CN111484628A - 一种MOFs-锌材料及其制备方法和用途 - Google Patents
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Abstract
本发明提供了一种MOFs‑锌材料，其分子式为Zn(CDC)(BPY)]·DMF·2H2O，其中，CDC为3,6‑咔唑二羧酸配体，BPY为4,4'‑联吡啶配体，晶体属于四方晶系的I4/mcm空间群，晶体学上，独立的Zn2+采用四配位的配位方式与来自两个3,6‑咔唑二羧酸配体的两个氧原子和来自两个4,4'‑联吡啶配体的两个氮原子配位，以两个3,6‑咔唑二羧酸配体和两个Zn2+先构成一个小环，再由两个所述小环和四个4,4'‑联吡啶配体、连带两个Zn2+构成六个顶点均为Zn2+的环状结构，晶胞参数为α＝β＝γ＝90°，
晶胞体积为
Z＝32。本发明具有如下的有益效果：将MOFs‑锌材料用于构建可识别Cr2O7 2‑的荧光传感器，实现快速检测。
Description
技术领域
本发明涉及一种锌MOFs-锌材料及其制备方法和用途，属于传感器制备技术领域。
背景技术
铬作为一种有毒化学元素，已广泛用于印刷，电镀，皮革鞣制，金属抛光等多种工业生产中。全世界已产生大量铬废料，严重引发了环境问题。铬在许多环境条件下均以高溶解性的六价铬酸盐阴离子形式(Cr2O7 2-)存在，这些阴离子的过量摄入带有明显的致癌性和致突变性，导致DNA损伤并破坏人体的蛋白质和酶系统。此外，铬酸根阴离子在核废料玻璃化的过程中是个解决难题，由于它们会在内部结晶形成尖晶石。因此，在许多环境和工业应用中，监测铬酸根阴离子的浓度至关重要。
在诸多的分析检测法中例如离子色谱法，电感耦合等离子体质谱法(ICP-MS)，光纤波传感器的使用，和高效液相色谱法与原子吸收光谱法均适用于定性和定量分析。其中，荧光法通常只需要较短的处理时间并且涉及较少的样品预处理，因此备受关注。在过去的十年中，金属有机骨架(MOF)引起了人们的极大兴趣，更具设计性的构造蕴藏了广阔的性能应用前景，常常被用于气体吸附与分离、催化、电化学等领域。其中，通过MOFs构建荧光传感器的例子也并不罕见。
通过金属中心和配体的置换进行MOFs结构的调控是常见方式，而本专利是在金属和配体的配比都相同的情况下，通过简单改变溶液酸碱性进行结构的调控，制备了FJU-82-Zn的同“分”异构体FJU-826。提升了MOF的荧光强度，同时实现非镧系MOF的铬(Ⅵ)氧阴离子荧光传感器的构建。
发明内容
本发明是为了解决现有的技术的难题，提供一种简单改变溶液酸碱度从而调控MOFs结构的制备方法及可识别Cr2O7 2-的荧光传感器。
本发明是通过以下技术方案实现的：
本发明提供一种MOFs-锌材料，其分子式为Zn(CDC)(BPY)]·DMF·2H2O，其中，CDC为3,6-咔唑二羧酸配体，BPY为4,4'-联吡啶配体，晶体属于四方晶系的I4/mcm空间群，晶体学上，独立的Zn2+采用四配位的配位方式与来自两个3,6-咔唑二羧酸配体的两个氧原子和来自两个4,4'-联吡啶配体的两个氮原子配位，以两个3,6-咔唑二羧酸配体和两个Zn2+先构成一个小环，再由两个所述小环和四个4,4'-联吡啶配体、连带两个Zn2+构成六个顶点均为Zn2+的环状结构，α＝β＝γ＝90°，
体积为
Z＝32。
一种如前述的MOFs-锌材料的制备方法，其包括如下步骤：
将水溶性锌盐、4,4'-联吡啶和3,6-咔唑二羧酸溶于二甲基甲酰胺和蒸馏水中，加入氢氧化钾水溶液，混匀后，在85℃下进行水热反应，得到所述锌-MOFs材料。
作为优选方案，所述水溶性锌盐为硝酸锌。
作为优选方案，所述硝酸锌、4,4'-联吡啶和3,6-咔唑二羧酸的摩尔比为1：1：1。
作为优选方案，所述水热反应的时间为24h。
一种如前述的MOFs-锌材料在识别Cr2O7 2-的荧光传感器中的用途。
一种如前述的荧光传感器的构建方法，其包括如下步骤：
将MOFs-锌材料溶于蒸馏水中，定容成0.5mg/mL的混合液；
取若干份1mL的所述混合液，分别加入不同已知浓度的Cr2O7 2-溶液后，均定容至10mL，得到若干份标准样；
