CN113801146B - 一种锌(ii)配合物单晶及其制备方法和应用 - Google Patents

一种锌(ii)配合物单晶及其制备方法和应用 Download PDF

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CN113801146B
CN113801146B CN202111190463.5A CN202111190463A CN113801146B CN 113801146 B CN113801146 B CN 113801146B CN 202111190463 A CN202111190463 A CN 202111190463A CN 113801146 B CN113801146 B CN 113801146B
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余彩霞
刘雷雷
李雪菁
王柯忠
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Abstract

本发明涉及配位化学和吸附去除水中污染物领域，具体涉及一种锌配合物单晶及其制备方法和应用。其化学式为：[Zn(BDC)L]·1.5H2O，其中H2BDC为5‑甲基‑1,3‑苯二甲酸）,L为(4‑吡啶基)亚甲基3‑(2‑(4‑((4‑吡啶基)甲氧基)苯基)二氮烯基)苯甲酸酯）；属于单斜晶系，空间群为P21/n,a=7.3767(15)Å,b=30.795(6)Å,c=18.080(4)Å,α=90°,β=97.38(3)°,γ=90°,V=4073.1(15)Å3。该锌配合物单晶在常温下能够较快地吸附去除水中碘单质，能够在120分钟以内，吸附去除94.4%的碘单质，300分钟内达到吸附平衡，去除率高达99.5%。且能实现较高的吸附容量，吸附容量可达到275.85mg/g。本发明合成工艺简单，收率较高。具有很好的应用前景。

Description

一种锌(II)配合物单晶及其制备方法和应用
技术领域
本发明涉及配位化学和吸附去除水中污染物领域，具体涉及一种锌配合物单晶及其制备方法和应用。
背景技术
碘是一种人类必须的微量元素，能够促进生长发育、调节水盐平衡。但是单质碘在常温下能升华、蒸发而放出碘蒸气，吸入碘蒸气或服碘剂会造成碘中毒。碘的腐蚀性强，会刺激皮肤和粘膜，过量致死。由于碘的高挥发性和对人体代谢的直接影响，必须通过有效手段对其进行捕获和可靠储存。目前活性炭、沸石分子筛等固体无机吸附剂虽然成功地应用于碘单质的捕获，但是仍存在难于功能化修饰、有限的表面积等因素，导致较低的吸附容量和吸附效率。
金属-有机框架(MOFs)是由有机配体和金属离子或团簇通过配位键自组装形成的具有分子内孔隙的有机-无机杂化材料。因其多孔性及较大的比表面积、结构与功能多样性等优异特性，被用于捕获碘单质，并显示出优异的吸附能力。纵观文献，我们发现具有富电子的官能团和多芳环的吸附剂，能够与碘单质发生静电作用，进而有效捕捉碘单质。因此，我们通过有目的的将富电子官能团(酯基、醚、偶氮基)载入到MOFs的孔道中，从而获得更多的活性吸附位点用于吸附去除碘单质是目前研究方向。
发明内容
针对目前技术现状，本发明目的在于提供一种具有更多活性吸附位点的锌配合物单晶；另一目的在于提供其制备方法和应用。
为实现上述发明目的，所述技术方案如下：
所述锌配合物单晶，化学式为：[Zn(BDC)L]·1.5H2O，其中H2BDC＝5-methyl-1,3-benzenedicarboxylic acid(5-甲基-1,3-苯二甲酸),L＝(pyridin-4-yl)methyl 3-(2-(4-((pyridin-4-yl)methoxy)phenyl)diazenyl)benzoate((4-吡啶基)亚甲基3-(2-(4-((4-吡啶基)甲氧基)苯基)二氮烯基)苯甲酸酯)；属于单斜晶系，空间群为P21/n,
Figure BDA0003300752900000011
α＝90°,β＝97.38(3)°,γ＝90°,
Figure BDA0003300752900000012
本发明所述锌配合物单晶的制备方法：
将六水合硝酸锌与H2BDC、(4-吡啶基)亚甲基3-(2-(4-((4-吡啶基)甲氧基)苯基)二氮烯基)苯甲酸酯溶于N,N'-二甲基甲酰胺和蒸馏水中，封入反应瓶中，室温下超声，在恒温的烘箱中放置，然后降至室温，得到橙色块状晶体，得到目标产物，即为Zn(II)单晶吸附剂。
该配合物可以作为吸附剂应用于吸附去除水中碘单质。
本发明优点在于：该Zn(II)配合物单晶不仅能够在水中稳定存在，并且在它的三维框架结构的孔道内修饰有酯基、醚、偶氮基等官能团和多个芳香环，有利于与碘单质作用，进而快速吸附去除水中碘单质，实现较高的吸附容量，吸附容量可达到275.85mg/g。另外，本发明制备的锌配合物单晶在常温下能够较快地吸附去除碘单质，比如碘单质起始浓度为130ppm，锌配合物单晶能够在120分钟以内，吸附去除94.4％的碘单质，300分钟内达到吸附平衡，去除率高达99.5％。而且，本发明合成工艺简单，收率较高。具有很好的应用前景。
附图说明
图1为本发明锌配合物晶体中锌的配位环境图。
图2为本发明锌配合物的单晶结构图。
图3为本发明锌配合物的实验粉末衍射图谱、模拟粉末衍射图谱；1为单晶模拟粉末衍射图谱，2为本发明锌配合物的粉末衍射图谱。
图4为本发明锌配合物吸附水中不同浓度碘的吸附等温线图。
图5为本发明锌配合物吸附水中碘单质(130ppm)的动力学图。
图6为本发明锌配合物吸附水中碘单质(130ppm)的紫外图。
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Zn(II)单晶吸附剂
将六水合硝酸锌(0.1780g,0.6mmol)与H2BDC(0.0540g,0.3mmol)、(4-吡啶基)亚甲基3-(2-(4-((4-吡啶基)甲氧基)苯基)二氮烯基)苯甲酸酯(0.1271g,0.3mmol)溶于N,N'-二甲基甲酰胺(15mL)和蒸馏水(75mL)中，封入耐高温蓝口丝瓶中，室温下超声3-5分钟，然后在100℃恒温的烘箱中放置24小时，以5℃/h的速率缓慢降至室温，得到橙色块状晶体，得到目标产物，该无色块状晶体的分子式为：[Zn(BDC)L]·1.5H2O，即为Zn(II)配合物吸附剂。
实施例2：锌配合物吸附碘单质试验
在80mL浓度为0-1200ppm的碘的水溶液(0、125、···1000、1200ppm)中分别加入15mg由实施例1制得的橙色块状晶体研磨1小时后的粉末作为吸附剂，在室温下搅拌300分钟。达到吸附平衡后，用紫外分光光度计对其进行吸光度检测。试验显示：本发明锌配合物单晶的吸附容量达到275.85mg/g，见图4。
在80mL浓度为130ppm的碘的水溶液中加入15mg由实施例1制得的橙色块状晶体研磨1h后的粉末作为吸附剂，在室温下搅拌300分钟。在不同的时间取样，用紫外分光光度计检测碘单质浓度。试验显示在120分钟内94.4％的碘单质被吸附去除，见图5和图6，证明本发明的新型锌配合物单晶具有较快的吸附速度。
在显微镜下选取合适大小的单晶在室温下进行X–射线衍射实验。在Bruker SmartApex-II CCD衍射仪上，用经石墨单色器单色化的Mo–Kα射线
Figure BDA0003300752900000032
Figure BDA0003300752900000033
以
Figure BDA0003300752900000034
方式收集衍射数据。用Bruker SAINT程序进行数据还原。部分结构的衍射数据用SADABS程序进行吸收校正。晶体结构由直接法结合差值Fourier合成解出。全部非氢原子坐标及各向异性参数进行全矩阵最小二乘法修正，C–H原子位置按理论模式计算确定。配合物中金属锌的配位环境见图1；配合物的晶体结构见图2；详细的晶体测定数据见表1。
表1本发明配合物的主要晶体学数据
Figure BDA0003300752900000031
Figure BDA0003300752900000041

