CN111072717B - 一种水中稳定性好有机-无机杂化钙钛矿材料的制备方法 - Google Patents
一种水中稳定性好有机-无机杂化钙钛矿材料的制备方法 Download PDFInfo
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Abstract
本发明公开了生物材料技术领域的一种水中稳定性好有机—无机杂化钙钛矿材料的制备方法，该工艺步骤如下：步骤一：合成制备DAT探针分子；步骤二：将热注入法制备的CsPbBr3中加入DAT配体在100℃～180℃的环境中在DMF中加热回流24h形成有机荧光传感材料；步骤三：将制备好的有机—无机杂化钙钛矿材料配成1umol/ml的标准液，分别向离心管各中加入100ul，然后加入100ul环己烷，再加入100ul水和100ul缓冲溶液；步骤四：将上述溶液超声分别加入不同浓度的Fe3+离子标准液100ul；步骤五：将上述混合溶液依次进行光谱分析，最终绘制成检测限图，提高水稳定性，同时具备荧光检测试剂优点。
Description
技术领域
本发明公开了一种水中稳定性好有机-无机杂化钙钛矿材料的制备方法，具体为生物材料技术领域。
背景技术
钙钛矿材料由于其具有吸收效率高、缺陷态密度低、载流子迁移率高、直接带隙可调等诸多优点,在光电材料领域中备受关注,在太阳能电池、发光二极管的应用中颇具潜力。同时,制备工艺简单、形貌调控方便,钙钛矿材料本身也是一种非常理想的激光增益介质。自2014年发现钙钛矿薄膜的放大自发辐射现象,钙钛矿激光成为了发光领域重要的研究方向之一。而当前如何解决钙钛矿材料本身稳定性差任然是巨大的挑战。
Fe3+离子广泛分布于天然水、蔬菜、水果、作物和动物体中。生物在新陈代谢的过程中，Fe3+离子参与着许多非常重要的生化过程。然而，生物体本身摄入过多或过少会产生不良的反应。科学发展的过程中投入了巨大的努力对于定性或定量的Fe3+测定，伴随着传感技术的发展已经开发和应用了多种方法，包括原子吸收，色谱法、电化学法、流动注射法和荧光传感材料均可应用于Fe3+离子检测，但是这些方法不仅检测成本高昂，检测程序复杂，时间慢，并且选择性大大不如有机荧光离子检测法。
有机荧光离子检测法是一项重要的技术。检测铁离子具有明显的优点；时间短、高效率、灵敏度高便于检测。但是无论是纯钙钛矿材料还是有机-无机杂化钙钛矿材料都有着遇水后离子化分解的缺点，一直无法应用于生物领域，所以开发一种水中稳定好并复合生物功能性的钙钛矿材料尤为重要。
因此尚需要一种水稳定性好，毒性低的同时还要兼备有机荧光检测试剂优点的钙钛矿材料。
发明内容
本发明的目的在于提供一种水中稳定性好有机-无机杂化钙钛矿材料的制备方法，以解决上述背景技术中提出的纯钙钛矿材料或有机-无机杂化钙钛矿材料在遇水后会导致离子化分解的问题。
为实现上述目的，本发明提供如下技术方案：一种水中稳定性好有机-无机杂化钙钛矿材料的制备方法，该工艺步骤如下：
步骤一：合成制备DAT探针分子；1)取6.6mmol的2,4-二羟基苯甲醛，4mmol的丙二酸二乙酯和0.1mL的哌啶放入50mL的单口烧瓶中，然后加入10mL无水乙醇，搅拌、冷凝回流2h，形成黄色沉淀，然后冷却，离心收集固体，用无水乙醇清洗，干燥、合成出Ethyl-7-hydroxy-3-carboxylate 2(乙基-7-羟基-3-羧酸乙酯2，简称化合物2)。2)取1mmol化合物2,1mmol三(羟甲基)氨基甲烷放入50单口烧瓶中，然后加入5的无水乙醇，将反应物回流8h，将反应物在真空的环境中浓缩，之后将粗产物经过柱层析得到DAT(柱层析二氯甲烷：甲醇＝10:1)。
步骤二：将热注入法制备的CsPbBr3中加入DAT配体在100℃～180℃的环境中在DMF中加热回流24h形成有机荧光传感材料；1)CsPbBr3的制备：取0.16g的溴化铅，1.5mL油酸，2.5mL油胺放入50mL的三口烧瓶中，然后将溶液加热到150℃，维持1h，然后加热到180℃，维持5分钟，接着迅速注入1mL前驱体(Cs的油酸盐),10s后快速冷却，离心，然后放入甲苯中溶解。2)复合荧光材料的合成：将制备的CsPbBr3钙钛矿溶在20mL DMF中,然后取0.02gDAT溶在甲酸中，去除多余甲酸，将两者混合加入到100mL单口烧瓶中，加入碘化亚铜作为作为催化剂，避光回流24h.
