CN105384947A - 一种Cd的3D配位聚合物及其制备方法和应用 - Google Patents
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Abstract
本发明涉及一种Cd的3D配位聚合物,其制备方法是:将Cd(NO3)2·4H2O,2,4′,5–联苯三羧酸,KOH和水加入容器中,于常温下,搅拌3h;将容器密封后放入烘箱中,于温度160℃下,保持3天;缓慢冷却到室温,得到白色块状晶体;洗涤、过滤并干燥,得目标产物。该Cd的3D配位聚合物,显示出很强的荧光性能,对Fe3+具有特异性识别功能,利用该配位聚合物作为催化剂,可以高效的降解水中的有机染料亚甲基蓝。
Description
技术领域
本发明涉及一种Cd的3D配位聚合物及其制备方法和应用,具体涉及一种由Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物,其对Fe3+具有特异性识别功能,利用该配位聚合物作为催化剂,可以高效的降解水中的有机染料亚甲基蓝。
背景技术
金属有机骨架(MOFs)配位聚合物在催化,气体吸附,分子识别,光学等领域已被广泛关注。以前的大多数关于配位聚合物的文献是集中在过渡金属与联苯二羧酸或是吡啶配体上,很少有报道由多元羧酸配体构成的多核配位聚合物。通过设计、选择有机配体和金属单元构建具有特殊结构和功能的金属有机骨架。配位聚合物独特的结构可能是由于通过不同的构建模块和反应条件调节金属与配体的配位方式。到目前为止,由Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物还没有被报道。
发明内容
本发明的目的是利用CdⅡ作为金属节点,利用2,4′,5-联苯三羧酸作为有机配体,在一定的温度下,利用水热的方法合成一种3D配位聚合物。
本发明采用的技术方案是:
一种Cd的3D配位聚合物,包括以下合成步骤:
1)将Cd(NO3)2·4H2O,2,4′,5–联苯三羧酸,KOH和水加入容器中,于常温下,搅拌2-3h;
2)将容器密封后放入烘箱中,于160℃下,保持3天;
3)缓慢冷却到室温,得到白色块状晶体;
4)洗涤、过滤并干燥,得目标产物。
所述的一种Cd的3D配位聚合物,步骤1)将0.2mmol的Cd(NO3)2·4H2O,0.1mmol的2,4′,5–联苯三羧酸,0.3mmol的KOH和10ml水加入容器中,于常温下,搅拌2h。
所述的一种Cd的3D配位聚合物,步骤3)所述的缓慢冷却到室温的降温速率为15-20℃·h-1。
所述的一种Cd的3D配位聚合物作为荧光探针在检测Fe3+中的应用。方法如下,将上述的Cd的3D配位聚合物配置成甲醇悬浊液,然后加入含有Fe3+的溶液,进行荧光检测。
所述的一种Cd的3D配位聚合物作为催化剂在降解有机染料中的应用。方法如下:于含有有机染料的N,N-二甲基甲酰胺溶液中加入Cd的3D配位聚合物,浸泡、吸附。所述的有机染料是亚甲基蓝。
本发明的有益效果是:
本发明选用2,4′,5-联苯三羧酸作为配体具有以下特点:(1)它具有三个羧酸基团提供不同的配位模式;(2)就去质子化的羧酸的数目来看,它不仅可以作为氢键的接受体,也可以作为氢键的提供者;(3)它可以在不同的方向连接金属离子。本发明所制备的Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物对Fe3+具有特异性识别功能。所制备的Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物可以高效的降解水中的有机染料亚甲基蓝。本发明的Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物制备方法简单,具有很大的应用前景。
附图说明
图1是本发明一种Cd的3D配位聚合物的合成示意图。
图2是本发明一种Cd的3D配位聚合物的结构图。
图3是本发明一种Cd的3D配位聚合物荧光光谱图。
图4是本发明一种Cd的3D配位聚合物的甲醇悬浊液在不同金属浓度下荧光强度图。
图5是本发明一种Cd的3D配位聚合物降解有机染料的紫外可见光谱图。
具体实施方式
实施例1一种Cd的3D配位聚合物
将0.2mmol的Cd(NO3)2·4H2O,0.1mmol的2,4′,5–联苯三羧酸,0.3mmol的KOH和10ml水加入体积为25ml的高压反应釜中,并且常温条件搅拌2小时。将高压反应釜密封好放入烘箱中。加热使烘箱的温度达到160℃,并保持温度在此条件下保温72小时。以15℃·h-1的降温速率缓慢冷却到室温,得到白色块状晶体;洗涤、过滤并干燥,即为目标产物Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物,产率为58%。
本发明合成的Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物的结构如图2所示,该晶体结构属于P-1空间群。分子式为:Cd3(L)2(H2O)4。如图所示,该化合物中有两种不同的Cd原子配位模式。Cd1是七配位模式,六个氧原子来自2,4′,5–联苯三羧酸配体,一个氧原子来自配位水;Cd2是六配位模式,四个氧原子来自2,4′,5–联苯三羧酸配体,两个氧原子来自配位水,2个七配位的Cd1和1个六配位的Cd2形成了一个三核簇。该化合物是由Cd-羧酸链构建的3D配位聚合物。
实施例2Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物的发光
