CN117447996B - 一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法 - Google Patents
一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法 Download PDFInfo
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Abstract
本发明公开了一种CsPbCl3:Mn2+/PEG纳米晶检测水中4‑硝基苯酚的方法，（1）将PbCl2、MnCl2和聚乙二醇溶解于DMF中，然后加入油酸、油胺和浓HCl搅拌得到浅绿色的前驱体溶液，搅拌条件下，将前驱体溶液注入到乙酸铯、油酸和二甲苯的混合溶液中，反应后离心，在沉淀中加入甲苯，超声分散后离心收集沉淀得到CsPbCl3:Mn2+/PEG纳米晶；（2）将CsPbCl3:Mn2+/PEG纳米晶分散在去离子水中，然后将纳米晶溶液稀释到pH为1的盐酸稀溶液中后在250nm荧光激发下检测4‑硝基苯酚。本发明将具有双发射峰的CsPbCl3:Mn2+钙钛矿量子点包覆在聚乙二醇中，合成水稳定性较好的纳米晶，将纳米晶作为荧光探针应用于水中4‑NP的检测，选择性好，在其他干扰离子的存在下，荧光强度仅对4‑NP表现较好的响应性。
Description
技术领域
本发明属于光致发光荧光探针技术领域，涉及聚合物PEG包覆的钙钛矿量子点在定量检测4-NP方面的应用，具体为一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法。
背景技术
4-硝基苯酚(4-NP)作为精细化工中间体，广泛应用于农药、医药、染料等领域。然而，4-NP也是一种难处理的环境污染物和有害废物。4-NP由于其高共轭结构和羟基，具有良好的化学稳定性和高水溶性，在环境水中逐渐积累。有报道称，4-NP可对人体健康造成严重威胁，急性吸入或误食可引起头痛、嗜睡、恶心，导致心血管、肾和中枢神经系统的损伤。因此，应严格控制和监督4-NP的使用。目前规定其在饮用水中的最大允许水平为60μg/L（0.43μM)。此外，由于4-NP稳定性高，可生物降解性差，从污染废水和土壤中去除难度极大。因此，开发一种简单、灵敏、高效的方法监测环境中4-NP方法具有重要意义。目前，已经设计了许多检测4-NP的策略，包括液相色谱-质谱串联法、电化学、毛细管电泳、光电化学、高效液相色谱法和荧光光谱法等。与其他方法相比，荧光法由于其操作简单、响应速度快、灵敏度高和高选择性等优点，越来越受到广泛的关注。目前已经建立了多种检测4-NP的荧光方法，其中包括无机纳米材料、有机荧光染料、半导体量子点(QDs)、金属-有机骨架材料等多种具有优异物理和化学性质的荧光材料。与其他荧光材料相比，钙钛矿基材料表现出优异的荧光特性、高荧光量子产率。因此，我们选择使用基于钙钛矿的荧光探针进行4-NP检测。近年来，CsPbX3(X=Cl,Br,I)钙钛矿纳米材料由于具有高光致发光量子产率(PLQYs)、极窄的半峰宽、低反应温度、低成本以及整个可见光谱发射波长可调等优异的光电性能，在各种光电器件和荧光探针等方面具有很大的潜力。然而，由于钙钛矿材料低形成能和离子性质，钙钛矿对湿度、光和温度极其敏感，其不稳定性极大地限制了其在许多领域的应用，特别是在生化检测方面。因此，提高钙钛矿材料的稳定性已成为近年来的主要研究方向。
发明内容
本发明所要解决的技术问题是针对现有技术的缺点而提供一种CsPbCl3:Mn2+/PEG纳米晶检测4-硝基苯酚的方法，本发明将具有双发射峰的CsPbCl3:Mn2+钙钛矿量子点包覆在具有良好生物相容性的两亲性聚乙二醇中，合成水稳定性较好的CsPbCl3:Mn2+/PEG纳米晶，将CsPbCl3:Mn2+/PEG纳米晶作为荧光探针应用于水中4-NP的检测。
为解决本发明的技术问题采用如下技术方案：
