辐射诱导合成水凝胶及其处理重金属废水的研究进展*

水凝胶是一种经适度交联而具有三维网络结构的新型功能高分子材料。制备水凝胶因操作简单、无须添加交联剂和引发剂等优点而受到关注。传统的处理重金属废水的方法或成本较高,或效率低,利用水凝胶处理重金属废水成为一种新的颇具潜力的方法。本文综述了辐射法制备水凝胶及其在重金属吸附去除方面的研究进展包括材料的制备、改性、去除重金属性能等方面的研究进展,并指出了水凝胶去除重金属的发展前景和今后的研究方向。     

聚丙烯酸盐-丙烯酰胺水凝胶的制备及对重金属离子吸附性能的研究

以丙烯酸(AA)、丙烯酰胺(AM)为单体,K2S2O8为引发剂,N,N'-亚甲基双丙烯酰胺为交联剂,采用水溶液聚合法合成P(AA-AM)水凝胶,通过正交实验优化了P(AA-AM)水凝胶的制备工艺.对制备的P (AA-AM)水凝胶进行了SEM和XPS分析,探讨了P(AA-AM)水凝胶对Cu2+、pb2+、Zn2+和Cd2+的吸附等温线和吸附动力学行为,研究了P(AA-AM)水凝胶的粒径、吸附温度、pH值和重金属离子的初始浓度对P(AA-AM)水凝胶吸附性能的影响.实验结果表明,所制备的P(AA-AM)水凝胶是一种具有三维网络结构的高分子材料,其表面的氨基和羧基残基能够与重金属离子发生螯合反应.减小P(AA-AM)水凝胶粒径、增大溶液pH值、升高吸附环境温度均有利于吸附反应的进行.粒径为0.097 ～0.15 mm的P(AA-AM)水凝胶粉末,在35℃、pH=5的条件下进行吸附等温线实验,得到水凝胶对重金属Cu2+,pb2+,Zn2+和Cd2+的理论最大吸附量分别为186,588,208和403 mg/g.P(AA-AM)水凝胶对重金属离子的吸附符合准二级动力学模型(R2＞0.98),吸附等温线符合Langmuir吸附等温线(R2＞0.95).干扰离子实验和理论模拟均证明P(AA-AM)水凝胶对pb2+具有良好的吸附性.     

纳米纤维素的改性及其吸附重金属离子的应用研究

纳米纤维素材料(cellulose nanomaterials,CNs)作为一种可再生材料,具有比表面积大、高结晶度、高强度、高杨氏模量、高表面活性、化学性质稳定等优异性能。纤维素作为天然高分子材料,在清除水体重金属离子中具有较好的应用的价值,因此本文对纤维素的改性及其吸附重金属的应用进行了综述。首先简要地介绍了纳米纤维素的结构与命名方法;其次,对纳米纤维素的改性(即小分子改性与高分子改性)进行了详细的介绍,并重点阐述了改性纳米纤维素基材以粉末、凝胶(包括水凝胶与气凝胶)两种不同的形态通过吸附清除水体重金属离子的应用研究。最后,对改性纳米纤维素基水吸附材料存在的优缺点进行了探讨,并指出了该材料在生产和应用过程中还需解决的问题。     

溶剂驱动四甲基六元瓜环桥联聚丙烯酸的苯酚派生物对杀菌剂的吸附和解析（英文）

根据苏氏一锅法,在过硫酸铵既作为氧化剂又作为引发剂的条件下合成了一系列四甲基六元瓜环桥联聚丙烯酸。研究了丙烯酸浓度、四甲基六元瓜环投入量和过硫酸铵浓度对聚合物形成的影响。四甲基六元瓜环桥联聚丙烯酸可以进一步与苯酚发生酯化反应,生成不溶于水的派生物,因此可用于吸附和解析杀菌剂。     

溶剂驱动四甲基六元瓜环桥联聚丙烯酸的苯酚派生物对杀菌剂的吸附和解析

根据苏氏一锅法,在过硫酸铵既作为氧化剂又作为引发剂的条件下合成了一系列四甲基六元瓜环桥联聚丙烯酸.研究了丙烯酸浓度、四甲基六元瓜环投入量和过硫酸铵浓度对聚合物形成的影响.四甲基六元瓜环桥联聚丙烯酸可以进一步与苯酚发生酯化反应,生成不溶于水的派生物,因此可用于吸附和解析杀菌剂.     