步骤三：将制备好的有机-无机杂化钙钛矿材料配成1umol/ml的标准液，分别向离心管各中加入100ul，然后加入100ul环己烷，再加入100ul水和100ul缓冲溶液；
步骤四：将上述溶液超声分别加入不同浓度的Fe3+离子标准液100ul；
步骤五：将上述混合溶液依次进行光谱分析，最终绘制成检测限图。
优选的，对混合溶液进行光谱分析的检测范围为25fmol/ml-0.25fmol/ml检测下限为0.04263fmol/ml。
优选的，有机荧光传感材料为DAT探针材料。
与现有技术相比，本发明的有益效果是：第一方面是提供了一种生物相容性好，水稳定性好的钙钛矿材料；第二方面是给出了该有机-无机杂化钙钛矿材料的检测范围为25nmol/ml-250nm/ml(水溶液中)、25fmol/ml-0.25fm/ml(环己烷中),其检测下限为0.04263fmol/ml。
附图说明
图1为本发明结构示意图；本发明中作为配套的香豆素分子简写为DAT，包括香豆素母环和铁离子特异性结合基团。香豆素母环上的羟基可以通过亲核反应取代卤素，进而结合到钙钛矿纳米晶表面。
图2为复合材料的发射光谱图；该有机-无机杂化钙钛矿材料在水溶液中蓝光发射、环己烷溶液中绿光发射、固体中呈现出蓝光绿光双发射。
图3为该有机-无机杂化钙钛矿材料的XPS铅元素的能谱分析图；图(a)为该有机-无机杂化钙钛矿材料的XPS能谱，随着DAT分子修饰量的增加，如图(b)可以看出修饰后的钙钛矿中心原子Pb的化合价随着配体与PbBr2比例1:1、1：10、1：100由+2价逐步升高至+3价。
图4为该有机-无机杂化钙钛矿材料红外光谱图。在1702.17nm位置吸收属于羟基的震动峰，出现在DAT材料和分子中，同时在杂化材料中消失证明PbBr2成功连接DAT；在3483.91nm位置吸收属于氨基的震动峰，出现在DAT材料和分子中；在3315.12nm位置吸收属于碳碳双键的震动峰，出现在DAT材料和分子中。
图5为该材料在水中和环己烷中能稳定存在的证据图；为该有机-无机杂化钙钛矿材料的水稳定性光谱测试，测试复合材料在环己烷和水中的吸收和发射光谱，测试结果表明：在环己烷中能够获得钙钛矿纳米晶的吸收，在水中，吸收消失，而出现配体DAT的特征性吸收，当再次溶入环己烷中时，钙钛矿纳米晶的吸收出现，并在水中只出现配体的吸收。真个过程均测试了结构，通过XRD测试，确定材料均是钙钛矿结构，没有发生变化。
图6为该有机-无机杂化钙钛矿材料选择性的图；该复合材料对Fe3+有很好的的选择性。
图7为该有机-无机杂化钙钛矿材料水中的发射光谱，以及该产品检测灵敏度图；取1mL浓度为1mol/mL的探针材料，加入1mL(PH＝7.4)PBS缓冲溶液，1mL浓度范围内的Fe(NO3)3待测溶液，图(a)为2.5mM到25uM范围的铁离子检测光谱，获得很好的线性范围，如图(b)检测下限为20uM。
图8为该有机-无机杂化钙钛矿材料环己烷-水体系的发射光谱，以及该产品检测线图；图(a)在2.50pM-250fM范围，测出发射光谱随Fe3+离子浓度变化图，绘制检测线图并计算检测下限,如图(b)检测下限为42fM。
图9为该材料在环己烷-水体系中稳定性图；为该有机-无机杂化钙钛矿材料处于水与环己烷的混合体系中的长时稳定性，可以看出纯钙钛矿材料在30分钟即彻底分解，杂化钙钛矿中可以稳定存在14天，而加入铁离子的杂化材料在最开始发光迅速增强，然后实现光谱稳定，时间可以达到21天。这种加入铁离子后的荧光增强可以应用于铁离子检测。