一种CsPbCl3:Mn2+/PEG纳米晶检测4-硝基苯酚的方法，具体工艺为：（1）配体辅助再沉淀法合成CsPbCl3:Mn2+/PEG纳米晶：将PbCl2、MnCl2和聚乙二醇PEG溶解于N,N-二甲基甲酰胺中，然后加入油酸、油胺和浓HCl搅拌得到浅绿色的前驱体溶液，搅拌条件下，将前驱体溶液注入到乙酸铯、油酸和二甲苯的混合溶液中，反应后离心弃去上清液，在沉淀中加入甲苯，超声分散后离心收集沉淀得到CsPbCl3:Mn2+/PEG纳米晶；（2）将得到的CsPbCl3:Mn2+/PEG纳米晶分散在去离子水中，然后将CsPbCl3:Mn2+/PEG纳米晶溶液稀释到pH为1的盐酸稀溶液中后在250nm荧光激发下检测4-硝基苯酚。
上述CsPbCl3:Mn2+/PEG纳米晶检测4-硝基苯酚的方法，具体方法为：（1）将0.25mmolPbCl2、0.25mmolMnCl2和40mg聚乙二醇PEG溶解于5mLN,N-二甲基甲酰胺中，然后加入0.5mL油酸和0.5mL油胺，最后加入0.5mL浓HCl搅拌得到浅绿色的前驱体溶液，搅拌下将1mL前驱体溶液注入到含有0.05mmol乙酸铯、1mL油酸和5mL二甲苯的混合溶液，反应30-38s后，用紫外灯照射观察到明亮的橙色荧光，将得到的样品离心弃去上清液，沉淀中加入3mL甲苯，超声分散后离心收集沉淀，即为CsPbCl3:Mn2+/PEG纳米晶；（2）将收集到的CsPbCl3:Mn2 +/PEG纳米晶分散在2mL的去离子水中形成CsPbCl3:Mn2+/PEG纳米晶水溶液，量取100μL的CsPbCl3:Mn2+/PEG纳米晶水溶液稀释到3mL、pH为1的盐酸稀溶液中用于检测水中4-硝基苯酚。
所述步骤（1）中在1700-2000r/min搅拌下将1mL前驱体溶液注入到含有0.05mmol乙酸铯、1mL油酸和5mL二甲苯的混合溶液。
所述步骤（1）中得到的样品以9000-10000r/min离心10-15min。
所述步骤（1）中在沉淀中加入3mL甲苯，使用频率为40KHz的超声波超声分散后继续以9000-10000r/min离心10-15min收集沉淀。
所述步骤（2）中CsPbCl3:Mn2+/PEG纳米晶检测4-硝基苯酚浓度范围为0.00029-0.40876mmol/L。
本发明CsPbCl3:Mn2+钙钛矿量子点是利用Mn2+取代Pb2+可以显著改变CsPbCl3钙钛矿量子点的光学性能，大大提高了PL量子产率。CsPbCl3：Mn2+PQDs在紫外光激发下表现出双发射，两个发射峰分别位于400nm和590nm，它们可归因于CsPbCl3的带边激子发射和Mn2+d-d跃迁(4T1→6A1跃迁)。在紫外光激发下，CsPbCl3:Mn2+钙钛矿量子点呈现橙红色荧光，主要来源于半导体基质到Mn2+的能量传递，导致Mn2+离子在4T1和6A1能级之间跃迁产生辐射发光。
CsPbCl3:Mn2+/PEG纳米晶的聚乙二醇（PEG）是由两个亚甲基和主链上重复的一个氧原子组成的合成高分子材料，它可以溶于水和一些有机溶剂。此外，它可以通过化学反应连接其他分子或表面形成生物相容性的保护膜，这不仅可以减少生物系统对材料的排斥机会，还可以大大减少蛋白质、细胞和细菌在材料表面的吸附。PEG的亲水性和高度的生物相容性，以及其温和清晰的化学反应性质，使其成为分子与分子之间或分子与表面之间理想的偶联或成键剂。选择PEG作为CsPbCl3:Mn2+钙钛矿量子点的保护层，可以有效避免外界环境的破坏，使得制备的CsPbCl3:Mn2+/PEG纳米晶具有优异水稳定性和水溶性。此外4-NP在380nm附近的吸收光谱与CsPbCl3:Mn2+/PEG纳米晶在400nm中心的发射光谱有部分的光谱重叠，导致CsPbCl3:Mn2+量子点通过荧光共振能量转移（FRET）机制发生荧光猝灭。
