基于聚乙烯亚胺纳米纤维亲和膜研究
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摘要
水资源短缺和水环境恶化是当今世界普遍存在的问题,重金属离子和有机染料污染废水由于对人和牲畜等生物体具有较高的毒性而受到研究人员的广泛关注。亲和膜分离技术同时具有亲和色谱选择性高、分离速度快、能耗低和膜分离技术操作条件温和、无污染、无相变、易放大的特点而被广泛用于环境修复领域。
本文的主要研究了基于聚乙烯亚胺纳米纤维亲和膜对水体重金属离子和阴离子染料分子的去除性能和检测。首先,以聚乙烯醇溶液对聚乙烯亚胺进行共混改性,采用湿法静电纺丝方法制备了交联聚乙烯亚胺／聚乙烯醇纳米纤维亲和膜,用于水体重金属离子废水的去除;然后,以聚醚砜溶液对聚乙烯亚胺进行共混改性,采用干法静电纺丝-溶剂刻蚀后处理工艺制备了一种具有微纳结构的聚乙烯亚胺／聚醚砜纳米纤维亲和膜,用于重金属离子和阴离子染料废水的脱除；经上述两种纳米纤维亲和膜处理之后的水溶液中金属离子的浓度需要对其进行检测以使其达到环保的要求。因此本文最后合成了一种对水体中铜离子具有选择性识别功能的荧光化合物,并将其共混到聚醚砜体系内,采用静电纺丝方法制备出对水体微量铜离子具有高效选择性识别功能的纳米纤维亲和膜传感器。
1、以聚乙烯亚胺(PEI)为吸附剂、聚乙烯醇(PVA)为助纺剂,采用湿法静电纺丝技术制备出对水体铜、铅、镉等重金属离子具有高效吸附功能的PEI/PVA纳米纤维亲和膜。湿法静电纺丝中凝固浴由交联剂戊二醛(GA)和PEI的不良溶剂N,N’-二甲基甲酰胺(DMF)组成。这种湿法静电纺丝方法可以消除在静电纺丝过程中溶剂挥发不完全导致纳米纤维表面粘结的现象。当PVA的掺杂量为10%时,PEI/PVA纳米纤维的微观形态结构最为理想,PEI/PVA纳米纤维的平均直径约为650nm,且纳米纤维表面光滑；PEI/PVA纳米纤维亲和膜对Cu(Ⅱ)、Cd(Ⅱ)和Pb(Ⅱ)三种金属离子的平衡吸附模型更适于用Langmuir等温模型来描述,且最大饱和吸附量分别为70.92mg/g、121.95mg/g和94.34mmg/g；PEI/PVA纳米纤维亲和膜能够在0.05MEDTA溶液中再生,经过3次吸附-脱附循环实验之后,对铜离子的吸附效率仍然能够保持95.6%。此外,和文献报道的流延膜相比,PEI/PVA纳米纤维亲和膜对铜和镉的最大吸附量分别增加了1.31倍和2.27倍。
2、以聚醚砜(PES)为助纺剂,采用干法静电纺丝技术制备PEI/PES纳米纤维。当聚合物总浓度为30%、PEI/PES质量比为1.4/1时,所得纳米纤维截面为圆形、表面光滑的良好微观形态结构,纳米纤维平均直径约为300nm。此外,从纳米纤维的SEM照片上可以看出,在静电纺丝的过程中,PEI组分倾向于迁移到纳米纤维的表面。采用丙酮/水/戊二醛交联体系对PEI/PES纳米纤维进行交联后处理,发现纳米纤维上PEI组分在交联中由于PEI大分子和溶剂水分子的溶剂化作用而刻蚀,以微球的形式沉积在纳米纤维的表面,并且这种微纳结构的形成与交联体系中水的含量有关,当交联体系中水的含量高于20%时,能够得到均匀的微纳结构的纳米纤维膜,且纳米纤维上的突起小球的直径范围为50-250nm。由氮吸附-脱附(BET)和铜离子吸附实验证明,当交联体系中水的含量为30%时,所制备的微纳结构PEI/PES纳米纤维膜的比表面积最大,为7.27m2/g。
3、研究了微纳结构PEI/PES纳米纤维亲和膜对水溶液中重金属离子和阴离子染料的吸附性能和机理。发现溶液起始pH值对微纳结构PEI/PES纳米纤维亲和膜表面的性质有着重要影响：在酸性条件下,微纳结构PEI/PES纳米纤维亲和膜对阴离子染料具有较好的吸附性能,而对重金属离子的吸附更需要起始溶液呈中性；微纳结构PEI/PES纳米纤维亲和膜对阴离子染料和重金属离子的吸附行为更适合用Langmuir等温吸附模型来描述,从Langmuir等温吸附模型计算出PEI/PES纳米纤维膜对日落黄、固绿、苋菜红、铅离子、铜离子和镉离子的饱和吸附量分别为1000mg/g、344.83mg/g、454.44mg/g、94.34mg/g、161.29mg/g和357.14mmg/g；微纳结构PEI/PES纳米纤维亲和膜对重金属离子的吸附速率要快于阴离子染料,吸附动力学更符合准二级动力学模型和颗粒内扩散模型；微纳结构PEI/PES纳米纤维亲和膜对重金属离子和阴离子染料的吸附过程都是自发进行且都属于物理吸附,但是对重金属离子的吸附则是放热反应,而对阴离子染料的吸附是吸热反应。亲和膜的再生研究结果表明,0.05MEDTA和0.05MNaOH分别是吸附重金属离子和阴离子染料PEI/PES纳米纤维亲和膜的理想再生溶液。
4、经上述两种纳米纤维亲和膜处理之后的水溶液中金属离子的浓度需要对其进行检测以使其达到环保的要求,本文合成了一种罗丹明酰肼水杨醛席夫碱荧光分子,发现当铜离子与该荧光分子络合之后会导致罗丹明分子内开环,使其从非共轭结构转变成共轭结构而具有较强的荧光性质,且该荧光分子对水体铜离子的检测限为1×10-6M。此外,将罗丹明酰肼水杨醛席夫碱荧光分子与聚醚砜共混,采用静电纺丝技术成功制备了一种新型纳米纤维荧光传感器,并将其用于水体微量铜离子的检测。发现纳米纤维上的荧光分子对铜离子的高效选择性识别功能得到了增强,对铜离子的检测限为1×10-8M。研究了纳米纤维传感器对铜离子的识别机理,发现铜离子和荧光分子是以化学计量比为1：1进行络合。
Water resources shortage and pollution have been common problems currently. Among the number of polluting species at issue, heavy metal ions and organic dyes are of special concern because of their high toxicity for human and animals'health. Affinity membrane separation technology has been widely used in environmental remediation application due to its high performance of affinity chromatography and membrane technology, such as high selectivity, high efficiency, and no pollution and so on.