物理交联聚乙烯醇/羟基末端聚酰胺-胺树型高分子水凝胶的制备与性质研究

聚乙烯醇(PVA)是一种水溶性的生物相容性好并可降解的合成高分子,PVA通过化学或物理方法交联可以形成水凝胶,PVA与聚丙烯酸(PAA)、聚N-异丙基丙烯酰胺(PNIPA)、聚乙烯基吡咯烷酮(PVP)及壳聚糖形成互穿网络型水凝胶,改善凝胶的性质,另一方面,树型高分子是一     

温度及pH敏感性水凝胶的合成及性能研究

乙烯基吡咯烷酮与丙烯酸共聚物／聚丙烯酸β-羟基丙酯互穿网络水凝胶具有温度及PH双重敏感特性。经验证,在蒸馏水中,聚丙烯酸β－羟基丙酯与丙烯酸间存在络合作用,在缓溶液中,没有这样络合作用。     

海藻酸钠-锌自修复水凝胶的制备及其对亚甲基蓝的吸附性能

废水处理中迫切需要制备多重刺激响应和具有自修复性能的吸附剂。基于此,本文选择海藻酸钠（ALG）和锌离子（Zn2+）为原料,通过一步法快速（仅2s）制备了超分子水凝胶。所制备的水凝胶显示出多重刺激（pH,金属盐等）响应性和自修复性能,这对吸附有机污染物至关重要。选择亚甲基蓝（MB）为模型染料研究了水凝胶的吸附性能。水凝胶对MB的最大吸附量为5.3 mg/g,对低浓度污染物具有良好的吸附能力（去除率超过80％）。吸附动力学均符合准二级动力学方程,Freundlich模型能很好地拟合等温吸附过程,表明ALG-Zn水凝胶对MB的吸附以多层吸附为主。制备出的ALG-Zn水凝胶适合作为吸附剂应用于废水处理。     

松香基功能高分子对Cu(Ⅱ)吸附性能的研究

以马来松香丙烯酸乙二醇酯和丙烯酸为功能单体,采用悬浮聚合法合成了松香基功能高分子,重点研究了其对水中Cu2+的静态吸附性能。结果表明,在溶液pH=5.0,Cu2+为3.0mg/mL,温度为308K的条件下,其对Cu2+的最大静态饱和吸附量为67.06mg/g;松香基功能高分子对Cu2+吸附速率符合一级动力学方程及颗粒内扩散方程,过程受液膜扩散阻力及颗粒内扩散阻力共同影响;松香基功能高分子对Cu2+吸附过程符合Freundlich和Langmuir方程;对吸附热力学的研究结果表明,该树脂对Cu2+的吸附为放热过程,而且是自发进行的。     

新型半纤维素基磁性水凝胶的制备及性能

采用H2O2-Vc氧化还原体系引发半纤维素衍生物,以表面修饰的Fe3O4粒子作为磁性组分,利用接枝共聚方法制备了新型半纤维素基磁性水凝胶.分别用傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)对水凝胶的结构及形貌进行了表征,利用X射线衍射(XRD)和振动样品磁强计(VSM)对水凝胶的晶型结构及磁性能进行了分析,发现Fe3O4粒子均匀分散在凝胶网络中,半纤维素基磁性水凝胶表现出良好的顺磁性.考察了丙烯酸/半纤维素比例、Fe3O4粒子含量及交联剂用量对水凝胶溶胀性能的影响,并探讨了该水凝胶的溶胀机理,它在pH 8缓冲溶液中的溶胀较好符合Fickian和Schott动力学模型.通过SEM和溶胀性能分析表明,随着pH值的升高水凝胶的孔径增大,水凝胶的溶胀率逐渐增大.制备的水凝胶被用于溶菌酶吸附研究,结果表明磁性凝胶的吸附量大于非磁性水凝胶,水凝胶的吸附行为符合Freundlich和Temkin等温模型.     

