CN113501832B - 一种稀土发光材料的荧光传感应用及其纸基薄膜器件 - Google Patents
一种稀土发光材料的荧光传感应用及其纸基薄膜器件 Download PDFInfo
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Abstract
本发明公开了一种对氨气有着选择性响应且灵敏度高的稀土配合物发光材料及其纸基荧光薄膜和制备方法；本发明的发光材料发光性能很好，将其置于含氨气氛中后，很快呈现荧光猝灭的传感响应特性；该材料的溶解性和稳定性都很好，易于制备成纸基荧光传感薄膜，薄膜在含氨气氛中也迅速表现出可肉眼观察的荧光猝灭响应，表现出快速响应和灵敏识别的荧光传感性能，且可将试纸灵活制造成各种所需规格，可作为便携式荧光传感试纸器件应用氨气的检测。
Description
技术领域
本发明涉及稀土发光材料技术领域，具体涉及发光材料的荧光传感应用领域。
背景技术
氨作为一种无色而具有强烈刺激性臭味的气体，比空气请（比重为0.5），可感觉最低浓度为5.3ppm。氨是一种碱性物质，对接触的皮肤组织都有腐蚀和刺激作用。可以吸收皮肤组织中的水分，使组织蛋白变性，并使组织脂肪皂化，破坏细胞膜结构。氨的溶解度极高，所以主要对动物或人体的上呼吸道有刺激和腐蚀作用，减弱人体对疾病的抵抗力。氨通常以气体形式吸入人体，进入肺泡内的氨,少部分为二氧化碳所中和，余下被吸收至血液，少量的氨可随汗液、尿或呼吸排出体外。氨被吸入肺后容易通过肺泡进入血液，与血红蛋白结合，破坏运氧功能。短期内吸入大量氨气后可出现流泪、咽痛、声音嘶哑、咳嗽、痰带血丝、胸闷、呼吸困难，可伴有头晕、头痛、恶心、呕吐、乏力等，严重者可发生肺水肿、成人呼吸窘迫综合征，同时可能发生呼吸道刺激症状。（科技与企业，2010(03)：70.）
为了证明空气中低浓度的氨对人体健康的危害和影响，专家们监测了在接触 3-13 毫克/立方米浓度的氨的室内环境中工作的工人们，历时8小时，每组10人，与不接触氨的健康人比较，发现接触13毫克/立方米的人，尿中尿素和氨含量均增加，血液中尿素则明显增加。另外，专家们提供的养鸡场鸡舍中氨气对鸡的影响的资料，也可作为参考。由于鸡粪中产生大量氨气，所以当鸡舍空气中氨气达20ppm(相当于15.2毫克/立方米)，持续6周以上,就会引起鸡肺充血、水肿、鸡群食欲下降，产蛋力降低，易感染疾病；如达 50ppm，数日后鸡发生喉头水肿、坏死性支气管炎、肺出血，呼吸频率降低，并出现死亡。所以，鸡舍空气中氨浓度要求控制在20ppm以下。（家畜生态学报，2020，41(09)：1-6.）从中我们可以看到室内空气中低浓度氨污染对人体健康的危害。因此对其进行快捷准确的检测非常重要。
纸基荧光传感薄膜是一种高亮度、宽视觉的光致发光器件，具有其他传感器件没有的优点：①结构简单，成本低，纸基荧光传感薄膜制备成本低，不需要过度精密的昂贵仪器；②响应速度快（几秒至几分钟），在检测挥发性有机物中的氨类时，所需时间短；③环境适应性强，具有良好的温度特性，可在低温环境下显示等；④ 可实现宽视角，能实现荧光传感检测可视化，高对比度。
Eu的配合物发光性能强，可以形成多配位，结合适当的配体，使其具备独特的发光性能。用Eu配合物作为荧光材料由来已久，只是目前将其应用在检测方面的较为稀少。因此开发Eu配合物的荧光传感器在检测方面具有广阔的开发潜力。而将Eu配合物作为荧光探针制造成为纸基便携式荧光传感薄膜器件，用于氨气等环境有害气体的传感检测应用，更是具有重大的实际应用价值。
发明内容
本发明的目的是提供一种对氨气有着选择性响应且灵敏度高的稀土配合物发光材料及其纸基荧光薄膜和制备方法。通过铕离子（或混入镧离子）与配体在溶液中发生配位反应，方便且廉价地制备获得了发光性能和热稳定性能良好的铕配合物发光材料，其红色荧光发光强度大、稳定性好，而且以其制备的纸基荧光薄膜对于氨气的响应有着明显的荧光猝灭效应，可以用来检测环境中的氨气。
本发明的技术方案之一，是提供一种对氨气有着明显荧光猝灭响应的稀土配合物发光材料应用，该稀土配合物发光材料由Eu(NO3)3 (或混入一定量的硝酸镧)与配体依次发生配位反应得到，其分子结构为LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)，式中BTA为苯甲酰三氟丙酮；式中2-PBO为中性杂环配体2-（2-吡啶）苯并噁唑。
