CN111574541B - 一种超低检测限、高灵敏度的比率型荧光氧气检测材料 - Google Patents
一种超低检测限、高灵敏度的比率型荧光氧气检测材料 Download PDFInfo
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Abstract
本发明公开了一种超低检测限、高灵敏度的比率型氧气检测材料及其制备方法，属于纳米材料和配位化学的交叉领域。所述材料是以12核银硫簇为结点，双齿有机配体桥联的银硫簇基金属‑有机框架材料，具有比率型氧气检测性能。该化合物的化学式为：[Ag12(SBut)8(CF3COO)4(bpy‑NH2)4]n，属于四方晶系；空间群为I‑42m。其在无氧条件下具有强的黄色荧光，包含456 nm和556 nm两个发射峰，荧光寿命分别为0.37 ns和3.12 ms；556 nm处的荧光对氧气极为敏感，在0–2.4 Pa的含氧量范围内，其荧光强度淬灭与氧气压力呈很好的线性关系，能对氧气进行定量检测。该材料具有检测线低，响应快速、灵敏度高、稳定性好等优点。
Description
技术领域
本发明属于纳米材料和配位化学的交叉领域，具体涉及一种新型超低检测限、高灵敏度的比率型氧气检测材料及其制备方法。
背景技术
氧气的定量检测在许多科学技术领域都是必不可少的，对氧气浓度进行原位、快速及精确的检测具有重要意义。与传统的氧气浓度检测方法相比(气相色谱法、奥氏分析仪法、电化学传感器法等)，基于荧光淬灭的光学氧气敏感材料具有检测灵敏度高、操作方便和在线检测能力等优点。具有双发射性能的比率型荧光氧传感材料具有自校准功能，可以有效避免因测试环境差异引起的误差。
金属-有机框架材料是由有机配体连接金属离子或金属簇形成的高度有序晶态多孔材料。传统的双发射金属-有机框架材料大多是主体框架作为一个发射中心，通过向材料孔道中填充荧光体引入另一个发射中心，这种多组分的复合材料很难实现对氧气的超灵敏、比率型定量检测。相对于单一金属离子，以具有特征荧光发射的巯基银簇为结点并引入具有荧光氧气淬灭的有机配体可以组装成具有双发射性能的单组分多孔材料。此外，由于金属-有机框架材料的孔道是由有机配体支撑构筑的，因此有机配体完全裸露于孔道中，从而提高氧气分子与配体的动态碰撞而提高荧光淬灭性能。
由于巯基银簇和有机连接配体的种类均具有较高的可选择性，加之其具有优异的光物理和光化学性能，基于巯基银簇的金属-有机框架材料在分子传感领域表现出了巨大的前景。
发明内容
本发明的目的在于提供具有超低检测限、高灵敏度的比率型氧气检测性能的银簇基金属-有机框架材料及其制备方法。
为实现本发明的目的，本发明公开了一种具有超低检测限、高灵敏度的比率型氧气检测性能的金属-有机框架材料，所述金属-有机框架材料的化学式是：[Ag12(SBut)8(CF3COO)4(bpy-NH2)4]n，属于四方晶系；空间群为I-42m。
其中bpy-NH2为3-氨基-4,4'-联吡啶，结构简式如下：
该超低检测限、高灵敏度的比率型氧气检测材料的制备方法通过如下步骤实现：
将叔丁硫银分散于二氯甲烷和氨水的混合溶液中，快速搅拌；加入三氟乙酸银，搅拌至溶液澄清；再加入bpy-NH2，继续搅拌。反应结束后，将溶液在室温下避光挥发，得晶体，过滤、洗涤、室温晾干后得氧气检测材料。