Recent advances on hydrogels based on chitosan and alginate for the adsorption of dyes and metal ions from water

In contemporary times, water resources have become increasingly scarce and suffer from anthropogenic pollution sources with an organic and inorganic origin that are products of industrial, agricultural, and everyday waste. Contamination with heavy metals and dyes in wastewater is considered a risk for water sources that can leak into underground and surface sources, leading to increased biological and chemical contamination. The pollutant removal process is performed by adsorption treatment methods, which is the most common method, and it is considered an effective method with a high and economical removal rate.In this review, we discuss the use of biobased hydrogel adsorbents in the removal of organic dyes and metal ions from water. The literature indicates that hydrogels exhibit rapid absorption kinetics and a dye removal absorption capacity that can reach more than 100 mg/g and sometimes more than 2000 mg/g, with a metal adsorption capacity ranging from 38 mg/g to more than 440 mg/g. These results are discussed and compared by taking into account hydrogel materials that contain biopolymers such as alginate, chitosan or both. In general, absorption depends mainly on biobased materials, which have a natural origin and can be utilized to synthesize hydrogels to remove pollutants, dyes and heavy metals. Chitosan and alginate are prominent materials for this use and they can be incorporated with other components to obtain hydrogels or nanocomposite materials with different efficacies to remove dyes and metal ions.     

Efficient Adsorption and Recovery of Pb(II) from Aqueous Solution by a Granular pH-Sensitive Chitosan-based Semi-IPN Hydrogel

A series of granular pH-sensitive semi-interpenetrating polymer network (semi-IPN) hydrogels based on chitosan (CTS), acrylic acid (AA) and gelatine (GE) were utilized for the adsorption and recycle of Pb(II) from aqueous solutions. The composite hydrogels have been characterized by FT-IR and TGA. The effects of contact time, pH value and initial Pb(II) concentration on the adsorption were investigated. Results indicated that the adsorption capacity of the hydrogel increased with increasing pH value and initial Pb(II) concentration, and a pH-sensitive adsorption characteristic was presented. The adsorption rate of the semi-IPN hydrogels on Pb(II) is fast with an adsorption rate constant of 14.9790 mg/(g·s), and adsorption equilibrium could be reached within 10 min. The adsorption isotherms of the hydrogels for Pb(II) could be described well by the Langmuir equation, rather than the Freundlich equation. The as-prepared hydrogels showed good reusability with 0.05 mol/l HNO₃ solutions as the desorbing agent and 0.1 mol/l NaOH solutions as the regeneration agent, respectively. After five consecutive adsorption-desorption processes, the semi-IPN hydrogel with 20 wt% GE may reach 85.26% of its initial adsorption capacity. In addition, the adsorbed Pb(II) can be quantitatively recovered by simply eluting the hydrogel with dilute HNO₃ solution, and a recovery ratio of 89.27% was reached for the semi-IPN hydrogel. The satisfactory adsorption amount is mainly derived from the chelating of functional groups (i.e. –COO^? and –NH₂) with Pb(II) ions. The hydrogel adsorbents exhibited excellent affinity for Pb(II), and can be applied to treat wastewater containing heavy metal ion and simultaneously recover the valuable metal sources.     

Facile synthesis of poly(DMC‐co‐HPA) hydrogels via infrared laser ignited frontal polymerization and their adsorption–desorption switching performance