This work mainly focuses on the removal of heavy metal ions and anionic dyes, and detection of trace heavy metal ions in aqueous solution. Fitstly, cross-linked electrospun poly(ethyleneimine)(PEI) nanofibrous membranes doped with PVA were fabricated by wet-electrospinning in a one-step method instead of the conventional electrospinning and subsequent crosslinking method and the PEI/PVA nanofibrous membranes were applied to metal ions adsorption from an aqueous solution; Secondly, micro-nano structure nanofibrous affinity membranes of poly(ether sulfones)(PES) blended with a functional polymer PEI were fabricated by electrospinning technique followed by solvent etching in crosslinking solution, and this novel micro-nano structure PEI/PES nanofibrous membrane was utilized as an adsorbent for anionic dyes and heavy metal ions from aqueous solutions; the concentrations of the heavy metal ions solutions treated by two kinds of nanofibrous affinity membranes should be detected whether it meet the demand of environmental protection. So, a novel nanofibrous affinity membrane sensor was fabricated from a fluorescence molecule doped PES solutions and its sensing properties to Cu2+were investaged systematically.
1. PEI and PVA were chosen as functional affinity polymer and fiber-forming agent, respectively. Crosslinked PEI nanofibrous affinity membranes for effective removing heavy metal ions were fabricated via wet-electrospinning from its aqueous solution. The coagulating bath for wet-electrospinning was composed of the crosslinking agent glutaraldehyde (GA) and N,N-dimethylformamide (DMF) as a non-solvent. This wet-electrospinning method provided a new approach for fabricating the crosslinked nanofibers from the polymers, in which sticky phenomenon could occur at the process of the electrospinning. When the PEI/PVA weight ratio was90/10, the PVA doped PEI nanofibrous membranes with ideal morphology was obtained. The nanofibers had an average diameter of650nm and the surface of the nanofibers was very smooth. The Langmuir equation gave a better fit to the experimental data than the Freundlich equation, and the maximum absorption capacities (from Langmuir isotherm data) for Cu(II), Cd(II) and Pb(II) were70.92mg/g,121.95mg/g and94.34mg/g, respectively. The PEI nanofibrous affinity membrane adsorbed with heavy metal ions could be regenerated successfully in EDTA aqueous solution without significantly affecting its adsorption efficiency, it was found that the desorption efficiency reached about95.6%after the third cycles. The Cu(II) and Cd(II) adsorption data were about1.31and2.27times higher than the reported values of PEI/PVA cast membrane.