对各份所述标准样进行荧光光度检测，设置荧光的激发波长为295nm，响应时间为0.1s，得到荧光吸收强度和Cr2O7 2-浓度的关系，并以荧光吸收强度和Cr2O7 2-浓度绘制标准曲线。
与现有技术相比，本发明具有如下的有益效果：
本发明利用简单改变溶液酸碱性的方法，实现快速调控MOFs结构提升材料的荧光性能，制备了FJU-82-Zn的同“分”异构体FJU-826。
其次将FJU-826用于构建可识别Cr2O7 2-的荧光传感器，实现快速检测。该传感器的线性范围为0.5～0.9mmol/L及5～90μmol/L，检测限为1.2μM。且该传感器还具有良好的稳定性、重现性和抗干扰性，对实际的水样进行了加标回收率实验，回收率为96.0～98.7％，得到较为理想的性能。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：
图1是本发明实施例1的FJU-826晶体结构的配位环境、构建方式以及三维结构分析；
图2是本发明对比例1的FJU-82-Zn晶体结构的配位环境、构建方式以及三维结构分析；
图3是本发明对比例1的FJU-82-Zn和FJU-826的红外光谱分析；
图4是本发明对比例1的FJU-82-Zn和FJU-826在紫外光照射下的光学显微镜图像；
图5是本发明对比例1的FJU-82-Zn和FJU-826的固体荧光测试结果；
图6是本发明实施例2的FJU-826于不同溶剂中的荧光谱图；
图7是本发明实施例2的FJU-826浸泡过不同溶剂后的XRD谱图；
图8是本发明实施例3的FJU-826在不同阴离子水溶液中的荧光谱图；
图9是本发明实施例4的FJU-826在不同浓度的Cr2O7 2-水溶液中的荧光响应谱图；
图10是本发明实施例4的线性拟合曲线；
图11是本发明实施例5的FJU-826荧光传感器对阴离子和氨基酸的抗干扰实验；
图12是本发明实施例5的FJU-826荧光传感器对阳离子的抗干扰实验；
图13是本发明实施例6的浸泡过Cr2O7 2-水溶液的FJU-826的荧光显微镜图像；
图14是本发明实施例6的浸泡Cr2O7 2-水溶液前后的FJU-826的XRD谱图；
图15是本发明实施例6的不同阴离子水溶液的紫外可见吸收光谱图；
图16是本发明实施例6的Cr2O7 2-水溶液的紫外可见吸收光谱图和FJU-826在水溶液中的荧光谱图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
本实施例提供了一种MOFs-锌材料的制备方法，具体包括如下步骤：
将六水合硝酸锌(Zn(NO3)2·6H2O,0.1mmol,29.8mg)，4,4'-联吡啶(BPY,0.1mmol,15.6mg),3,6-咔唑二羧酸(CDC,0.1mmol,25.5mg)溶于二甲基甲酰胺(DMF,4mL)和蒸馏水(2mL)中，最后加入1mL 1.0M的KOH水溶液，得到透明混合物。然后，将透明混合物密封在透明玻璃瓶中在85℃下反应24h，得到淡黄色块状晶体MOFs-锌材料，记为FJU-826，分子式为[Zn(CDC)(BPY)]·DMF·2H2O，产率为60％。元素分析结果，实验值:C,55.80；H,4.53；N,10.03，理论值:C,55.40；H,4.27；N,10.05。
通过Agilent Technologies Super Nova单晶衍射仪收集关于MOFs-锌材料的衍射强度数据。MOFs-锌材料相关晶体数据与结构精修参数列于表1中。单晶X射线衍射分析结果显示出MOFs-锌材料属于四方晶系的I4/mcm空间群。
表1MOFs-锌材料(FJU-826)的相关晶体数据
详细分析MOFs-锌材料的晶体结构，如图1a所示，晶体学上独立的Zn2+采用四配位的配位方式与两个氧原子(来自两个CDC)和两个氮原子(来自两个BPY)配位。FJU-826的框架中，先由两个CDC配体和两个Zn2+构成一个小环，再由两个小环和四个BPY配体，连带两个金属Zn2+构成六个顶点均为Zn2+的类似六元环结构，如图1b所示。每个六元环结构通过共用金属顶点的方式形成蜂窝状二维网格的单层结构，其中每个金属顶点被三个六元环共用，如图1c所示。从c轴方向上看平行网格构成的堆积图，发现相邻的平行网格间出现滑移现象，如图1d所示。如图1e，将二维网格的单层结构抽拓扑，通过Topos 4.0软件分析发现MOFs-锌材料属于hcb类型的拓扑，其中节点对应金属Zn2+。在堆积着的平行网格结构的垂直方向上穿插堆积着同样层间滑移的平行网格，从而形成MOFs-锌材料的三维框架结构，如图1f所示。