图10为一组该有机荧光探针材料的生物毒性的测试(MTT法)图；实验前后，细胞的活性基本没有发生变化，表明我们的荧光探针材料毒性很低，适合生物体的检测。
图11为该材料自然光可视化检测的应用图；因为该钙钛矿复合纳米材料具有很高的发光效率，在太阳光激发下既可以看到光谱变化。而且其发光颜色变化可以通过裸眼观察。为证实其裸眼检测性能，我们利用了光纤光谱仪和太阳能模拟器，在一个太阳能常数的辐照下，图(a)可以看到具体操作：100ul(2.5fMm-25mM)Fe3+与100ul 1uM发光材料混合后加入500ul的比色皿中拿光纤光谱仪和太阳能模拟器下测试。利用发射蓝光的染料分子DAT作为参比试剂，观察加入铁离子后的光谱变化，同时利用裸眼观察与光谱向印证。图(b)可以观察到在绿光位置(520nm)，荧光强度随着铁离子增加而增强，绘制比率荧光检测线，检测下限如图(c)中所示为1nM。
图12为CsPbCI3，CsPbI3的XRD图谱及发射光谱。该有机-无机杂化钙钛矿材料中仍然具备钙钛矿材料的性质，利用不同的卤素原子X(X＝Cl、Br、I)可以实现带隙可调的特点。
图13为该有机-无机杂化钙钛矿材料(X＝CI、I)对Fe3+的检测线。对于不同的卤素原子(X＝CI、I)制备的有机-无机杂化钙钛矿材料对Fe3+仍然具备很好的检测能力。
图14为该有机-无机杂化钙钛矿材料钙钛矿量子点/DAT复合材料结构示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
请参阅图1-14，本发明提供一种水中稳定性好有机-无机杂化钙钛矿材料的制备方法，该工艺步骤如下：
步骤一：合成制备DAT探针分子；
步骤二：将热注入法制备的CsPbBr3中加入DAT配体在100℃～180℃的环境中在DMF中加热回流24h形成有机荧光传感材料；
步骤三：将制备好的有机-无机杂化钙钛矿材料配成1umol/ml的标准液，分别向离心管各中加入100ul，然后加入100ul环己烷，再加入100ul水和100ul缓冲溶液；
步骤四：将上述溶液超声分别加入不同浓度的Fe3+离子标准液100ul；
步骤五：将上述混合溶液依次进行光谱分析，最终绘制成检测限图。
此合成方法适用于ABX3(X＝Cl、Br、I)全系卤代钙钛矿的修饰，同时此种合成材料适用于Fe3+传感、荧光标记和裸眼可视等方面。
其中，对混合溶液进行光谱分析的检测范围为25fmol/ml-0.25fmol/ml检测下限为0.04263fmol/ml，根据目前已有报道的Fe3+离子有机荧光探针材料中，检测下限处于领先水平。
其中，有机荧光传感材料为DAT探针材料。
工作原理：通过该工艺步骤的制备方法，将该有机-无机杂化钙钛矿材料在水中进行发射光谱检测，同时绘制该产品的检测线图，其检测方法如下：取1umol/ml 1ml材料分子，1ml(PH＝7.4)PBS缓冲溶液，1ml浓度范围空Fe(NO3)3配成待测液，测出发射光谱随Fe3+离子浓度变化图，绘制检测线图并计算检测下限；将该有机-无机杂化钙钛矿材料环己烷-水体系进行发射光谱检测及绘制该产品检测图，其检测方法如下：取1umol/ml 1ml材料分子，1ml环己烷溶液，1ml去离子水，1ml浓度范围空Fe(NO3)3配成待测液，测出发射光谱随Fe3+离子浓度变化图，绘制检测线图并计算检测下限；绘制该有机-无机杂化钙钛矿材料选择性的图，其操作方法如下：配置1umol/ml 1ml荧光材料、1ml(PH＝7.4)PBS缓冲溶液、1mmol/ml不同种金属离子溶液(Na+、K+、Zn2+、Ca2+、Fe2+、Fe3+、Sn2+、Cu2+、Ba2+、Mn2+、Ni2+、Co2+)混合后通过对其发射光谱强度的变化从而绘制出选择性图；最后进行该材料的自然光可视化检测，具体操作：100ul(1nmol/ml-4um/ml)Fe3+与100ul 1umol/ml发光材料混合后加入500ul的比色皿中拿到太阳光下裸眼观察颜色变化。