CN106947088B - 一种多孔三核镉金属有机骨架材料的制备方法与应用 - Google Patents
一种多孔三核镉金属有机骨架材料的制备方法与应用 Download PDFInfo
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Abstract
本发明提供了一种多孔三核镉金属有机骨架材料及其制备方法和应用，骨架材料分子式为：[Cd3(CPOTA)2(phen)3]n·5nH2O，其中H3CPOTA为2‑(4‑羧基苯氧基)对苯二甲酸，phen为邻菲罗啉。制备方法：将Cd(NO3)2·6H2O、phen、H3CPOTA、KOH置于聚四氟乙烯管中，加水搅拌，在反应釜中140℃反应72小时；通过程序降温冷却至室温，得到白色块状晶体，用水洗涤后，真空干燥。该材料晶体结构中包含镉三聚体结构单元，并且是具有直径约为7.4
一维孔道的三维金属有机骨架材料。该材料在水溶液中对重铬酸根离子具有很好的选择性响应，可作为化学传感器用于探测重铬酸根离子。
Description
技术领域
本发明涉及金属有机骨架材料，特别涉及一种基于过渡金属镉(II)，2-(4-羧基苯氧基)对苯二甲酸和邻菲罗啉构筑形成的具有孔道的金属有机骨架材料的制备，以及该材料在水溶液中作为一种重铬酸根离子荧光探针的应用。
背景技术
铬是一种银白色的坚硬金属。主要以金属铬、三价铬和六价铬三种形式出现。铬的化合物都有毒性，其中六价铬毒性最大。铬的工业用途很广，主要有金属加工、电镀、制革行业，这些行业排放的废水和废气是环境中的主要污染源。六价铬是很容易被人体吸收的，它可通过消化、呼吸道、皮肤及粘膜侵入人体。通过呼吸空气中含有不同浓度的铬酸酐时有不同程度的沙哑、鼻粘膜萎缩，严重时还可使鼻中膜穿孔和支气管扩张等。经消化道侵入时可引起呕吐、腹疼。经皮肤侵入时会产生皮炎和湿疹。危害最大的是长期或短期接触或吸入时有致癌危险。因此分析和检测人体内或环境中六价铬近年来备受关注。与普通的分析方法相比，荧光探针可以提供简单，快速，选择性准确和低成本的实时监测，所以设计合成对金属离子具有选择性识别功能的荧光探针是目前研究的一个重点。
发明内容
本发明的目的在于提供一种多孔三核镉金属有机骨架材料及其制备方法，以及该金属有机骨架材料在水溶液中作为一种铬离子荧光探针的应用。
本发明提供的一种多孔三核镉金属有机骨架材料，其分子式为：[Cd3(CPOTA)2(phen)3]n·5nH2O，其中H3CPOTA代表2-(4-羧基苯氧基)对苯二甲酸,phen为邻菲罗啉。结构式为：
该金属有机骨架材料的晶体属单斜晶系，空间群为C2/c，晶胞参数为：
α＝90°，β＝90.444(2)°，γ＝90°。该材料是由中心的镉原子通过桥连羧酸氧原子连接两个端位镉原子形成的三核镉配位环境。中心的Cd1分别与四个不同羧酸中的四个O原子，两个N原子配位；端位的Cd2分别与五个个不同羧酸中的O原子，两个N原子配位。Cd-O键长的范围为
Cd-N键长的范围为
Cd1-O-Cd2键角为111.402(4)°，Cd1与Cd2间的距离为
配体2-(4-羧基苯氧基)对苯二甲酸采用三种不同的配位模式，将镉离子连接形成具有一维孔道的金属有机骨架材料，该孔道由溶剂水分子占据，热重分析表明水分子占据孔道。X射线粉末衍射证实晶体样品均一稳定。
本发明提供的该金属有机骨架材料的制备方法，包括如下步骤：
(1)按摩尔比2:2:1:5将Cd(NO3)2·6H2O、邻菲罗啉和2-(4-羧基苯氧基)对苯二甲酸置于聚四氟乙烯管中，加水控制填充度在50％-70％并搅拌，缓慢滴加入KOH，继续搅拌30分钟；
(2)将此聚四氟乙烯管置于不锈钢反应釜中密封，在140℃下反应72h，然后每小时降温10℃直至室温，即可析出白色块状晶体，用蒸馏水洗涤后真空干燥，得到目的产物。该材料在330℃以下能稳定存在。
本发明的优点和效果：
本发明的镉金属有机骨架材料是在水热合成条件下得到，制取工艺简单，产率、纯度较高。热重分析表明结构在330℃以上发生分解，实用的温度范围在330℃以下。本发明提供的金属有机骨架材料是基于2-(4-羧基苯氧基)对苯二甲酸配体构筑的，2-(4-羧基苯氧基)对苯二甲酸配体是一种半刚性的配体，更易形成穿插性的结构，而邻菲罗啉也是一种端位阻断配体。两种不易形成多孔材料的配体与金属镉却形成了多孔三维结构，其中，四个μ2-COO-将Cd1与两个Cd2离子相连形成[Cd3(μ2-COO)4]2+三核次级结构单元。随后，每个[Cd3(μ2-COO)4]2+三核次级单元连接六个μ5-η1:η1:η2:η1:η1:η1完全去质子化的CPOTA3-配体，每个CPOTA3-配体连接三个Cd3簇，形成具有直径约为
一维孔道的三核镉金属有机骨架材料。该材料可以作为水相中重铬酸根离子的荧光探针。
附图说明