对比例1
本对比例与实施例的区别仅在于，在水热反应中未加入KOH水溶液，得到的产物命名为MOFs-锌材料异构体，记为FJU-82-Zn。通过Agilent Technologies SuperNova单晶衍射仪收集关于MOFs-锌材料异构体的衍射强度数据。MOFs-锌材料异构体相关晶体数据与结构精修参数列于表2中。
表2MOFs-锌材料异构体(FJU-82-Zn)的相关晶体数据
3,6-咔唑二羧酸(CDC)和4,4'-联吡啶(BPY)在DMF和水的混合溶剂中与Zn(NO3)2反应合成FJU-82-Zn，化学式为[Zn(CDC)(BPY)]·DMF·3H2O。在混合溶剂中添加KOH溶液后，反应合成的是FJU-826，化学式为[Zn(CDC)(BPY)]·DMF·2H2O。发现除去溶剂分子外，FJU-82-Zn和FJU-826是同分异构体。单晶X射线衍射分析结果显示出FJU-82-Zn属于三斜晶系的P-1空间群。详细分析FJU-82-Zn的晶体结构，如图2a所示，晶体学上独立的Zn2+采用六配位的配位方式与四个氧原子(来自两个CDC)和两个氮原子(来自两个BPY)配位。FJU-82-Zn的框架中，先由配体CDC和Zn2+形成一维双核金属链,如图2b，并通过配体BPY桥接形成二维菱形网格的单层结构，如图2c所示。二维菱形网格通过不同二维层中相邻配体(CDC)之间的π…π堆叠作用构成三维超分子构型如图2d，两个CDC分子重心之间的距离为
如图2e所示。
通过傅立叶变换红外光谱(FTIR)仪测试了FJU-82-Zn和FJU-826的红外光谱，从图3可以发现，两者红外光谱图十分相似。这主要是由于FJU-82-Zn和FJU-826都是使用CDC和BPY作为有机连接体，Zn2+作为金属中心合成的两例组成相同但结构不同的MOFs。根据所得的结果，3500cm-1附近的峰对应N-H伸缩振动，3300cm-1左右的峰对应O-H伸缩振动。大约1650cm-1和1370cm-1处的峰分别对应于羧基上的C＝O不对称伸缩振动和C-O对称伸缩振动。3050cm-1附近的峰和1490cm-1附近的峰分别属于苯环上的C-H特征峰和C＝C伸缩振动。基于以上的红外分析结果，表明FJU-82-Zn和FJU-826均包含了CDC和BPY的相关官能团。
将制备好的FJU-82-Zn和FJU-826分别放置在干净的载玻片上，用紫外光进行照射，置于光学显微镜下进行观察。如图4a中的棒状淡黄色晶体是FJU-82-Zn，图4b中发着青色光的块状晶体是FJU-826。而且，通过固体荧光测试发现在激发波长为295nm的条件下，FJU-826的最强发射峰在520nm左右，强度远远大于FJU-82-Zn(图5)。由于FJU-82-Zn晶体结构中邻近配体CDC之间存在相互堆叠，而FJU-826中两个CDC配体和金属离子连接形成小环构成共平面，距离最近的两个小环所在的平面互相垂直不存在堆叠，这使得它们的荧光性能差别较大。
因此，通过实施例1和对比例1的对比可知，与FJU-82-Zn相比，FJU-826升级了晶系。
实施例2
本实施例涉及FJU-826荧光传感器溶剂体系的选择方法，具体包括如下步骤：
将制备好的FJU-826用玛瑙研钵研磨成极细的粉末状，分别称取4mg的粉末和6mL的不同溶剂混合，超声30min确保FJU-826在各溶剂中分散均匀。测试参数设置：激发波长295nm，响应时间为0.1s，其结果如图6所示。在不同溶剂中，FJU-826的荧光性能也有所不同。其中，在380nm附近，六种溶剂中以水的荧光性能最佳，甲醇、乙醇、四氢呋喃、乙酸乙酯及DMF次之。此外，将FJU-826浸泡在不同溶剂中，一天后过滤晾干回收样品进行粉末衍射测试，结果如图7所示，和模拟的粉末图谱对比后，发现FJU-826能稳定存在于这六种溶剂中。基于FJU-826在水中荧光响应信号最强，且实际应用体系水环境居多，所以选择水环境作为构建荧光传感器的检测体系。
