聚丙烯胺肟螯合纤维的合成及其对铜（Ⅱ）离子的吸附

利用预辐照接枝法合成了聚丙烯胺肟螯合纤维，研究了影响接枝率，胺肟基团含量及离子吸附的因素，该纤维对铜的离子的吸附容量达０．６７ｍｍｏｌ／ｇ干纤维。     

聚乙烯醇胺肟型螯合纤维的合成及其对铜（Ⅱ）离子的吸附

本文报导通过预辐照接枝法首次合成了聚乙烯醇胺肟(PVAAO) 型螯合纤维,并且研究了影响接枝率和胺肟基因含量的因素。该纤维对铜(Ⅱ)离子的吸附容量最高达2.41毫克当量/克千纤维。     

一种新型PAN基强碱离子交换纤维的合成、表征及对Cr(Ⅵ)的吸附性能研究

以聚丙烯腈纤维为原料,经同步接枝与交联及季铵化二步反应制得一种富含强碱基团的PAN基阴离子交换纤维(SW-APAN)。该方法有效避免了复杂的辐照接枝和致癌试剂氯甲基甲醚的使用,所得功能纤维形貌良好、物理化学性质稳定,其总交换容量和强碱交换容量分别超过4mmol/g和2mmol/g。通过批量吸附实验和柱吸附实验初步考察了SW-APAN纤维对Cr(Ⅵ)的吸附性能,实验结果表明,该纤维具有较高吸附容量(298K下192.00mg/g)和优异的吸附动力学性能,且经5次吸附-脱附循环后,吸附容量仍保持稳定。     

偕胺肟化聚丙烯腈纳米纤维的制备及在含金属离子废水处理中的应用

利用电纺丝技术制备了聚丙烯腈纳米纤维无纺布, 然后在水溶液原位偕胺肟化得到偕胺肟化聚丙烯腈纳米纤维, 该纳米纤维可用于吸附再生含金属离子废水. 采用氯化铜溶液模拟含金属离子废水, 探讨不同肟化率的偕胺肟化纳米纤维对铜离子的吸附效果; 发现肟化率78.8%的偕胺肟化纳米纤维的吸附能力最好, 利用Langmuir吸附方程得到最大吸附值为56.5 mg/g, 同时吸附后可将含铜废水浓度从100 mg/L降至13 μg/L, 远远低于国标GB8978-1996规定的铜排放的一级标准(总铜浓度<0.5 mg/L). 吸附铜离子的纳米纤维在1 mol/L稀硝酸中, 100 min后铜离子的解吸附率超过98%. 经4次吸附-解吸附循环后, 偕胺肟化纳米纤维的吸附能力仍能达到首次吸附最大吸附值的50%以上, 表明偕胺肟化纳米纤维具有一定的循环再生能力.     

聚丙烯纤维预辐照接枝制备弱碱性离子交换纤维及其对链霉素的吸附

以γ-射线预辐照,在聚丙烯(PP)纤维上接枝丙烯酰胺(AAm),再经过Hofmarm降解反应制备弱碱性离子交换纤维(PP-g-YAm)交换容量达到5.47mmol/g干纤维.研究了PP-g-VAm纤维对链霉素的吸附和解吸性能.其吸附等温曲线符合Langmiur吸附等温式.静态吸附试验表明,PP-g-AAm纤维对链霉素的吸附量可以达到446.96mg/g千纤维,脱附率达到98.9%.     

硫脲基纳米螯合纤维对水溶液中Cd(Ⅱ)的吸附和密度泛函理论计算

以聚丙烯腈为原料, 利用静电纺丝技术和化学接枝制备得到硫脲基纳米螯合纤维, 并用于水溶液中 Cd(Ⅱ)的去除. 结合样品的表征和密度泛函(DFT)理论计算结果, 揭示了所制备纳米纤维材料对Cd(Ⅱ)的吸附机理. 借助静态吸附和动态吸附实验, 考察了硫脲基纳米螯合纤维对Cd(Ⅱ)的吸附性能. 结果表明, 纳米纤维吸附材料对Cd(Ⅱ)的最大吸附容量可达349.46 mg/g, 吸附过程在90 min以内即可达到基本平衡. 整个吸附过程符合准二级动力学模型和Langmuir等温吸附模型. 硫脲基纳米螯合纤维吸附Cd(Ⅱ)的吸附机理为表面配位络合, 增加纳米纤维表面硫脲基团的含量是提高吸附容量的重要途径. 该吸附材料经6次循环使用后, 最大动态吸附容量并未发生明显改变.     