Claims (3)

1.一种锌配合物晶体，其特征在于，化学式为：[Zn(BDC)L]·1.5H2O，其中BDC代表5-甲基-1,3-苯二甲酸失去两个氢原子后的羧基，L＝(4-吡啶基)亚甲基3-(2-(4-((4-吡啶基)甲氧基)苯基)二氮烯基)苯甲酸酯；属于单斜晶系，空间群为P21/n, a = 7.3767(15) Å, b= 30.795(6) Å, c = 18.080(4) Å, α= 90°, β = 97.38(3)°, γ = 90°, V = 4073.1(15) Å3。
2.如权利要求1所述的锌配合物晶体，其特征在于，具有附图2所示的单晶结构。
3.如权利要求1或2所述的锌配合物晶体的应用，其特征在于，作为吸附剂应用于吸附去除水中碘单质。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9139599B1 (en) * 2012-06-06 2015-09-22 University Of South Florida 2-periodic metal-organic frameworks (MOFs) as supermolecular building layers (SBLs) for making targeted 3-periodic MOFs
CN111363162A (zh) * 2020-05-12 2020-07-03 烟台大学 一种锌配合物单晶及其制备方法和吸附水中铅离子应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9139599B1 (en) * 2012-06-06 2015-09-22 University Of South Florida 2-periodic metal-organic frameworks (MOFs) as supermolecular building layers (SBLs) for making targeted 3-periodic MOFs
CN111363162A (zh) * 2020-05-12 2020-07-03 烟台大学 一种锌配合物单晶及其制备方法和吸附水中铅离子应用

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Highly efficient and selective removal of anionic dyes from aqueous solution by using a protonated metal-organic framework;Cai-Xia Yu et al.;《Journal of Alloys and Compounds》;20200928;15783 *

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