实施例3
本实施例涉及FJU-826荧光传感器检测物的确定，具体包括如下步骤：
将25mg的FJU-826于50.00mL容量瓶，蒸馏水定容后冷水浴超声30min分散均匀。然后取1.00mL的分散液于不同的10mL容量瓶中，再移取1.00mL(0.1mol/L)的不同阴离子水溶液，最后用蒸馏水定容，冷水浴超声30min确保FJU-826均匀分散于溶液中。测试参数设置：激发波长295nm，响应时间为0.1s。结果如图8所示，在不同阴离子的相同浓度均为0.01mol/L的条件下，荧光强度的大小有明显的不同，其中Cr2O7 2-离子的影响较大，淬灭率远远高于其他阴离子。因此选择Cr2O7 2-离子作为检测的对象。
实施例4
本实施例涉及对FJU-826荧光传感器体系检测线性范围与检出限的确定，具体包括如下步骤：
称取FJU-826置于容量瓶中，用蒸馏水定容配成0.5mg/mL的混合液。混合液超声分散后分别取1.00mL于10mL的容量瓶中，配置成含有不同浓度Cr2O7 2-的混合液，冷水浴超声30min。测试参数设置：激发波长295nm，响应时间为0.1s，测试结果如图9所示。线性拟合结果如图10所示，Cr2O7 2-离子浓度与FJU-826混合液的荧光强度分两个范围呈现线性关系，0.5mmol/L到0.9mmol/L之间的线性关系I＝-1308.65c(mmol/L)+1366.78，R2＝0.986，最低检出限为0.10mmol/L；5μmol/L到90μmol/L之间的线性关系为I＝-18.57c(μmol/L)+3140.99，R2＝0.999，最低检出限为1.20μmol/L。与其他同类材料(MOFs)对比，结果如下表3所示，FJU-826的检出限在锌基MOFs里相对优秀，但是与镧系MOFs还有差距。
表3.各种发光MOFs传感器用于水相中Cr2O7 2-检测的性能比较
实施例5
本实施例涉及FJU-826荧光传感器体系的检测抗干扰能力的评估，本实验对含有干扰物和50μmol/LCr2O7 2-的样品同理掺入定量FJU-826进行荧光检测，结果表明，在存在有100倍缬氨酸(Val)、甘氨酸(Gly)、丙氨酸(Ala)、F-、Cl-、Br-、SO3 2-、SO4 2-、NO3 -、Li+、Mg2+、K+、Cd2+，10倍I-、NO2 -、组氨酸(His)、尿素(UA)，同倍PO4 3-、Na+、Ca2+、Mn2+、Ni2+时，对Cr2O7 2-的测定不存在影响(如图11和图12所示)，FJU-826荧光传感器具有很好的抗干扰性和适用性。
实际水样的测定：同理掺入定量FJU-826构建荧光传感体系，采用加标回收法对实际水样中Cr2O7 2-含量进行荧光检测。结果如表4所示，Cr2O7 2-的回收率范围为96.0～98.7％，说明了FJU-826构建的荧光传感器对Cr2O7 2-检测具备实际应用性。
表4.实际水样中Cr2O7 2-的测定(平均值±SD，n＝3)
SD：standarddeviation；ND：notdetected；RSD：relative standarddeviation；
实施例6
FJU-826在0.01M的Cr2O7 2-水溶液中浸泡15天后，过滤后经蒸馏水润洗，在荧光显微镜下进行观察。如图13a所示，FJU-826依旧是方块状的淡黄色晶体。给予激发光照射，如图13b所示，FJU-826依旧是发着青色光的块状晶体。通过X射线粉末衍射测试，发现FJU-826在浸泡前后仍然保持其结构稳定性，如图14所示。表明Cr2O7 2-水溶液并未使FJU-826结构发生破坏，荧光猝灭的原因不是由于FJU-826的结构改变引起的。
将浸泡Cr2O7 2-水溶液前后的FJU-826进行能量色散X射线光谱(EDS)面扫分析，结果如下表5所示，浸泡前后的Cr元素含量基本一致，属于背景干扰范畴。说明浸泡后的FJU-826样品表面并未吸附Cr2O7 2-离子，排除了表面吸附Cr2O7 2-离子导致荧光猝灭的可能。
表5.相关的EDS面扫元素分析结果