所述稀土配合物发光材料结构表现为中性单核配合物，其中铕（或镧）和配体2-PBO、BTA螯合形成的配位；该配合物中的Eu (或La) 采用八配位模式，其中一个N和一个O来自于一个双齿螯合配体2-PBO，另外六个O来自三个苯甲酰三氟丙酮配体；其分子结构如式（I）：
（I）；
所述稀土配合物发光材料在氨气存在的环境中放置后，其红色荧光强度会随时间降低，且氨气浓度越高表现出越强的猝灭响应效果，因此可作为检测氨气的荧光传感材料应用。
所述稀土配合物发光材料的纸基荧光薄膜在氨气存在的环境中放置后，其红色荧光强度迅速随时间降低，且氨气浓度越高表现出越强的猝灭响应效果，表现出快速响应和灵敏识别的荧光传感性能，因此可作为便携式荧光传感试纸器件应用氨气的检测。
本发明的技术方案之二，是提供一种基于稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的纸基荧光传感薄膜的制备方法。该制备方法是由Eu(NO3)3 (或混入一定量的硝酸镧)与配体2-PBO、BTA和氢氧化钠溶液混合发生配位反应，析出得到晶体粉末的产物后，以该晶体粉末的溶液涂覆纤维素薄膜而实现。其具体实施方案分为六个步骤：
（1）室温下将Eu(NO3)3·6H2O (或混入一定量的硝酸镧)粉末溶解在乙腈中；
（2）室温下将BTA与氢氧化钠粉末溶解在乙腈与水混合溶剂中；
（3）将上述两种溶液混合，并搅拌使之充分反应，得到澄清溶液A；
（4）室温下将2-PBO粉末溶解在乙腈中，再加入溶液A中混合搅拌，使之充分发生配位反应得溶液B；
（5）将溶液B过滤，然后将滤液减压蒸发，真空干燥，得到晶态粉末。
（6）按物质的量浓度配置一定浓度LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的二氯甲烷溶液，以浸涂等方式将溶液涂覆于纤维素薄膜（即试纸原纸）上，干燥后即得到纸基荧光传感薄膜器件。
本发明的有益效果首先是，所提供的稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO)(X=0～0.6)的传感应用，该配合物本身的荧光性能很好，极少量的材料粉末都能发出强烈的荧光，因此实际应用时只需少量荧光粉，便于降低应用成本，而且易于操作的掺杂途径也为应用的成本控制提供方便；而将相同工艺制备的材料置于氨气气氛中后，都能很快观察到荧光猝灭的传感响应特性；且其溶解性和稳定性都很好，便于作为荧光传感材料使用。
本发明的有益效果其次是，所提供的基于稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的纸基荧光薄膜的氨气传感应用，该纸基荧光薄膜的使用类似于一般的气体检测试纸一样简便，具体应用时，将纸基荧光薄膜在氨气存在的环境中短时放置后，用紫外光源照射薄膜，可观察到其红色荧光强度迅速随时间降低，且氨气浓度越高表现出越强的猝灭响应效果，表现出快速响应和灵敏识别的荧光传感性能，因此可作为便携式荧光传感试纸器件应用氨气的检测；该荧光传感薄膜可灵活制造成各种所需形状，质量很轻，非常便于携带，且也易于制备，为发光材料的进一步应用提供了技术支持。也易于和八羟基喹啉铝等荧光参比物复合，制成比率型的传感薄膜。
本发明的有益效果再次是，制备基于稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO)(X=0～0.6)的纸基荧光传感薄膜的制备方法，具有工艺简便，所用设备简单，原材料简单易得，生产成本低，可在很短的时间内得到大量产品易于推广等优点。
附图说明
图1. 稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0)分子的单晶结构图；
图2. 稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的紫外可见吸收光图谱，横坐标表示波长，纵坐标表示吸光度。
图3. 稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)晶态粉末的发射光图谱，激发波长为369nm，最大发射峰位于610nm处；横坐标为波长，纵坐标为强度。
图4. 稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6) 纸基薄膜的发射光图谱，激发波长为369nm，最大发射峰位于610nm处；横坐标为波长，纵坐标为强度。
图5. 稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的纸基传感薄膜在氨气气氛中响应不同时间后的荧光发射图谱；横坐标为波长，纵坐标为强度。
