CN111848654A - 具有催化光降解甲基橙染料性质的锌配合物及其制备方法 - Google Patents
具有催化光降解甲基橙染料性质的锌配合物及其制备方法 Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 36
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- 239000011701 zinc Substances 0.000 title claims abstract description 36
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 title claims abstract description 22
- 229940012189 methyl orange Drugs 0.000 title claims abstract description 22
- 239000001048 orange dye Substances 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000001782 photodegradation Methods 0.000 title description 7
- RWHRIIMYBNGFEV-UHFFFAOYSA-N 2-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=CC=C1C(O)=O RWHRIIMYBNGFEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- DRJQEQQHTVMVJN-UHFFFAOYSA-N 1-[[4-[4-(imidazol-1-ylmethyl)phenyl]phenyl]methyl]imidazole Chemical group C1=CN=CN1CC(C=C1)=CC=C1C(C=C1)=CC=C1CN1C=CN=C1 DRJQEQQHTVMVJN-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 229940111759 benzophenone-2 Drugs 0.000 claims abstract description 3
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 claims abstract description 3
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- -1 zinc nitrate hexahydrate 4, 4 '-bis (imidazol-1-ylmethyl) biphenyl benzophenone-2, 4' -dicarboxylic acid Chemical compound 0.000 claims description 2
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 2
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Abstract
本发明提供一种具有光催化降解甲基橙染料性质的锌配合物及其制备方法。所述配合物的分子式为[Zn(BPDC)(BIMBP)0.5]n，其中，BIMBP＝4，4′‑双(咪唑‑1‑基甲基)联苯，H2BPDC＝二苯甲酮‑2，4′‑二羧酸。所述配合物中每个锌原子与来自于四个二苯甲酮‑2，4′‑二羧酸的氧原子、一个4，4′‑双(咪唑‑1‑基甲基)联苯的氮原子配位，形成无限二维层状结构。实验结果表明：该锌配合物具有良好的催化光降解去除水中甲基橙有机染料性质，70分钟内甲基橙基本降解完全，降解率为92.8％，在环境污染治理领域具有潜在的应用价值。该配合物合成工艺简单，反应条件温和，使用方便，为环境中有害物质的治理提供了一种新的手段，同时也为多孔材料在环境工程中的应用提供了新的思路。
Description
技术领域
本发明属于有机合成和金属有机化学技术领域，具体涉及到以4，4′-双(咪唑-1-基甲基) 联苯和二苯甲酮-2，4′-二羧酸为配体的锌配合物的制备及其在光催化降解方面的应用。
背景技术