本发明的有益效果是：1.采用良好生物相容性的聚乙二醇为表面包覆材料，制备的CsPbCl3:Mn2+/PEG纳米晶水溶性良好。2.PEG包覆极大的提高了CsPbCl3:Mn2+钙钛矿量子点在水中的荧光稳定性。CsPbCl3:Mn2+/PEG纳米晶在水中存储25天后，荧光强度仍为初始强度的40%以上。3.利用CsPbCl3:Mn2+/PEG纳米晶在250nm激发光下荧光光谱相对强度与4-NP浓度间的关系I0/I(400nm)=1.0683+4.2545C4-NP，和I0/I(590nm)=1.1235+5.3868C4-NP，可应用于水中4-NP浓度的定量检测。4.检测限低，用3σ/K公式计算的检测限(LOD)值分别为0.40563μM(400nm)和0.36362μM(590nm)，低于饮用水中4-NP的最大允许浓度0.43μM。5.选择性好，在其他干扰离子的存在下，CsPbCl3:Mn2+/PEG纳米晶荧光强度仅对4-NP表现较好的响应性。6.CsPbCl3:Mn2+/PEG纳米晶制备方法绿色、经济，这为钙钛矿量子点在水中4-NP检测中的应用提供了一种新的方法。
附图说明
图1为本发明CsPbCl3:Mn2+/PEG纳米晶在不同标尺下的TEM图；
图2为本发明CsPbCl3:Mn2+/PEG纳米晶在水中的稳定性，图a为CsPbCl3:Mn2+/PEG纳米晶在自然光下的拍摄的照片，图b、图c、图d分别是水中存储1天，12天以及33天后CsPbCl3:Mn2+/PEG在紫外光(250nm)下的拍摄发光照片；
图3为本发明在分散CsPbCl3:Mn2+/PEG纳米晶的水溶液中加入不同浓度的4-NP与其反应，在250nm激发下监测得到的荧光光谱图；
图4为本发明CsPbCl3:Mn2+/PEG纳米晶在400nm和590nm波长处的荧光猝灭值(I0/I)与4-NP浓度间的Sternee-Volmer关系图；
图5为本发明4-NP与干扰离子在相同浓度7.5μg/mL下，CsPbCl3:Mn2+/PEG纳米晶对4-NP和干扰离子的选择性图。
具体实施方式
实施例1
一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法，包括以下步骤：
（1）配体辅助再沉淀法合成CsPbCl3:Mn2+/PEG纳米晶
将PbCl2(0.25mmol)、MnCl2(0.25mmol)和聚乙二醇PEG(40mg)溶解于5mLN,N-二甲基甲酰胺中，加入油酸(0.5mL)和油胺(0.5mL)，最后加入浓HCl(0.5mL)搅拌10min，得到浅绿色的前驱体溶液，在剧烈搅拌（1700r/min）下，将1mL前驱体溶液注入到含有乙酸铯(0.05mmol)、油酸(1mL)和二甲苯(5mL)的混合溶液，立即出现白色的沉淀物，反应38s后，用紫外灯照射观察到明亮的橙色荧光；将得到的样品以9000r/min离心10min，弃去上清液，沉淀中加入甲苯(3mL)，超声分散（频率为40KHz）后继续以10000r/min离心10min，收集沉淀，即为CsPbCl3:Mn2+/PEG纳米晶；最后将其超声分散在2mL的去离子水中进行表征。
（2）CsPbCl3:Mn2+/PEG纳米晶定量检测水中4-NP的使用方法
将收集到的CsPbCl3:Mn2+/PEG纳米晶分散在2mL去离子水中形成CsPbCl3:Mn2+/PEG纳米晶水溶液，精确量取100μLCsPbCl3:Mn2+/PEG纳米晶水溶液并稀释至3mL、pH为1的盐酸稀溶液中，并与不同浓度的4-NP溶液(0.00029mmol/L、0.00071mmol/L、0.00359mmol/L、0.00719mmol/L、0.01438mmol/L、0.02875mmol/L、0.04633mmol/L、0.06387mmol/L、0.08137mmol/L、0.11628mmol/L、0.15105mmol/L、0.20295mmol/L、0.25455mmol/L、0.30586mmol/L、0.34023mmol/L、0.40876mmol/L)反应1min，在250nm激发下记录荧光发射光谱。