如以2,4二羟基苯甲醛为原料，修饰了可以特异性结合Fe3+的结合位点，为了增加钙钛矿材料的水溶性以及生物相容性，将合成出的DAT修饰在CsPbBr3钙钛矿材料的表面。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (2)
1.一种水中稳定性好有机—无机杂化钙钛矿材料的制备方法，其特征在于：该工艺步骤如下：
步骤一：合成制备DAT探针分子；
1）取6.6 mmol的2,4-二羟基苯甲醛，4 mmol的丙二酸二乙酯和0.1mL的哌啶放入50 mL的单口烧瓶中，然后加入10 mL无水乙醇，搅拌、冷凝回流2h，形成黄色沉淀，然后冷却，离心收集固体，用无水乙醇清洗，干燥、合成出乙基-7-羟基-3-羧酸乙酯2，简称化合物2；
2）取1 mmol化合物2,1 mmol三（羟甲基）氨基甲烷放入50mL单口烧瓶中，然后加入5mL的无水乙醇，将反应物回流8h，将反应物在真空的环境中浓缩，之后将粗产物经过柱层析得到DAT；
步骤二：将热注入法制备的CsPbBr3中加入DAT配体在100°C~180 °C的环境中在DMF中加热回流24h形成有机荧光传感材料；
1）CsPbBr3的制备：取0.16g的溴化铅，1.5 mL油酸，2.5 mL油胺放入50 mL的三口烧瓶中，然后将溶液加热到150℃，维持1h，然后加热到180℃，维持5分钟，接着迅速注入1 mL前驱体Cs的油酸盐,10s后快速冷却，离心，然后放入甲苯中溶解；
2）复合荧光材料的合成：将制备的CsPbBr3钙钛矿溶在20 mL DMF中,然后取0.02 gDAT溶在甲酸中，去除多余甲酸，将两者混合加入到100 mL单口烧瓶中，加入碘化亚铜作为催化剂，避光回流24 h；
步骤三：将制备好的有机—无机杂化钙钛矿材料配成1umol/ml的标准液，分别向离心管各中加入100ul，然后加入100ul环己烷，再加入100ul水和100ul缓冲溶液；
步骤四：将上述溶液超声分别加入不同浓度的Fe3+离子标准液100ul；
步骤五：将上述混合溶液依次进行光谱分析，最终绘制成检测限图。
2.根据权利要求1所述的一种水中稳定性好有机—无机杂化钙钛矿材料的制备方法，其特征在于：对混合溶液进行光谱分析的检测范围为25fmol/ml-0.25fmol/ml检测下限为0.04263fmol/ml。
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| 香豆素修饰SBA-15材料及其对Fe~(3+)的识别和吸附性能;山少斌等;《齐齐哈尔大学学报(自然科学版)》;20150315(第02期);第8-11页 * |
| 高效高稳定性钙钛矿太阳能电池中的关键材料研究;张飞;《中国博士学位论文全文数据库 工程科技II辑》;20180815(第8期);第C042-43页 * |
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