改性罗布麻纤维的吸附功能研究

以Ce~(4+)引发丙烯腈与罗布麻纤维接枝共聚反应,用红外光谱表征了接枝纤维的结构。并探讨了接枝纤维皂化物时汞离子的吸附性能。C_(AN)为1.2×10~(-1)mol/L、C_(Ce)~(4+)为10×10~(-3)mol/L时接枝率较高,该接枝共聚物经皂化后能有效地吸附汞离子,pH值在10～11时吸附率最高,达0.583mg Hg~(2+)/g。     

接枝改性羧甲基纤维素对铜离子的吸附研究

将离子型单体丙烯酸(AA)及非离子型单体丙烯酰胺(AM)接枝在羧甲基纤维素(CMC)上,通过协同作用提高材料的吸水性及吸水速率,并研究了其对铜离子的吸附性能.通过傅里叶红外(FTIR)对材料分析表明,从及AM成功接枝在CMC上;对吸附物进行了表面分析,扫描电镜图(SEM)显示吸附物表面有大量颗粒状物质,X射线能谱(XPS)证实材料表面吸附了铜离子;在浓度为10mmol/L的铜离子溶液中,CMC-g-P(AA-co-AM)材料的吸附容量为20.30mmol/g.     

含羧基和吡啶基两性离子交换纤维的制备研究

采用γ射线预辐照PP纤维引发 4VP和AA(或AANa)或 4VP和MAA(或MAANa)接枝共聚 ,制得不同接枝率和不同链段结构的弱酸弱碱两性离子交换纤维。采用 4VP/AANa共接枝时 ,在不同单体投料比范围内获得高于 4 2 0 %的总接枝率。研究了纤维的预辐照剂量、单体浓度、摩尔盐含量、交联剂含量以及接枝温度和时间等条件对接枝共聚反应的影响。适宜的接枝共聚反应条件为 :预辐照剂量为 8× 10 4Gy ,单体浓度 10 % ,摩尔盐加入量约 0 .0 5 % ,交联剂用量 2 % ,接枝温度 65℃ ,时间 4h。发现两性纤维呈现双螺旋结构形态。对比自制的弱酸、弱碱离子交换纤维 ,所制备的两性纤维对酸性、中性、碱性氨基酸的吸附量比较大 ,对不同氨基酸具有不同的吸附分离能力     

丁二酸酐接枝纤维素纳米纤维膜及其重金属离子吸附

采用热致相分离(TIPS)法以三醋酸纤维素(TCA)为原料成功制备直径为(110±28)nm TCA多孔纳米纤维膜。将TCA纤维膜通过水解转化为纤维素(Cell)、接枝制备丁二酸酐接枝改性纤维素(Cell-g-SAA)膜。将Cell膜和Cell-g-SAA膜用于吸附水中Cu~(2+)、Pb~(2+),并对膜样品的吸附动力学、等温吸附和吸附热力学进行了研究。结果表明,二级动力学拟合和Langmuir模型更适合于该体系。与Cell膜相比,改性后Cell-g-SAA膜对Cu~(2+)和Pb~(2+)的最大吸附容量分别从51.73和34.29 mg/g增加到116.41和51.73 mg/g。纤维膜对Cu~(2+)、Pb~(2+)的吸附更趋近于单层吸附且化学吸附占主导地位。     

The Application of Polytetrafluoroethylene (PTFE) Fiber Grafted Acrylic Acid as a Cation Exchanger for Removing Cu~(12)

There are many advantages for ion exchange fibers prepared from the natural fiber, i.e. the strong hydrophilicity, the large surface area and the high speed of both adsorption and desorption for organic compounds and metal ions. It has been used widely in biochemical separation, analysis, the recovery of precious metals and the environmental protection1-2. But its application still is limited because of the poor anticorrosion property. Polytetrafluoroethylene (PTFE) possesses excellent che…     

γ-射线辐照接枝制备几种功能性高分子材料

概述了近几年来本研究组在高分子材料辐照接枝制备功能性高分子材料方面的研究进展.分别以丙烯酸、顺丁烯二酸、苯乙烯接枝聚四氟乙烯纤维,制备了不同酸性的聚四氟乙烯功能纤维.以N-异丙基丙烯酰胺接枝壳聚糖制备温度及pH敏感材料,获得了性能特异的新型功能性高分子材料.报道了该类新型功能高分子材料的各种特异性能,如对金属离子优异的分离、吸附和解吸性能、超强酸性和一系列潜在用途.     