能源短缺和环境污染是进入新世纪人类面临的关键问题，而开发新能源，如风能、太阳能、核能等是应对这一问题的主要途径。光催化是一项利用太阳能来解决目前全球能源短缺和环境危机的重要手段。近年来为了进一步提升光催化活性，不同结构类型的类半导体光催化剂被开发出来，特别是多孔材料，在光催化领域呈现出迷人的前景。光催化剂的多孔结构允许暴露尽可能多的反应活性位点，并通过减少扩散阻力促进反应底物与活性位点的接触；更重要的是，多孔结构丰富的内表面使得光生电子和空穴的传输距离大大缩短，一定程度上避免了光催化过程中的体相复合，从而提高光生电子和空穴的分离和利用效率，大大改善光催化性能。
工业的快速发展带来了日趋严峻的生态环境问题，人类的生存环境不断遭到破坏，水污染问题日趋严重。目前，我国水体污染的主要来源是工业废水，其中印染废水占工业废水的比重已超过35％。印染废水具有废水量大、色度高、毒性大、水质复杂等特点，属于高浓度难降解有机废水。甲基橙(MO)等偶氮型染料在水体中的危害极大，不但严重危害河流、海洋的生态平衡，而且还会通过皮肤吸收进入人体内，导致头痛、呕吐，甚至照成多种器官不可逆的伤害乃至致癌。因此，高效处理水体中偶氮型染料污染物是一个重要课题。
由金属离子或金属簇合物与有机配体自组装形成的配合物是一类较新颖的多孔晶态固体材料，具有高孔隙率、高比表面积、结构可剪裁性、易功能化、多活性位点等优点，在催化光降解染料领域展现出重要的应用前景。一系列的具有光降解染料性质配合物已被报道，但是基于二苯甲酮-2，4′-二羧酸配体可光降解甲基橙性质的配合物报道比较少。
二苯甲酮-2，4′-二羧酸是配位能力较强的桥连配体：在这个配体的两端具有两个羧酸基，有利于配合物的合成；它可以部分或完全去质子化，允许与金属离子有不同的配位模型，易合成具有不同维数的金属配合物，而合成不同维数的结构是完成器件化至关重要的一步。
本发明属于有机合成和金属有机化学技术领域，涉及具有二维锌配合物的合成，更具体的说是4，4′-双(咪唑-1-基甲基)联苯和二苯甲酮-2，4′-二羧酸为配体的锌配合物的合成及其催化光降解甲基橙染料方面的应用。本文分别采用二价锌离子作为主体，以4，4′-双(咪唑-1- 基甲基)联苯和二苯甲酮-2，4′-二羧酸作为配体，探究该配合物催化光降解去除水中甲基橙有机染料的性质。
本发明锌配合物在常温下具有稳定和高效的的催化光降解染料性质，尤其是针对甲基橙染料，70分钟内甲基橙基本降解完全，降解率为92.8％，而且易于分离并多次循环使用，催化效率基本保持不变。此外，在本发明中，该锌配合物具有制备方法简单、成本低、重现性好等优点。
发明内容
本发明旨在提供一种用作降解有机染料的二维锌配合物及其制备方法。本发明选用4，4′- 双(咪唑-1-基甲基)联苯，二苯甲酮-2，4′-二羧酸为配体和六水合硝酸锌构筑锌配合物。该化合物对甲基橙染料有很好的降解效果，可高速高效的降解水中的甲基橙。该化合物合成工艺简单、成本低、效率高、重现性好、易于分离、收益高，可应用于工业化生产，在印染废水水处理领域具有潜在的应用前景。
本发明所涉及的用作降解甲基橙的锌配合物的化学式为：[Zn(BPDC)(BIMBP)0.5]n，其中， BIMBP＝4，4′-双(咪唑-1-基甲基)联苯，H2BPDC＝二苯甲酮-2，4′-二羧酸。4，4′-双(咪唑-1- 基甲基)联苯和二苯甲酮-2，4′-二羧酸结构如下：
本发明所涉及的一种具有光催化降解质的锌配合物结构如图1(a)所示，它的基本结构参数为：本发明的锌配合物的晶体属于三斜晶系，空间群为P-1，晶胞参数为
α＝97.381(5)°，β＝96.181(5)°，γ＝104.139(5)°；所述配合物中每个锌原子与来自于四个二苯甲酮-2，4′-二羧酸的氧原子、一个4，4′-双(咪唑-1-基甲基) 联苯的氮原子配位，形成无限二维层状结构(如图1(b))。
本发明所涉及的锌配合物的制备方法包括下述步骤：
(1)制备方法：4，4′-双(咪唑-1-基甲基)联苯∶二苯甲酮-2，4′-二羧酸∶六水合硝酸锌＝1∶1∶1，加入H2O(3mL)，后转移到4mL的高硼硅玻璃管中，超声振荡30min后使其形成悬浊液，随即置于白色聚四氟乙烯内衬的密封水热反应釜中，使用程序控温精确控制反应条件；
(2)将上述混合液在150℃下烘制72小时，取出产物后将固体分离；
(3)用H2O将上述固体洗涤三次，得到白色块状晶体。
进一步地，本发明提供上述锌配合物用作催化光降解去除水中甲基橙方面的应用，用于治理自然水体中的甲基橙类偶氮型染料废水。
本发明的优点是：该制备方法工艺简单，重现性好，可以得到单一晶型、高纯度的晶体材料，易工业化生产；该产品能够快速有效的降解水体中的甲基橙并且多次循环使用的催化效率基本保持不变，该方法具有高效、操作简便和去除效果好等优点。
附图说明
图1(a)本发明锌配合物的晶体结构图；图1(b)本发明锌配合物的二维结构图。
图2本发明锌配合物的固体荧光图。
图3本发明锌配合物光催化10mg/L甲基橙的吸光度变化图。
具体实施方式