实施例2
一种CsPbCl3:Mn2+/PEG纳米晶检测4-硝基苯酚的方法，包括以下步骤：
（1）配体辅助再沉淀法合成CsPbCl3:Mn2+/PEG纳米晶
将PbCl2(0.25mmol)、MnCl2(0.25mmol)和聚乙二醇PEG(40mg)溶解于5mLN,N-二甲基甲酰胺中，加入油酸(0.5mL)和油胺(0.5mL)，最后加入浓HCl(0.5mL)搅拌20min，得到浅绿色的前驱体溶液，在剧烈搅拌(2000r/min)下，将1mL前驱体溶液注入到含有乙酸铯(0.05mmol)、油酸(1mL)和二甲苯(5mL)的混合溶液，立即出现白色的沉淀物，反应30s后，用紫外灯照射观察到明亮的橙色荧光；将得到的样品以10000r/min离心15min，弃去上清液，沉淀中加入甲苯(3mL)，超声分散（频率为40KHz）后继续以9000r/min离心15min，收集沉淀，即为CsPbCl3:Mn2+/PEG纳米晶；最后将其超声分散在2mL的去离子水中进行表征。
（2）CsPbCl3:Mn2+/PEG纳米晶定量检测水中4-NP的使用方法
将收集到的CsPbCl3:Mn2+/PEG纳米晶分散在2mL去离子水中形成CsPbCl3:Mn2+/PEG纳米晶水溶液，精确量取100μLCsPbCl3:Mn2+/PEG纳米晶水溶液并稀释至3mL、pH为1的盐酸稀溶液中，并与不同浓度的4-NP溶液(0.00029mmol/L、0.00071mmol/L、0.00359mmol/L、0.00719mmol/L、0.01438mmol/L、0.02875mmol/L、0.04633mmol/L、0.06387mmol/L、0.08137mmol/L、0.11628mmol/L、0.15105mmol/L、0.20295mmol/L、0.25455mmol/L、0.30586mmol/L、0.34023mmol/L、0.40876mmol/L)反应1min，在250nm激发下记录荧光发射光谱。
如图1所示，采用生物相容性良好的聚乙二醇为表面包覆材料，制备的CsPbCl3:Mn2 +/PEG纳米晶粒径均一，CsPbCl3:Mn2+钙钛矿量子点被包覆在PEG结晶纳米晶内部，极大的提高了CsPbCl3:Mn2+钙钛矿量子点在水中的荧光稳定性。如图2所示，CsPbCl3:Mn2+/PEG纳米晶在水中存储25天后，荧光强度仍为初始强度的40%以上，在水中存储33天后，荧光强度仍为初始强度的20%。如图3所示，将荧光稳定性良好的CsPbCl3:Mn2+/PEG纳米晶作为荧光探针用于检测水中4-NP。纳米晶的荧光强度随着4-NP浓度的增加而逐渐降低。如图4表明，CsPbCl3:Mn2+/PEG纳米晶的荧光强度与4-NP浓度的关系符合Stern-Volmer方程，可以用公式I0/I=1+KsvC4-NP表示，其中I和I0分别为添加和不添加4-NP的CsPbCl3:Mn2+/PEG纳米晶的荧光强度。Ksv为与猝灭效率有关的Stern-Volmer常数，C4-NP为4-NP的摩尔浓度。从0.00029mmol/L到0.40876mmol/L范围内，400nm和590nm处发射峰强度比值I0/I与4-NP浓度间都有良好的线性关系(R2=0.98224和0.98823)，拟合的线性方程分别为I0/I(400nm)=1.0683+4.2545C4-NP，和I0/I(590nm)=1.1235+5.3868C4-NP。其中Ksv分别为4.2545×103和5.3868×103。因此，利用CsPbCl3:Mn2+/PEG纳米晶相对荧光强度可用于水中4-NP浓度的定量检测，且检测范围广。本发明方法中检测4-NP浓度的检测限很低，用3σ/K公式计算的检测限(LOD)值分别为0.40563μM(400nm)和0.36362μM(590nm)。