图6. 稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)与8-羟基喹啉铝复合纸基传感薄膜样品在氨气气氛中响应前后的荧光发射谱对比图。
图7. 稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)纸基薄膜样品在氨气气氛中的响应15min前后峰强比随浓度的变化情况。
图8. 稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)纸基薄膜样品在饱和的氨气气氛中的气氛中响应不同时间的荧光强度情况。
具体实施方式
本发明的实现过程和材料的性能由实施例说明：
实施例1
稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的制备,由如下四个步骤实现：
A．称取0.5mmol的Ln(NO3)3·6H2O (Ln为Eu和一定量混入的La)和1.5mmol苯甲酰三氟丙酮，加入10ml乙腈溶解，并逐滴加入7.5ml 0.2mol/L的氢氧化钠溶液，充分搅拌，得到澄清溶液1；
B．称取0.5mmol 2-(2-苯并恶唑)吡啶，加入5ml乙腈溶解，得到澄清溶液2；
C．将溶液2缓慢滴加到溶液1中，室温下搅拌1小时，得到溶液3；
D．将溶液3减压下旋转蒸发除去溶剂，得到粉末状晶态产物，最后用去离子水洗涤并在50℃下干燥，得到稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)，产率约84%。
实施例2
稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的纸基荧光薄膜的制备：称量0.0008g（0.0001mmol）的LaxEu1-x(BTA)3(2-PBO) (X=0)；加入5ml的二氯甲烷溶液中，充分搅拌使之充分完全溶解，得到无色澄清溶液，再将该溶液于事先准备好的试纸条上进行微喷涂，制作成荧光传感的敏感面，等待干燥后得到比率型荧光试纸（纸基荧光薄膜）；该纸基荧光传感薄膜对氨的响应非常灵敏，在环境中存在少量氨时即会发生荧光猝灭。
实施例3
稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的纸基荧光薄膜的制备：称量0.0008g（0.0001mmol）的LaxEu1-x(BTA)3(2-PBO) (X=0)；加入5ml的二氯甲烷溶液中，充分搅拌使之充分完全溶解，得到无色澄清溶液，再将事先准备好的纤维素薄膜试纸条浸入溶液中，完全浸泡均匀后取出并压干后晾干，等待干燥后即得到便携式荧光试纸（纸基荧光薄膜）；该纸基荧光传感薄膜对氨的响应非常灵敏，在环境中存在少量氨气时即会发生荧光猝灭。
实施例4
红色荧光配合物材料Eu(BTA)3（2-PBO）与八羟基喹啉铝的比率型纸基荧光薄膜制备：称量0.0096g（0.0096mmol）的Eu(BTA)3（2-PBO）与0.0001g（0.0002mmol）的八羟基喹啉铝混合溶于5ml二氯甲烷中，得到无色澄清溶液；再将该溶液于事先准备好的试纸条上进行微喷涂，制作成荧光传感的敏感面，等待干燥后得到比率型荧光试纸（纸基荧光薄膜）；该荧光试纸（纸基荧光薄膜）保留了对氨的灵敏响应；另外相对于单纯铕配合物传感器件在红光猝灭后的发光暗淡影响视觉判断，此比率型传感薄膜在红光猝灭后显现出八羟基喹啉铝的黄绿光，在可视化检测氨中便于辨别。
对LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)的纯相粉末及其薄膜样品，以及以八羟基喹啉铝荧光强度参比制作成的比率型纸基荧光薄膜进行了一系列性能测试。对以上薄膜进行了稳态荧光测试，结果表明LaxEu1-x(BTA)3(2-PBO) (X=0～0.6)在不同的激发波长作用下，都能发射出强烈的红色荧光，而对该材料的氨气VOC响应荧光测试表明，其确实在氨气氛中有着明显的荧光猝灭型传感响应现象。可见，该材料可应用于氨气检测的荧光传感材料;八羟基喹啉铝在氨的气氛中一定时间荧光强度并无明显变化；比率型纸基荧光薄膜的红光荧光强度随着在氨气氛中响应而猝灭显现为黄绿色光，表现出显著的比率型荧光传感特性；具体的发射光谱如附图3，图4，图5，图6，图7，图8所示。
Claims (5)