In this work, we report a versatile infrared laser ignited frontal polymerization technique for the fabrication of a series of poly(DMC‐co‐HPA) hydrogels (DMC = methacryloxyethyltrimethyl ammonium chloride, HPA = hydroxypropyl acrylate). Because the method is based on the exothermic reaction, no further energy is required in the reaction once it is initiated. Moreover, we have found the polymerization process is a pure frontal polymerization model without involving any other reaction process. The dependence of frontal velocity and temperature on the reaction time is thoroughly discussed. The as‐prepared hydrogels are pH‐responsive and their maximum equilibrium swelling ratio could reach ～3,890%. Also, the as‐prepared poly(DMC‐co‐HPA) hydrogels capable of adsorption/desorption switching performance can be utilized for heavy metal ion removal in wastewater treatments. Interestingly, the hydrogels can float on the water surface after intaking heavy metal ions by the combination of kerosene and polyoxyethylene sorbitan monolaurate (Tween 20) in hydrogel components, greatly enhancing treatment efficiency. We believe the method described herein to rapidly construct functional hydrogels with the ability to remove heavy metal ions may find unique applications in emergency processing of water pollution. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2085–2093     

金属组学方法识别水中络合态重金属形态及其吸附净化技术研究进展

Cu²⁺、Pb²⁺和Ni²⁺等重金属离子可与水中乙二胺四乙酸、柠檬酸、酒石酸等有机分子形成络合态重金属。相比于游离态离子,络合态重金属具有更高的水溶性和环境毒性,在广泛的pH值范围内稳定存在且形态复杂,难以通过化学沉淀等常规方法高效去除。对近年来基于金属组学方法的水中络合态重金属复杂形态分析方法进行总结,对吸附净化技术在络合态重金属废水处理中的研究进展进行综述,并对上述领域需要解决的问题进行了探讨和展望。     

香蕉皮对重金属离子铅的吸附性能研究

建立了香蕉皮快速、高效对重金属离子铅吸附性能的方法。采用分光光度法测定重金属离子铅的浓度,分别研究了7种不同形态的吸附剂对废水中重金属离子铅的吸附性能。在优化的实验条件下,重金属离子铅浓度与吸光度的线性相关系数R=0.999 83,且方法相对标准偏差(RSD)低于3%。结果表明,香蕉皮对废水中的重金属离子铅有良好的吸附效果,吸附率达到91.3%。利用香蕉皮去除废水中的重金属离子,可以变废为宝,且方法吸附率高、准确可靠、精密度高,可用于吸附废水中重金属离子铅。     

Itaconic copolymer modified loess for high-efficiently removing copper ions from wastewater

Using Loess of clay (LC) which is low-cost, highly hydrophilic and small granule materials, biocompatible itaconic acid (IA), 2-hydroxyethyl methacrylate (HEMA) and N-vinyl-2-pyrrolidone (NVP) as functional monomers, a novel biocompatible polymer composite adsorbent (LC/PIHN) was prepared by in-situ copolymerization. It was applied to remove copper ions from wastewater, and the mechanism of adsorption was investigated. It showed that the Cu(II) removal was more than 99.8% at room temperature. The adsorption kinetics and isotherms of LC/PIHN fit the pseudo-second-order model and the Freundlich model, respectively. In summary, LC/PIHN is a kind of biocompatible, low-cost and excellent polymer composite adsorbent for removing heavy metal ions from wastewater.     

Encapsulated zerovalent iron/nickel-fly ash zeolite foam for treating industrial wastewater contaminated by heavy metals

Pollution due to heavy metal discharge into water systems is a global issue that has attracted growing attention in recent years. Thus, we had synthesized encapsulated zerovalent iron/nickel-fly ash zeolite foam (SA-ZFN foam) by freeze-drying method for the simultaneous removal of various heavy metals from industrial wastewater. The resulting SA-ZFN foam’s structural characterization was performed using advanced instrumental techniques. In addition, factors influencing heavy metal removal were discussed including the pH, reaction time, temperature, initial metal concentration, and their competition with each other; and the adsorption mechanism was investigated. The Langmuir maximum capacity of as-prepared foam was 75.76, 49.78, 44.89, and 7.31 mg/g for Cu(II), As(V), Hg(II), and Cr(VI), respectively. Furthermore, isotherms and kinetic data revealed that the rate-limiting step is monolayer adsorption on a homogeneous surface.Furthermore, thermodynamic studies indicated that ΔG° decreases as temperature rises, i.e. the adsorption process becomes more favorable at higher temperatures. The results suggest the no significant decrease of adsorption capacity on each cycle was observed by re-sustaining over three times in the first two cycles. When applied to real industrial wastewater, the SA-ZFN foam reduced the residual heavy metals to acceptable levels. Continuous column experiment also suggested that the SA-ZFN foam could simultaneously remove the heavy metals from aqueous solutions. From these results, it is demonstrated that the SA-ZFN foam is a promising, efficient, and economical material for wastewater treatment.     