2. PEI/PES nanofibers were fabricated by electrospinning and PES was an excellent candidate for the matrix due to its good electrospinnability. In order to obtain PEI/PES nanofibrous membrane with high PEI content and finer fiber diameter, the blend ratio of1/1.4(w/w) and the total polymer concentration of30wt%were chosen in the electrospinning process. From the SEM images, it was found that the average diameter of the nanofibers was300nm and in addition most joints of PEI/PES nanofibers were stuck together, indicating that liquid PEI with high viscocity was concentrated at the fiber surface. The nanofibrous PEI/PES membranes were crosslinked in a mixture of acetone and water with glutaraldehyde (crosslinking agent, GA), and the micro-nano structural surface of the nanofibrous membranes was created by solvent etching due to the solvation between PEI and the solvent water in the crosslinking solution during the crosslinking process. The influence of the component of the crosslinking bath on the mophology of the resulting PEI/PES nanofibers was investigated. It was found that the relatively uniform micro-nano spherules grew on the surface of the nanofibers when the content of water in crosslinking solution was more than20wt%, and the diameters of the spherules were in the range of50-250nm. From the data of BET results and Cu2+adsorption performance, it was found that when the water content in crosslinking solution was30%, the resulting PEI/PES nanofibrous membrane has the maximum specific surface area, which was7.27m2/g.
3. Adsorption performance of the micro-nano structure PEI/PES nanofibrous membrane for anionic dyes or heavy metal ions from aqueous solutions was investigated. A series of adsorption experiments were carried out to investigate the influence of membrane dosage, initial solution pH value, contact time, initial solution concentration and adsorption temperature on the adsorption performance. The experimental results showed that the removal of the anionic dyes and metal ions on this PEI/PES nanofibrous membrane was a pH-dependent process with the maximum adsorption capacity at the initial solution pH of1for anionic dyes and5-7for metal ions, respectively. The adsorption equilibrium data were all fitted well to the Langmuir isotherm equation, with a maximum adsorption capacity values of1000mg/g,344.83mg/g,454.44mg/g,94.34mg/g,161.29mg/g and357.14mg/g for Sunset Yellow FCF, Fast Green FCF, Amaranth, Pb(II), Cu(II) and Cd(II), respectively. The kinetic study indicated that the adsorption of metal ions and anionic dyes could be well fitted by the pseudo-second-order model and intraparticle diffusion model, suggesting intra-particle diffusion process as the rate-limiting step of the adsorption process. Thermodynamic parameters such as free energy, enthalpy and entropy of adsorption of anionic dyes and metal ions were also evaluated and the results showed that the adsorption was a spontaneous physical adsorption process. In addition, the adsorption process of heavy metal ions was exothermic; however, the adsorption process of anionic dyes was endothermic. This micro-nano structure PEI/PES nanofibrous membrane could be regenerated successfully in0.05M NaOH and0.05M EDTA aqueous solution used for removal of anionic dyes and heavy metal ions, respectively.
4. The concentrations of the heavy metal ions solutions treated by two kinds of nanofibrous affinity membranes should be detected whether it meet the demand of environmental protection. Firstly, a fluorescence molecule, rhodamine hydrazone salicylaldehyde Schiff base, was synthesized as the sensing material and its chemical structure was obtained. It was found that the ion-recognition was based on the Cu+induced spirolactam ring "close-open" switch of the fluorescence molecule, with their advantages of significant absorption and fluorescence enhancement and the detection limit was1×10-6M. Secondly, the fluorescence molecule was blended with PES solution and electrospun to prepare a novel nanofibrous membrane sensor. It was found that this novel nanofirous membrane sensor showed high selectivity and sensitivity for Cu2+. In addition, the sensitivity of the fluorescence probe on the nanofibrous membrane sensor was much higher than that in the aqueous solution and the detection limit of the nanofibrous membrane sensor was1×10-8M. The complex mechanism between rhodamine hydrazone salicylaldehyde Schiff base and Cu2+was investigated by Job method, and it was found the nonlinear fitting of the titration curve assumed a1:1stoichiometry for the Cu-complex.