方法:以实施例1制备的Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物的发光性能。
1)以波长为361nm光为激发光,测得晶体的荧光发射光谱的发射峰为421nm。结果如图3所示,图3是Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物的固体荧光发射光谱图。
2)取Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物的晶体于甲醇溶剂中,得到Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物的晶体与甲醇溶剂的浓度为1×10-4M的混合溶液。
分别取混合溶液5ml,依次加入25ul的1×10-4M的Cd2+,Cu2+,Hg2+,Mg2+,Na+,Ni2+,Pb2+,Zn2+,Ag+,Co2+,Cr3+,Al3+,Fe3+的甲醇溶液。用荧光光度计检测混合溶液中Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物的晶体的荧光强度的变化。
由图3可见,图谱中出现了Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物为特征发射波长的发射光谱。说明本发明的Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物在常温下有很强的固体荧光性能。由图4可见,Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物的晶体在甲醇溶剂中荧光最强,而遇Fe3+荧光淬灭。这说明本发明的一种由Cd(Ⅱ)和2,4′,5-联苯三羧酸构筑的3D配位聚合物的晶体可作为荧光探针检测Fe3+。
实施例3Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物降解有机染料
方法:以实施例1制备的Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物对有机染料进行降解。
取有机染料亚甲基蓝溶于DMF溶液中,得到亚甲基蓝的浓度都为10ppm的染料溶液。
取染料溶液50ml,加入Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物晶体10mg,于室温下浸泡。用紫外可见光谱检测混合染料溶液中染料浓度的变化。结果如图5所示,图中峰值从上到下依次为0min,10min,20min,30min,40min,50min,60min,70min,80min,90min,100min,110min,120min和130min。由图5可见,有机染料溶液亚甲基蓝在650nm的特征峰强度逐渐减小。这说明本发明的Cd(Ⅱ)和2,4′,5–联苯三羧酸构筑的3D配位聚合物的晶体结构对亚甲基蓝具有很好的降解作用。
Claims (8)
1.一种Cd的3D配位聚合物,其特征在于,包括以下合成步骤:
1)将Cd(NO3)2·4H2O,2,4′,5–联苯三羧酸,KOH和水加入容器中,于常温下,搅拌2-3h;
2)将容器密封后放入烘箱中,于160℃下,保持3天;
3)缓慢冷却到室温,得到白色块状晶体;
4)洗涤、过滤并干燥,得目标产物。
2.根据权利要求1所述的一种Cd的3D配位聚合物,其特征在于,步骤1)将0.2mmol的Cd(NO3)2·4H2O,0.1mmol的2,4′,5–联苯三羧酸,0.3mmol的KOH和10ml水加入容器中,于常温下,搅拌2h。
3.根据权利要求1所述的一种Cd的3D配位聚合物,其特征在于,步骤3)所述的缓慢冷却到室温的降温速率为15-20℃·h-1。
4.根据权利要求1所述的一种Cd的3D配位聚合物作为荧光探针在检测Fe3+中的应用。
5.根据权利要求4所述的应用,其特征在于,方法如下,将权利要求1所述的Cd的3D配位聚合物配置成甲醇悬浊液,然后加入含有Fe3+的溶液,进行荧光检测。
6.根据权利要求1所述的一种Cd的3D配位聚合物作为催化剂在降解有机染料中的应用。
7.根据权利要求6所述的应用,其特征在于,方法如下:于含有有机染料的N,N-二甲基甲酰胺溶液中加入Cd的3D配位聚合物,浸泡、吸附。
8.根据权利要求7所述的应用,其特征在于:所述的有机染料是亚甲基蓝。
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CN106967219A (zh) * | 2017-03-23 | 2017-07-21 | 山西师范大学 | 基于3,3′,5,5′‑联苯四羧酸的镉金属有机框架材料及其制备方法和应用 |
CN106967219B (zh) * | 2017-03-23 | 2020-05-22 | 山西师范大学 | 基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料及其制备方法和应用 |
CN108912341A (zh) * | 2018-07-23 | 2018-11-30 | 重庆师范大学 | 主-客体型铅配位聚合物、制备方法及其在阳离子检测中的应用 |
CN108912341B (zh) * | 2018-07-23 | 2020-11-27 | 重庆师范大学 | 主-客体型铅配位聚合物、制备方法及其在阳离子检测中的应用 |
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