1.一种对氨气有着灵敏选择性响应的稀土配合物发光材料的应用，其特征在于：作为检测氨气的荧光传感材料的应用，该稀土配合物发光材料在氨气存在的环境中放置后，其红色荧光强度会随时间降低，且氨气浓度越高表现出越强的猝灭响应效果；发光材料的结构式为LaxEu1-x(BTA)3(2-PBO),式中X＝0～0.6，式中BTA为苯甲酰三氟丙酮，式中2-PBO为中性杂环配体2-(2-吡啶)苯并噁唑；该稀土配合物发光材料结构表现为中性单核配合物，其中中心稀土离子Eu或La和配体2-PBO、BTA螯合形成的配位；该配合物中的Eu或La采用八配位模式，其中一个N和一个O来自于一个双齿螯合配体2-PBO，另外六个O来自三个苯甲酰三氟丙酮配体；其分子结构如式(I)：
其中中心稀土离子Ln为LaxEu1-x，所述X＝0～0.6。
2.一种对氨气有着灵敏选择性响应的稀土配合物荧光传感薄膜的应用，其特征在于：作为便携式荧光传感试纸器件应用于氨气的便捷检测，稀土配合物荧光传感薄膜是将稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO)溶解后涂覆在试纸原纸上制成；该稀土配合物荧光传感薄膜在氨气存在的环境中放置后，其红色荧光强度迅速随时间减弱，且氨气浓度越高表现出越强的猝灭响应效果，表现出快速响应和灵敏识别的荧光传感性能；其中，所述稀土配合物发光材料的结构式为LaxEu1-x(BTA)3(2-PBO),式中X＝0～0.6，式中BTA为苯甲酰三氟丙酮，式中2-PBO为中性杂环配体2-(2-吡啶)苯并噁唑；该稀土配合物发光材料结构表现为中性单核配合物，其中中心稀土离子Eu或La和配体2-PBO、BTA螯合形成的配位；该配合物中的Eu或La采用八配位模式，其中一个N和一个O来自于一个双齿螯合配体2-PBO，另外六个O来自三个苯甲酰三氟丙酮配体；其分子结构如式(I)：
其中中心稀土离子Ln为LaxEu1-x，所述X＝0～0.6。
3.根据权利要求2所述的应用，其中对氨气有着灵敏选择性响应的稀土配合物荧光传感薄膜的制备方法包括以下步骤：
(1)室温下将Eu(NO3)3·6H2O或混入一定量硝酸镧的Eu(NO3)3·6H2O粉末溶解在乙腈中；
(2)室温下将BTA与氢氧化钠粉末溶解在乙腈与水混合溶剂中；
(3)将上述两种溶液混合，并搅拌使之充分反应，得到澄清溶液A；
(4)室温下将2-PBO粉末溶解在乙腈中，再加入溶液A中混合搅拌，使之充分发生配位反应得溶液B；
(5)将溶液B过滤，然后将滤液减压蒸发，真空干燥，得到晶态粉末；
(6)按物质的量浓度配置一定浓度LaxEu1-x(BTA)3(2-PBO)的二氯甲烷溶液，以浸涂、微喷涂的方式将溶液涂覆于试纸原纸上，干燥后即得到稀土配合物荧光传感薄膜。
4.一种对氨气有着灵敏选择性响应的比率型荧光传感薄膜，其特征在于：比率型荧光传感薄膜是将稀土配合物发光材料LaxEu1-x(BTA)3(2-PBO)溶解后与八羟基喹啉铝和聚甲基丙烯酸甲酯一起制备成稳定的均匀混合液，然后将该混合液涂覆在试纸原纸上制成；该比率型荧光传感薄膜在氨气存在的环境中放置后，其红色荧光强度迅速随时间减弱，从而发光从红色可见地向绿色转变，且氨气浓度越高表现出越强的可视化响应效果，表现出快速响应和灵敏识别的荧光传感性能，作为可视化的便携式荧光传感试纸器件应用于氨气的便捷检测；其中，所述稀土配合物发光材料的结构式为LaxEu1-x(BTA)3(2-PBO),式中X＝0～0.6，式中BTA为苯甲酰三氟丙酮，式中2-PBO为中性杂环配体2-(2-吡啶)苯并噁唑；该稀土配合物发光材料结构表现为中性单核配合物，其中中心稀土离子Eu或La和配体2-PBO、BTA螯合形成的配位；该配合物中的Eu或La采用八配位模式，其中一个N和一个O来自于一个双齿螯合配体2-PBO，另外六个O来自三个苯甲酰三氟丙酮配体；其分子结构如式(I)：
其中中心稀土离子Ln为LaxEu1-x，所述X＝0～0.6。
5.根据权利要求4所述的对氨气有着灵敏选择性响应的比率型荧光传感薄膜，其制备方法包括以下步骤：
(1)按物质的量浓度配置一定浓度LaxEu1-x(BTA)3(2-PBO)的二氯甲烷溶液A；
(2)按物质的量浓度配置一定浓度八羟基喹啉铝和聚甲基丙烯酸甲酯的二氯甲烷溶液B；
(3)将上述两种溶液混合，并搅拌使之充分混合均匀，得到混合液C；
(4)以微喷涂的方式将溶液C涂覆于纤维素薄膜上，干燥后即得到比率型荧光传感薄膜。
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