本文的主要研究了基于聚乙烯亚胺纳米纤维亲和膜对水体重金属离子和阴离子染料分子的去除性能和检测。首先,以聚乙烯醇溶液对聚乙烯亚胺进行共混改性,采用湿法静电纺丝方法制备了交联聚乙烯亚胺／聚乙烯醇纳米纤维亲和膜,用于水体重金属离子废水的去除;然后,以聚醚砜溶液对聚乙烯亚胺进行共混改性,采用干法静电纺丝-溶剂刻蚀后处理工艺制备了一种具有微纳结构的聚乙烯亚胺／聚醚砜纳米纤维亲和膜,用于重金属离子和阴离子染料废水的脱除；经上述两种纳米纤维亲和膜处理之后的水溶液中金属离子的浓度需要对其进行检测以使其达到环保的要求。因此本文最后合成了一种对水体中铜离子具有选择性识别功能的荧光化合物,并将其共混到聚醚砜体系内,采用静电纺丝方法制备出对水体微量铜离子具有高效选择性识别功能的纳米纤维亲和膜传感器。
1、以聚乙烯亚胺(PEI)为吸附剂、聚乙烯醇(PVA)为助纺剂,采用湿法静电纺丝技术制备出对水体铜、铅、镉等重金属离子具有高效吸附功能的PEI/PVA纳米纤维亲和膜。湿法静电纺丝中凝固浴由交联剂戊二醛(GA)和PEI的不良溶剂N,N’-二甲基甲酰胺(DMF)组成。这种湿法静电纺丝方法可以消除在静电纺丝过程中溶剂挥发不完全导致纳米纤维表面粘结的现象。当PVA的掺杂量为10%时,PEI/PVA纳米纤维的微观形态结构最为理想,PEI/PVA纳米纤维的平均直径约为650nm,且纳米纤维表面光滑；PEI/PVA纳米纤维亲和膜对Cu(Ⅱ)、Cd(Ⅱ)和Pb(Ⅱ)三种金属离子的平衡吸附模型更适于用Langmuir等温模型来描述,且最大饱和吸附量分别为70.92mg/g、121.95mg/g和94.34mmg/g；PEI/PVA纳米纤维亲和膜能够在0.05MEDTA溶液中再生,经过3次吸附-脱附循环实验之后,对铜离子的吸附效率仍然能够保持95.6%。此外,和文献报道的流延膜相比,PEI/PVA纳米纤维亲和膜对铜和镉的最大吸附量分别增加了1.31倍和2.27倍。
2、以聚醚砜(PES)为助纺剂,采用干法静电纺丝技术制备PEI/PES纳米纤维。当聚合物总浓度为30%、PEI/PES质量比为1.4/1时,所得纳米纤维截面为圆形、表面光滑的良好微观形态结构,纳米纤维平均直径约为300nm。此外,从纳米纤维的SEM照片上可以看出,在静电纺丝的过程中,PEI组分倾向于迁移到纳米纤维的表面。采用丙酮/水/戊二醛交联体系对PEI/PES纳米纤维进行交联后处理,发现纳米纤维上PEI组分在交联中由于PEI大分子和溶剂水分子的溶剂化作用而刻蚀,以微球的形式沉积在纳米纤维的表面,并且这种微纳结构的形成与交联体系中水的含量有关,当交联体系中水的含量高于20%时,能够得到均匀的微纳结构的纳米纤维膜,且纳米纤维上的突起小球的直径范围为50-250nm。由氮吸附-脱附(BET)和铜离子吸附实验证明,当交联体系中水的含量为30%时,所制备的微纳结构PEI/PES纳米纤维膜的比表面积最大,为7.27m2/g。
3、研究了微纳结构PEI/PES纳米纤维亲和膜对水溶液中重金属离子和阴离子染料的吸附性能和机理。发现溶液起始pH值对微纳结构PEI/PES纳米纤维亲和膜表面的性质有着重要影响：在酸性条件下,微纳结构PEI/PES纳米纤维亲和膜对阴离子染料具有较好的吸附性能,而对重金属离子的吸附更需要起始溶液呈中性；微纳结构PEI/PES纳米纤维亲和膜对阴离子染料和重金属离子的吸附行为更适合用Langmuir等温吸附模型来描述,从Langmuir等温吸附模型计算出PEI/PES纳米纤维膜对日落黄、固绿、苋菜红、铅离子、铜离子和镉离子的饱和吸附量分别为1000mg/g、344.83mg/g、454.44mg/g、94.34mg/g、161.29mg/g和357.14mmg/g；微纳结构PEI/PES纳米纤维亲和膜对重金属离子的吸附速率要快于阴离子染料,吸附动力学更符合准二级动力学模型和颗粒内扩散模型；微纳结构PEI/PES纳米纤维亲和膜对重金属离子和阴离子染料的吸附过程都是自发进行且都属于物理吸附,但是对重金属离子的吸附则是放热反应,而对阴离子染料的吸附是吸热反应。亲和膜的再生研究结果表明,0.05MEDTA和0.05MNaOH分别是吸附重金属离子和阴离子染料PEI/PES纳米纤维亲和膜的理想再生溶液。
4、经上述两种纳米纤维亲和膜处理之后的水溶液中金属离子的浓度需要对其进行检测以使其达到环保的要求,本文合成了一种罗丹明酰肼水杨醛席夫碱荧光分子,发现当铜离子与该荧光分子络合之后会导致罗丹明分子内开环,使其从非共轭结构转变成共轭结构而具有较强的荧光性质,且该荧光分子对水体铜离子的检测限为1×10-6M。此外,将罗丹明酰肼水杨醛席夫碱荧光分子与聚醚砜共混,采用静电纺丝技术成功制备了一种新型纳米纤维荧光传感器,并将其用于水体微量铜离子的检测。发现纳米纤维上的荧光分子对铜离子的高效选择性识别功能得到了增强,对铜离子的检测限为1×10-8M。研究了纳米纤维传感器对铜离子的识别机理,发现铜离子和荧光分子是以化学计量比为1：1进行络合。
Water resources shortage and pollution have been common problems currently. Among the number of polluting species at issue, heavy metal ions and organic dyes are of special concern because of their high toxicity for human and animals'health. Affinity membrane separation technology has been widely used in environmental remediation application due to its high performance of affinity chromatography and membrane technology, such as high selectivity, high efficiency, and no pollution and so on.