烷氧磺酸盐功能化的聚乙撑二氧噻吩水凝胶

通过氧化偶联聚合方法成功地制备出一种基于烷氧磺酸盐功能化的聚乙撑二氧噻吩水凝胶, 揭示了零维单体胶束向二维纳米片层及三维水凝胶的转变过程, 发现通过改变反应温度或初始单体浓度, 可以诱导水凝胶网络结构单元的维度变化, 即由零维纳米粒子向二维纳米片层进行转化. 提出了一种导电高分子水凝胶的合成方法, 即采用一种氧化剂与一种多价金属盐的混合物作为引发剂, 其中前者用于诱导单体聚合, 后者则充当离子交联试剂, 并发现可以通过引入不同金属离子来改变凝胶的形貌. 此外, 导电高分子水凝胶具有良好的电化学电容, 并具有选择性吸附与可控脱附某些染料分子的特性.     

Preparation of poly(vinylalcohol)/poly(acrylamide‐co‐vinyl imidazole)/γ‐Fe2O3 semi‐IPN nanocomposite and their application for removal of heavy metal ions from water

A series of magnetic semi‐interpenetrating polymer network (semi‐IPN) hydrogels was prepared in one‐stage strategy composed of linear poly(vinyl alcohol) (PVA) chains and magnetic γ‐Fe₂O₃ nanoparticles entrapped within the cross‐linked poly(acrylamide‐co‐vinylimidazole) (poly(AAm‐co‐VI)) network. The influence of PVA, weight ratio of AAm:VI, γ‐Fe₂O₃, and MBA on the swelling properties of the obtained nanocomposite hydrogels was evaluated. The prepared magnetic semi‐IPN hydrogels were fully characterized and used as absorbent for removal of Pb(II) and Cd(II) from water. Factors that influence the metal ion adsorption such as solution pH, contact time, initial metal ion concentration, and temperature were studied in details. The experimental results were reliably described by Langmuir adsorption isotherms. The adsorption capacity of semi‐IPN nanocomposite for Pb(II) and Cd(II) were175.80 and 149.76 mg g^?1, respectively. The kinetic experimental data indicated that the chemical sorption is the rate‐determining step. According to thermodynamic studies, Pb(II) and Cd(II) adsorption on the hydrogels was endothermic and also chemical in nature. The prepared magnetic PVA/poly(AAm‐co‐VI) semi‐IPN hydrogels could be employed as efficient and low‐cost adsorbents of heavy metal ions from water. Copyright © 2016 John Wiley & Sons, Ltd.     

Industrial wastes as low-cost potential adsorbents for the treatment of wastewater laden with heavy metals

Industrial wastes, such as, fly ash, blast furnace slag and sludge, black liquor lignin, red mud, and waste slurry, etc. are currently being investigated as potential adsorbents for the removal of the heavy metals from wastewater. It was found that modified industrial wastes showed higher adsorption capacity. The application of low-cost adsorbents obtained from the industrial wastes as a replacement for costly conventional methods of removing heavy metal ions from wastewater has been reviewed. The adsorption mechanism, influencing factors, favorable conditions, and competitive ions etc. on the adsorption of heavy metals have also been discussed in this article. From the review, it is evident that certain industrial waste materials have demonstrated high removal capacities for the heavy metals laden with wastewater. However, it is to be mentioned that adsorption capacities of the adsorbents vary depending on the characteristics of the adsorbents, the extent of chemical modification and the concentration of adsorbates. There are also few issues and drawbacks on the utilization of industrial wastes as low-cost adsorbents that have been addressed. In order to find out the practical utilization of industrial waste as low-cost adsorbents on the commercial scale, more research should be conducted in this direction.