所述材料是一个以12核巯基银簇为结点，通过bpy-NH2双齿配体桥联形成的二维层状结构；层和层之间以ABAB形式堆积，且通过强的氢键作用形成稳定的三维超分子结构；孔道壁由拉长的巯基银簇和有机配体bpy-NH2组成(图2所示)。材料的孔隙率为17.5％。
本发明超低检测限、高灵敏度的比率型氧气检测材料用于氧气的快速定量检测。具体描述如下：
超低检测限氧气检测：所述材料在无氧环境中具有亮黄色的荧光，其真空下有两个发射峰，最佳发射波长位置分别为456nm(激发波长370nm)和556nm(激发波长370nm)；其中456nm处的发射寿命为0.37ns，556nm处的发射寿命为3.12ms；荧光量子产率为14.62％。因为激发态的寿命越长，氧气通过动态碰撞转移激发态的能量而使荧光淬灭的几率就越大，淬灭效率越高，所以氧气对456nm处荧光发射峰的淬灭效应和556nm处的相比是可以忽略不计的。因此，456nm处的发射可以作为自校准基线，氧气对材料的淬灭效应集中于556nm处荧光发射，使该材料具有比率型荧光氧传感功能。在44.3Pa氧气压力下，荧光强度淬灭达到99.9％。通过氧气压力与荧光强度淬灭的关系计算得Stern-Volmer淬灭常数为2.25kPa-1，最低检测限为11.4mPa。
高灵敏度氧气检测：材料在真空和氧气环境的交替中，其荧光被氧气完全淬灭的响应时间小于0.3s，且在超过100次的真空和氧气循环实验中，材料的荧光发射强度没有发生明显的变化，说明材料在长时间、多次循环氧气检测中能保持优异的稳定性。
本发明优点：该材料在556nm处的荧光对氧气极为敏感，在0–2.4Pa的含氧量范围内，其荧光强度淬灭与氧气压力呈很好的线性关系，不仅能实现对氧气的超低检测限、高灵敏检测，并且具有超长的检测寿命，能够循环使用。
附图说明
图1为本发明所述超低检测限、高灵敏度的比率型氧气检测材料的结构单元图。
图2为本发明所述超低检测限、高灵敏度的比率型氧气检测材料的结构示意图。
图3为本发明所述超低检测限、高灵敏度的比率型氧气检测材料的XRD图。
图4为本发明所述超低检测限、高灵敏度的比率型氧气检测材料的荧光光谱(激发波长为370nm)。
图5为本发明超低检测限、高灵敏度的比率型氧气检测材料在不同氧气压力下荧光强度比例响应的光学图及Stern-Volmer淬灭常数拟合曲线(0–44.3Pa)。
图6为本发明超低检测限、高灵敏度的比率型氧气检测材料在不同氧气压力下荧光强度比例响应的光学图及Stern-Volmer淬灭常数拟合曲线(0–2.4Pa)。
图7为本发明所述超低检测限、高灵敏度的比率型氧气检测材料在真空与空气交替循环下的动态荧光曲线(监测波长550nm，激发波长370nm)。
图8为本发明所述超低检测限、高灵敏度的比率型氧气检测材料在真空与空气交替循环下的动态荧光曲线局部放大图。
具体实施方式
下面通过实例对本发明做进一步的说明：
实施例1：合成超低检测限、高灵敏度的比率型氧气检测材料
将0.15g(0.75mmol)叔丁硫银(ButSAg)分散于40mL二氯甲烷和0.1mL氨水组成的混合溶液中，快速搅拌；加入0.06g(0.27mmol)三氟乙酸银(CF3COOAg)，搅拌至溶液澄清；再加入0.1g(0.058mmol)3-氨基-4,4'-联吡啶(bpy-NH2)，继续搅拌1分钟。反应结束后，将溶液在室温下避光挥发，3天后得约0.079g无色块状晶体，产率30％，过滤、用乙醇洗涤、室温晾干后得氧气检测材料。
实施例2：超低检测限、高灵敏度的比率型氧气检测现象