This work mainly focuses on the removal of heavy metal ions and anionic dyes, and detection of trace heavy metal ions in aqueous solution. Fitstly, cross-linked electrospun poly(ethyleneimine)(PEI) nanofibrous membranes doped with PVA were fabricated by wet-electrospinning in a one-step method instead of the conventional electrospinning and subsequent crosslinking method and the PEI/PVA nanofibrous membranes were applied to metal ions adsorption from an aqueous solution; Secondly, micro-nano structure nanofibrous affinity membranes of poly(ether sulfones)(PES) blended with a functional polymer PEI were fabricated by electrospinning technique followed by solvent etching in crosslinking solution, and this novel micro-nano structure PEI/PES nanofibrous membrane was utilized as an adsorbent for anionic dyes and heavy metal ions from aqueous solutions; the concentrations of the heavy metal ions solutions treated by two kinds of nanofibrous affinity membranes should be detected whether it meet the demand of environmental protection. So, a novel nanofibrous affinity membrane sensor was fabricated from a fluorescence molecule doped PES solutions and its sensing properties to Cu2+were investaged systematically.
1. PEI and PVA were chosen as functional affinity polymer and fiber-forming agent, respectively. Crosslinked PEI nanofibrous affinity membranes for effective removing heavy metal ions were fabricated via wet-electrospinning from its aqueous solution. The coagulating bath for wet-electrospinning was composed of the crosslinking agent glutaraldehyde (GA) and N,N-dimethylformamide (DMF) as a non-solvent. This wet-electrospinning method provided a new approach for fabricating the crosslinked nanofibers from the polymers, in which sticky phenomenon could occur at the process of the electrospinning. When the PEI/PVA weight ratio was90/10, the PVA doped PEI nanofibrous membranes with ideal morphology was obtained. The nanofibers had an average diameter of650nm and the surface of the nanofibers was very smooth. The Langmuir equation gave a better fit to the experimental data than the Freundlich equation, and the maximum absorption capacities (from Langmuir isotherm data) for Cu(II), Cd(II) and Pb(II) were70.92mg/g,121.95mg/g and94.34mg/g, respectively. The PEI nanofibrous affinity membrane adsorbed with heavy metal ions could be regenerated successfully in EDTA aqueous solution without significantly affecting its adsorption efficiency, it was found that the desorption efficiency reached about95.6%after the third cycles. The Cu(II) and Cd(II) adsorption data were about1.31and2.27times higher than the reported values of PEI/PVA cast membrane.