Natural vermiculite as an exchanger support for heavy cations in aqueous solution

The natural highly charged lamellar silicate vermiculite was investigated as an exchanger matrix in doubly distilled water solution to exchange magnesium inside the lamella with the heavy cations copper, nickel, cobalt, and lead at the solid/liquid interface. The extension of each exchange reaction was dependent on time of reaction, pH, and cation concentration. The maximum time presented the following order Pb2+ < Ni2+ < Cu2+ < Co2+, which corresponds to 12, 24, 48, and 72 h, respectively. The best performance was observed for nickel, as represented by the exchange capacity Nf, which gave values 0.59, 0.76, 0.84, and 0.93 mmol g(-1) for Pb2+ < Co2+ < Cu2+ < Ni2+, respectively. This capacity is dependent on pH interval variation from 1 to 9, being significantly increased in alkaline condition. The isotherm data were adjusted to a modified Langmuir equation and from the data the spontaneous Gibbs free energy was calculated. Linear correlations were obtained through Gibbs free energy or the maximum capacity against the cationic radius plot, with the lowest values for the largest cation lead. An exponential correlation was also observed for the maximum capacity versus enthalpy of hydration plot, indicating a difficulty of the less hydrated cation, lead, in exchanging with magnesium inside the lamellar space, as suggested by the proposed mechanism. The saturated matrices with cations presented a decrease in interlayer distance in comparison with the original vermiculite, which can be related to the hydrated phases, characteristic for each cation, with a lowest value for lead.     

Cation exchange selectivity of some fission products on strongly acidic cation exchanger of sulfonic acid type-nitric acid system

Distribution coefficients of fission products in nitric acid for strongly acidic cation exchanger of sulfonic acid type with different cross-linking and structure were measured by a column method. Uptake of cationic fission products increases with resin cross-linking and decreases of nitric acid concentration. The distribution coefficient of the ion, [Kd_Mn+]^*, in a given system is expressed as log [Kd_Mn+]^*=B·log[Kd_Mn+]+A where [Kd_Mn+] is the distribution coefficient of the ion at 1M nitric acid for 10% crosslinked gel type cation exchanger, while A and B constants. Deviation from the above relation were observed for Y³⁺ and complex ions of ruthenium upward for macroporous type cation exchanger and downward for highly porous type cation exchanger. Upward deviation of Y³⁺ for 10% cross-linked gel type cation exchanger increased with concentration of nitric acid. Consequently, elution sequence varied from Y³⁺–Eu³⁺–Pm³⁺–Ce³⁺⁺ at 1M nitric acid to Eu³⁺–Pm³⁺–Y³⁺–Ce³⁺ for the same cation exchanger at 2M nitric acid. The same elution sequence, Eu³⁺–Pm³⁺–Y³⁺–Ce³⁺, was observed for 8% cross-linked gel type cation exchanger and 10% cross-linking macroporous type cation exchanger at 1M nitric acid.     

Comparative studies on the ion exchange behaviour of UO2(II), Ce(III) and Am(III) with Chelex-100 from thiocyanate media

The distribution of UO ₂ ²⁺ , Ce³⁺ and Am³⁺ between Chelex-100 and 0.2 and 5.0M ammonium thiocyanate solutions of different hydrogen ion concentrations has been investigated. The results obtained are compared with parallel experimental results using the anion exchanger Dowex-1×4 and the cation excharger Dowex-50×8. It is found that Chelex-100 can act as anion exchanger at pH<2 and as cation and chelate exchanger at higher pH. A main feature of the distribution results of UO ₂ ²⁺ , Am³⁺ and Ce³⁺ with Chelex-100 is the very high distribution coefficient for the three cations at pH higher than 3.5 from aqueous solutions containing 0.2 or 5.0M ammonium thiocyanate.     