图1本发明镉的金属有机骨架材料的晶体结构图。
图2本发明镉的金属有机骨架材料的空间填充图(沿c轴方向)。
图3本发明镉的金属有机骨架材料在298K的X射线粉末衍射图。
图4本发明镉的金属有机骨架材料的热重分析图。
图5本发明金属有机骨架材料在水溶液中与各种阴离子溶液混合物的荧光光谱图。
图6本发明金属有机骨架材料水溶液中加入不同浓度重铬酸根离子的荧光图。
图7本发明金属有机骨架材料水溶液中加入不同浓度重铬酸根离子的荧光线性校准曲线。
具体实施方式
实施例1镉金属有机骨架材料的制备及表征
称取0.1mmol H3CPOTA,0.2mmol phen与0.2mmol Cd(NO3)2·6H2O加入含6mL H2O的13mL聚四氟乙烯管中，将1mL浓度为0.5mol/L KOH缓慢滴加到搅拌中的该混合物中，并继续搅拌30分钟。将此聚四氟乙烯管密封于不锈钢反应釜中，在140℃下加热72h后，每小时降温10℃至室温，即可析出无色块状晶体，用水洗涤后真空干燥，产率为69％。元素分析：理论值：C 50.56,H 3.06,N 5.36；实验值:C 50.64,H 3.51,N 5.13。
镉金属有机骨架材料晶体结构测定：
晶体结构测定采用X射线衍射，以Bruker Smart Apex II探测器通过石墨单色器单色化的Mo-Kα射线，扫描方式ω，收集数据的温度为293K。原始数据经SAINT还原后，使用SADABS进行吸收校正。晶体结构由SHELXL-2014直接法解得。最终结构省略无序的水分子贡献，无序水由元素分析与热重分析确定，每式量含5分子水。详细的晶体测定数据见表1；晶体结构见图1以及图2所示空洞。
表1镉金属有机骨架材料的晶体学数据
粉末衍射：
X-射线粉末衍射结果得到实验衍射图谱与模拟图谱一致，表明本发明的镉金属有机骨架材料晶体样品物相均一，见图3。
配合物的热重分析：
热重分析结果表明该聚合物在54.5℃-108.3℃之间逐渐失重约6.02％，说明在聚合物中存在配位水(理论值5.75％)，这一结果进一步佐证了该材料晶体结构中游离水分子的存在。另外从热重分析图4也可以看出，其主体结构在330℃以上发生分解，说明该发明的金属有机骨架材料适用于330℃以下温度，见图4。
实施例2本发明金属骨架材料在水中对重铬酸根离子的选择性识别。
首先，配制10mL浓度为5×10-3mol/L的不同阴离子溶液,(阴离子＝F-,Cl-,Br-,I-,SO4 2-,SCN-,CH3COO-,ClO4 -,CO3 2-,HPO4 2-,MoO4 2-and Cr2O7 2-)。将2毫克的该金属有机骨架材料分别加入到不同的阴离子溶液中，并用超声处理30分钟，并沉化三天，使其形成并入无机阴离子的金属有机骨架材料的悬浊液。取上层清液，在激发波长为300nm，狭缝宽度均为10nm的条件下，测其荧光发射光谱强度，如图5所示，该化合物对重铬酸根离子有独特的荧光选择性。
实施例3本发明金属骨架材料在水中识别重铬酸根离子的灵敏度。
于10mL水中加入2mg该探针材料，超声处理30分钟，沉化三天，使其形成金属有机骨架材料的悬浊液。取上层清液，逐渐滴加重铬酸根离子，从图6可以看出，在300nm激发波长下，金属有机骨架材料的悬浊液在365nm处显示非常强的荧光。如图6滴定曲线显示，随着体系中重铬酸根离子浓度的增加，该溶液的荧光显著降低。此外，如图7所示，在低浓度时，淬灭效应可以用Stern-Volmer方程来处理：I0/I＝1+Ksv×[M]，I0为金属有机骨架材料的悬浊液的荧光强度，I为向金属有机骨架材料的悬浊液加入重铬酸根离子后的荧光强度，[M]为重铬酸根离子的浓度，Ksv为猝灭常数。Ksv计算值为1.2×104M-1，这个Ksv值与很好的用于感测重铬酸根离子的有机化合物的值相当(典型值104M-1)。另外，该探针材料对重铬酸根离子检出限为8.31×10-7M。表明探针分子在水溶液中对重铬酸根离子具有较高灵敏的响应，该探针具有较大的应用前景。
Claims (3)
1.一种多孔三核镉金属有机骨架材料，其特征在于，结构式为：
2.如权利要求1所述的一种多孔三核镉金属有机骨架材料的制备方法，其特征在于，包括如下步骤：
(1)按摩尔比2:2:1:5将Cd(NO3)2·6H2O、邻菲罗啉和2-(4-羧基苯氧基)对苯二甲酸置于聚四氟乙烯管中，加水控制填充度在50％-70％并搅拌，缓慢滴加入KOH，继续搅拌30分钟；
(2)将此聚四氟乙烯管置于不锈钢反应釜中密封，在140℃下反应72h，然后每小时降温10℃直至室温，即可析出白色块状晶体，用蒸馏水洗涤后真空干燥，得到目的产物。
3.如权利要求1所述的多孔三核镉金属有机骨架材料作为重铬酸根离子荧光探针的应用。
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