该方法线性范围宽，LOD低，在水样中4-NP的测定中展现良好的潜力。如图5所示，在CsPbCl3:Mn2+/PEG纳米晶的水溶液，加入其他干扰离子(K+,Na+,Ca2+,Cu2+,Mg2+,Zn2+,Fe2+)后，在相同浓度下(7.5μg/mL)，4-NP和干扰金属离子分别与CsPbCl3:Mn2+/PEG纳米晶反应后，只有4-NP对CsPbCl3:Mn2+/PEG纳米晶的荧光有明显的猝灭作用，4-NP的检测不受金属离子存在的影响。因此，即使存在干扰化合物，CsPbCl3:Mn2+/PEG纳米晶对4-NP也具有很高的选择性。
Claims (6)
1.一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法，其特征在于具体工艺为：
（1）配体辅助再沉淀法合成CsPbCl3:Mn2+/PEG纳米晶：将PbCl2、MnCl2和聚乙二醇PEG溶解于N,N-二甲基甲酰胺中，然后加入油酸、油胺和浓HCl搅拌得到浅绿色的前驱体溶液，搅拌条件下，将前驱体溶液注入到乙酸铯、油酸和二甲苯的混合溶液中，反应后离心弃去上清液，在沉淀中加入甲苯，超声分散后离心收集沉淀得到CsPbCl3:Mn2+/PEG纳米晶；（2）将得到的CsPbCl3:Mn2+/PEG纳米晶分散在去离子水中，然后将CsPbCl3:Mn2+/PEG纳米晶溶液稀释到pH为1的盐酸稀溶液中后在250nm荧光激发下用于检测水中4-硝基苯酚。
2.根据权利要求1所述的一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法，其特征在于具体方法为：（1）将0.25mmolPbCl2、0.25mmolMnCl2和40mg聚乙二醇PEG溶解于5mLN,N-二甲基甲酰胺中，然后加入0.5mL油酸和0.5mL油胺，最后加入0.5mL浓HCl搅拌得到浅绿色的前驱体溶液，搅拌下将1mL前驱体溶液注入到含有0.05mmol乙酸铯、1mL油酸和5mL二甲苯的混合溶液，反应30-38s后，用紫外灯照射观察到明亮的橙色荧光，将得到的样品离心弃去上清液，沉淀中加入3mL甲苯，超声分散后离心收集沉淀，即为CsPbCl3:Mn2+/PEG纳米晶；（2）将收集到的CsPbCl3:Mn2+/PEG纳米晶分散在2mL的去离子水中形成CsPbCl3:Mn2+/PEG纳米晶水溶液，量取100μL的CsPbCl3:Mn2+/PEG纳米晶水溶液稀释到3mL、pH为1的盐酸稀溶液中用于检测水中4-硝基苯酚。
3.根据权利要求2所述的一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法，其特征在于：所述步骤（1）中在1700-2000r/min搅拌下将1mL前驱体溶液注入到含有0.05mmol乙酸铯、1mL油酸和5mL二甲苯的混合溶液。
4.根据权利要求2或3所述的一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法，其特征在于：所述步骤（1）中得到的样品以9000-10000r/min离心10-15min。
5.根据权利要求4所述的一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法，其特征在于：所述步骤（1）中在沉淀中加入3mL甲苯，使用频率为40KHz的超声波超声分散后继续以9000-10000r/min离心10-15min收集沉淀。
6.根据权利要求1或5所述的一种CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚的方法，其特征在于：所述步骤（2）中CsPbCl3:Mn2+/PEG纳米晶检测水中4-硝基苯酚浓度范围为0.00029-0.40876mmol/L。
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