为了更好的理解本发明，下面结合实施实例进一步阐述本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1配合物的合成：
将4，4′-双(咪唑-1-基甲基)联苯(15.7mg，0.05mmol)，二苯甲酮-2，4’-二羧酸(11.0mg， 0.05mmol)、六水合硝酸锌(14.9mg，0.05mmol)、水(3mL)，加入到4mL的高硼硅玻璃管中，超声振荡30min后使其形成悬浊液，随即置于白色聚四氟乙烯内衬的密封水热反应釜中，后升温至150℃，溶剂热条件下恒温72h，然后降温至室温得到白色块状晶体。用去离子水清洗2次，在室温下晾干，得到白色块状晶体。
实施例2配合物的结构表征：
用显微镜选取合适大小的单晶，室温下采用Siemens(Bruker)SMART CCD衍射仪(石墨单色器，Mo-Ka，
)收集衍射数据。衍射数据使用SADABS程序进行吸收校正。数据还原和结构解析分别使用SAINT和SHELXTL程序完成。最小二乘法确定全部非氢原子坐标，并用理论加氢法得到氢原子位置。采用最小二乘法对晶体结构进行精修。如图 1(a)和图1(b)的展示了基本配位情况和堆积方式。其晶体学衍射点数据收集与结构精修的部分参数如下表所示。
表1配合物的晶体学数据
R1＝∑||Fo|-|Fc||/∑|Fo|.ωR2＝∑[w(Fo 2-Fc 2)2]/∑[w(Fo 2)2]1/2
实施例3：配合物的固体荧光性质测试：
在室温下测试本发明的锌配合物的固体荧光，使用电子天平准确称量5.0mg的样品，置于固体荧光模具中间，测试得到本发明的锌配合物荧光最大发射峰388nm(激发波长为243 nm)(图2)。
实施例4：配合物的光降解性质测试：
对本发明的锌配合物进行光催化性质研究，在光催化反应器中加入30mg的本发明的锌配合物，50mL浓度为10mg/L的甲基橙。打开紫外光源，10min取样一次，用紫外分光光度计测试其吸光度。测试结果为在70min内，本发明的锌配合物可以使甲基橙降解92.8％(图3)。
Claims (3)
1.一种具有光催化降解甲基橙染料性质的锌配合物，其特征在于，其化学式为[Zn(BPDC)(BIMBP)0.5]n，其中，BIMBP＝4，4′-双(咪唑-1-基甲基)联苯，H2BPDC＝二苯甲酮-2，4′-二羧酸；所述的锌配合物的晶体属于三斜晶系，空间群为P-1，晶胞参数为
α＝97.381(5)°，β＝96.181(5)°，γ＝104.139(5)°；所述配合物中每个锌原子与来自于四个二苯甲酮-2，4′-二羧酸的氧原子、一个4，4′-双(咪唑-1-基甲基)联苯的氮原子配位，形成无限二维层状结构。
2.如权利要求1所述的锌配合物的制备方法，其特征在于，所述的原料采用的摩尔比为：六水合硝酸锌∶4，4′-双(咪唑-1-基甲基)联苯∶二苯甲酮-2，4′-二羧酸＝1∶1∶1。
3.根据权利要求2所述的制备方法，其特征在于，其中：六水合硝酸锌∶4，4′-双(咪唑-1-基甲基)联苯∶二苯甲酮-2，4′-二羧酸的摩尔比为1∶1∶1，每0.05mmol的六水合硝酸锌对应3mL去离子水，温度为150℃，反应时间为三天。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113698615A (zh) * | 2021-07-20 | 2021-11-26 | 吉林师范大学 | 一种零价银掺杂的银基配位聚合物及其制备方法和应用 |
| CN114672228A (zh) * | 2022-03-23 | 2022-06-28 | 山东沃丰新材料有限公司 | 一种环保型彩钢板及制备方法 |
| CN115353637A (zh) * | 2022-08-23 | 2022-11-18 | 常州大学 | 一种高效吸附甲基橙的材料及其制备方法 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698615A (zh) * | 2021-07-20 | 2021-11-26 | 吉林师范大学 | 一种零价银掺杂的银基配位聚合物及其制备方法和应用 |
| CN114672228A (zh) * | 2022-03-23 | 2022-06-28 | 山东沃丰新材料有限公司 | 一种环保型彩钢板及制备方法 |
| CN114672228B (zh) * | 2022-03-23 | 2023-02-28 | 山东沃丰新材料有限公司 | 一种环保型彩钢板及制备方法 |
| CN115353637A (zh) * | 2022-08-23 | 2022-11-18 | 常州大学 | 一种高效吸附甲基橙的材料及其制备方法 |
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