2. PEI/PES nanofibers were fabricated by electrospinning and PES was an excellent candidate for the matrix due to its good electrospinnability. In order to obtain PEI/PES nanofibrous membrane with high PEI content and finer fiber diameter, the blend ratio of1/1.4(w/w) and the total polymer concentration of30wt%were chosen in the electrospinning process. From the SEM images, it was found that the average diameter of the nanofibers was300nm and in addition most joints of PEI/PES nanofibers were stuck together, indicating that liquid PEI with high viscocity was concentrated at the fiber surface. The nanofibrous PEI/PES membranes were crosslinked in a mixture of acetone and water with glutaraldehyde (crosslinking agent, GA), and the micro-nano structural surface of the nanofibrous membranes was created by solvent etching due to the solvation between PEI and the solvent water in the crosslinking solution during the crosslinking process. The influence of the component of the crosslinking bath on the mophology of the resulting PEI/PES nanofibers was investigated. It was found that the relatively uniform micro-nano spherules grew on the surface of the nanofibers when the content of water in crosslinking solution was more than20wt%, and the diameters of the spherules were in the range of50-250nm. From the data of BET results and Cu2+adsorption performance, it was found that when the water content in crosslinking solution was30%, the resulting PEI/PES nanofibrous membrane has the maximum specific surface area, which was7.27m2/g.
3. Adsorption performance of the micro-nano structure PEI/PES nanofibrous membrane for anionic dyes or heavy metal ions from aqueous solutions was investigated. A series of adsorption experiments were carried out to investigate the influence of membrane dosage, initial solution pH value, contact time, initial solution concentration and adsorption temperature on the adsorption performance. The experimental results showed that the removal of the anionic dyes and metal ions on this PEI/PES nanofibrous membrane was a pH-dependent process with the maximum adsorption capacity at the initial solution pH of1for anionic dyes and5-7for metal ions, respectively. The adsorption equilibrium data were all fitted well to the Langmuir isotherm equation, with a maximum adsorption capacity values of1000mg/g,344.83mg/g,454.44mg/g,94.34mg/g,161.29mg/g and357.14mg/g for Sunset Yellow FCF, Fast Green FCF, Amaranth, Pb(II), Cu(II) and Cd(II), respectively. The kinetic study indicated that the adsorption of metal ions and anionic dyes could be well fitted by the pseudo-second-order model and intraparticle diffusion model, suggesting intra-particle diffusion process as the rate-limiting step of the adsorption process. Thermodynamic parameters such as free energy, enthalpy and entropy of adsorption of anionic dyes and metal ions were also evaluated and the results showed that the adsorption was a spontaneous physical adsorption process. In addition, the adsorption process of heavy metal ions was exothermic; however, the adsorption process of anionic dyes was endothermic. This micro-nano structure PEI/PES nanofibrous membrane could be regenerated successfully in0.05M NaOH and0.05M EDTA aqueous solution used for removal of anionic dyes and heavy metal ions, respectively.
4. The concentrations of the heavy metal ions solutions treated by two kinds of nanofibrous affinity membranes should be detected whether it meet the demand of environmental protection. Firstly, a fluorescence molecule, rhodamine hydrazone salicylaldehyde Schiff base, was synthesized as the sensing material and its chemical structure was obtained. It was found that the ion-recognition was based on the Cu+induced spirolactam ring "close-open" switch of the fluorescence molecule, with their advantages of significant absorption and fluorescence enhancement and the detection limit was1×10-6M. Secondly, the fluorescence molecule was blended with PES solution and electrospun to prepare a novel nanofibrous membrane sensor. It was found that this novel nanofirous membrane sensor showed high selectivity and sensitivity for Cu2+. In addition, the sensitivity of the fluorescence probe on the nanofibrous membrane sensor was much higher than that in the aqueous solution and the detection limit of the nanofibrous membrane sensor was1×10-8M. The complex mechanism between rhodamine hydrazone salicylaldehyde Schiff base and Cu2+was investigated by Job method, and it was found the nonlinear fitting of the titration curve assumed a1:1stoichiometry for the Cu-complex.
引文
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