将0.01M各种不同阴离子的水溶液进行紫外吸收光谱分析，测试结果如图15和图16所示，发现除了Cr2O7 2-外，所测试的阴离子水溶液的紫外吸收峰所在范围均小于260nm。Cr2O7 2-水溶液的紫外吸收光谱显示了两个宽带(在260、370nm出现了λmax)。其中370nm附近的吸收峰与FJU-826的荧光发射峰之间存在光谱重叠，表明由于两者之间的弱相互作用，电子能量有可能从FJU-826转移到分析物Cr2O7 2-，从而引发选择性猝灭现象。未观察到其他阴离子的光谱与FJU-826的发射峰之间有重叠现象，这表明FJU-826对Cr2O7 2-离子选择性猝灭的原因。因此，由于与分析物的光谱重叠而引起电子能量转移的静态猝灭过程可以被认为是当前情况下可行的猝灭机制。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。
Claims (7)
1.一种MOFs-锌材料，其特征在于，分子式为Zn(CDC)(BPY)]·DMF·2H2O，其中，CDC为3,6-咔唑二羧酸配体，BPY为4,4'-联吡啶配体，晶体属于四方晶系的I4/mcm空间群，晶体学上，独立的Zn2+采用四配位的配位方式与来自两个3,6-咔唑二羧酸配体的两个氧原子和来自两个4,4'-联吡啶配体的两个氮原子配位，以两个3,6-咔唑二羧酸配体和两个Zn2+先构成一个小环，再由两个所述小环和四个4,4'-联吡啶配体、连带两个Zn2+构成六个顶点均为Zn2 +的环状结构，晶胞参数为α＝β＝γ＝90°，
晶胞体积为
Z＝32。
2.一种如权利要求1所述的MOFs-锌材料的制备方法，其特征在于，包括如下步骤：
将水溶性锌盐、4,4'-联吡啶和3,6-咔唑二羧酸溶于二甲基甲酰胺和蒸馏水中，加入氢氧化钾水溶液，混匀后，在85℃下进行水热反应，得到所述锌-MOFs材料。
3.如权利要求2所述的MOFs-锌材料的的制备方法，其特征在于，所述水溶性锌盐为硝酸锌。
4.如权利要求3所述的MOFs-锌材料的的制备方法，其特征在于，所述硝酸锌、4,4'-联吡啶和3,6-咔唑二羧酸的摩尔比为1：1：1。
5.如权利要求2所述的MOFs-锌材料的的制备方法，其特征在于，所述水热反应的时间为24h。
6.一种如权利要求1所述的MOFs-锌材料在识别Cr2O7 2-的荧光传感器中的用途。
7.一种如权利要求6所述的荧光传感器的构建方法，其特征在于，包括如下步骤：
将MOFs-锌材料溶于蒸馏水中，定容成0.5mg/mL的混合液；
取若干份1mL的所述混合液，分别加入不同已知浓度的Cr2O7 2-溶液后，均定容至10mL，得到若干份标准样；
对各份所述标准样进行荧光光度检测，设置荧光的激发波长为295nm，响应时间为0.1s，得到荧光吸收强度和Cr2O7 2-浓度的关系，并以荧光吸收强度和Cr2O7 2-浓度绘制标准曲线。
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| CN112175193A (zh) * | 2020-09-29 | 2021-01-05 | 陈燕 | 一种发白色荧光的柔性金属有机框架的制备方法 |
| CN112649573A (zh) * | 2020-12-17 | 2021-04-13 | 北京交通大学 | 双信号响应的余氯传感器及其制备方法以及检测系统 |
| CN113603897A (zh) * | 2021-08-25 | 2021-11-05 | 北京工业大学 | 一种锌基金属有机骨架材料的制备及其选择性吸附应用 |
| CN113603897B (zh) * | 2021-08-25 | 2022-06-07 | 北京工业大学 | 一种锌基金属有机骨架材料的制备及其选择性吸附应用 |
| CN116376047A (zh) * | 2023-05-23 | 2023-07-04 | 山西大学 | 一种六核锌配位聚合物及其制备方法和应用 |
| CN116376047B (zh) * | 2023-05-23 | 2024-05-28 | 山西大学 | 一种六核锌配位聚合物及其制备方法和应用 |
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