Reactions of palladium(II) and rhodium(III) with pyridylazo-2-naphthol and dithizone on PANV–KU-2 and PANV–AV-17 fibrous materials

Reactions of palladium(II) and rhodium(III) with dithizone (DT) on polyacrylonitrile fiber filled with an AV-17 anion exchanger (PANV–AV-17) and 1-(2-pyridylazo)-2-naphthol (PAN) immobilized on polyacrylonitrile fiber filled with a KU-2 cation exchanger (PANV–KU-2–PAN) are studied by diffuse reflection spectroscopy. Conditions of rhodium complexation on PANV–KU-2–PAN (ascorbic acid concentration, pH of solution in adsorption, and the duration of heating samples) and palladium complexation with DT after adsorption from a 0.1 M NaCl solution (pH 2) on PANV–AV-17 in the dynamic mode are found. The limits of detection for rhodium and palladium are 10 and 5 ng/mL, respectively. At 640 nm, the calibration graphs are linear in the ranges of palladium and rhodium concentrations 0.008–0.06 µg/mL and 0.02–0.2 µg/mL, respectively. The mutual influence of rhodium and palladium is studied. It is shown that the determination of palladium with DT on a PANV–AV-17 solid phase is not affected by the presence of a 5-fold amount of rhodium, and rhodium can be determined on PANV–KU-2–PAN at 590 nm in the presence of 2-fold amounts of palladium.     

Speciation of aluminum in soil extracts using cation and anion exchangers followed by a flow-injection system with fluorescence detection using lumogallion.

Flow-injection analysis (FIA) with fluorescence detection of aluminum using lumogallion was applied to the chemical speciation of aluminum in soil extracts after the separation of aluminum species with ionic exchangers. Aluminum complexes with organic substances (anion species) can be specified from other species by using a strongly acidic cation exchanger in the pH range of 3 to 5. Furthermore, aluminum can be separated into three categories, namely, (i) the Al3+ and Al-OH complex, (ii) aluminum organic complexes (cation species), and (iii) its anion species by using a strongly acidic and a weakly acidic cation exchanger at around pH 5. A considerable percentage of water-soluble aluminum in soils was found to be complexes with humic substances.     

Three-component systems for conventional and window-shaped response fluorescent pH indicators

Three-component systems made of a tetradentate bis-amino bis-quinoline ligand, a transition metal cation (Ni2+ or Cu2+) and a fluorescent indicator (Coumarin 343) have been studied in a water-dioxane (1 : 4 v/v) mixture, through potentiometric, pH-spectrophotometric and pH-fluorimetric titrations. For the Cu2+ containing systems, an "on-off-on" variation of fluorescence intensity vs. pH has been observed, whereas in the presence of Ni2+ a simple "on-off" profile of the fluorescence intensity vs. pH was obtained. These ternary systems thus behave as window-shaped or conventional pH-indicators, depending whether Cu2+ or Ni2+ is used as the cation.     

CdTe/CdS荧光探针测定痕量铜(Ⅱ)

以巯基乙酸为稳定剂,在水溶液中合成CdTe/CdS量子点,基于量子点与Cu2+混合后发生荧光猝灭作用,建立CdTe/CdS量子点作为荧光探针检测微量铜的新方法。在pH 4.60的HAc-NaAc缓冲溶液中,反应时间为10 min时,Cu2+质量浓度在0.01～1.00μg/mL范围与CdTe/CdS量子点的荧光猝灭程度呈良好的线性关系,相关系数为0.9978,检出限为9.90×10-3μg/mL。方法可以用于雨水、自来水和延河水中Cu2+的分析。     

Determination of creatinine in serum by high-performance liquid chromatography: a comparison of three ion-exchange methods

Three ion-exchange high-performance liquid chromatographic methods for the determination of creatinine in serum have been compared. In method 1 a strong cation exchanger was used. In method 2 a reversed-phase column was given strong cation-exchange properties by the addition of N-methyloleoyl taurate to the mobile phase. In method 3 a weak cation exchanger was used. Elution was with a pH gradient in methods 1 and 2, and isocratic elution was used in method 3. The imprecision was similar for the three methods and varied between 0.9 and 2.5% as studied within-day and between 1.4 and 3.2% from day-to-day. The lowest coefficient of variation was obtained around the upper reference limit. Analytical recoveries were quantitative for the three methods. The method with N-methyloleoyl taurate showed no advantages over the conventional strong cation exchanger. With the weak cation exchanger no interferences were detected from compounds investigated, but with the strong cation exchanger a slight interference was obtained with uric acid. We prefer the weak cation-exchange method because of its simplicity, higher throughput and absence of interference from hitherto tested compounds.