取实施例1制得的超低检测限、高灵敏度的比率型氧气检测材料样品，在370nm紫外灯的照射下，无氧环境中材料具有亮黄色的荧光；而在空气中，556nm处的荧光被氧气所淬灭，材料呈现蓝色荧光。
实施例3：超低检测限、高灵敏度的比率型氧气检测材料荧光光谱测定
取实施例1制得的超低检测限、高灵敏度的比率型氧气检测材料样品，装入气体吸附仪的样品管中，利用两束光纤分别输送激发光源和接受发射光源。利用气体吸附仪控制氧气分压，在370nm激发光下测不同氧气压力下材料的荧光光谱。从图6中可以看出，含氧量在0–2.4Pa范围内，氧气的压力与556nm处荧光强度的淬灭呈现很好的线性关系，说明本材料可以在超低氧含量下对氧气定量检测。
实施例4：超低检测限、高灵敏度的比率型氧气检测材料的动态荧光曲线测定
取实施例1制得的超低检测限、高灵敏度的比率型氧气检测材料，在真空和空气交替循环下测其550nm处的时间相关荧光强度变化曲线(动态荧光曲线)。从图7可以看到在经过多次的真空和氧气循环实验中，材料的荧光发射强度没有发生明显的变化，说明材料在长时间、多次循环氧气检测中具有优异的稳定性。从图8可以看出，空气淬灭真空下的材料的荧光所需时间小于0.3s，即材料对氧气具有超快的响应特性。
取实施例1制得的超低检测限、高灵敏度的比率型氧气检测材料做进一步表征，其过程如下：
(1)晶体结构测定
配合物的X射线单晶衍射数据用大小合适的单晶样品在Rigaku XtaLAB Pro单晶衍射仪上测定。数据均用Cu Kα射线
为衍射源在室温下收集，使用CrysAlisPro程序进行数据收集和还原。结构用直接法SHELXS求解，并用OLEX2中SHELXL-2015模块进行全矩阵最小二乘法精修。除一些溶剂分子和氢原子外，所有原子均采用各向异性精修，并将其放置在计算的理想几何位置。所有非氢原子均采用各向异性热参数法精修。配体的氢原子坐标由理论加氢得到。详细的晶体测定数据见表1。
表1：超低检测限、高灵敏度的比率型氧气检测材料的主要晶体学数据
表1主要晶体学数据
aR1＝∑||Fo|-|Fc||/∑|Fo|.bwR2＝[∑w(Fo 2-Fc 2)2/∑w(Fo 2)2]1/2
超低检测限、高灵敏度的比率型氧气检测材料的X射线粉末衍射(XRD)表征
本超低检测限、高灵敏度的比率型氧气检测材料的XRD图见图3。通过用材料的单晶结构数据模拟所得的XRD数据和实验所测的XRD数据作图。{仪器型号：Rigaku D/max-3B衍射仪(Cu-Kα,
)}。
Claims (3)
1.一种比率型氧气检测材料，其特征在于，其单晶化学式为：[Ag12(SBut)8(CF3COO)4(bpy-NH2)4]n，属于四方晶系；空间群为I-42m；
α＝90°，β＝90°，γ＝90°，
Z＝2；
其中bpy-NH2为3-胺基-4,4'-联吡啶，结构简式如下：
2.如权利要求1所述的比率型氧气检测材料，其特征在于，以12核巯基银簇为结点，通过bpy-NH2双齿配体桥联形成的二维层状结构；层和层之间以ABAB形式堆积，且通过氢键作用形成三维分子结构。
3.一种制备如权利要求1所述的比率型氧气检测材料的方法，其特征在于，通过以下步骤实现：将叔丁硫银分散于二氯甲烷和氨水的混合溶液中，搅拌；加入三氟乙酸银，搅拌至溶液澄清；再加入bpy-NH2，继续搅拌；反应结束后，将溶液在室温下避光挥发，得晶体，过滤、洗涤、室温晾干后得氧气检测材料。
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