CN105924459B - 一种钕配合物及其制备方法和应用 - Google Patents
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Abstract
本发明涉及一种钕配合物及其制备方法，结构简式为：[Nd(D‑DTTA)3(CH3O)3]n，其中D‑H2DTTA为(+)‑2,3‑二乙酰对甲苯‑D‑酒石酸，CH3OH为甲醇。制备方法：将D‑H2DTTA的甲醇溶液和NdCl3·3H2O水溶液混合，加入一定量的KOH水溶液调pH至3.0～4.5，搅拌，静置，直到有淡紫色三棱柱状晶体充分析出，过滤，收集产品，产率为40％。该配合物结构中包含九配位的钕离子，配体分别为D‑DTTA2‑和CH3O‑阴离子。在室温、日光照射下该配合物对亚甲基蓝染料具有很好的催化降解效果，可以用作降解亚甲基蓝染料的催化剂。
Description
技术领域
本发明涉及金属配合物，具体涉及一种一维链状钕配合物，特别是一种基于钕(III)离子和(+)-2,3-二乙酰对甲苯-D-酒石酸钕配合物的制备，以及该钕配合物在降解亚甲基蓝染料中的应用。
背景技术
我国是全球染料业第一大国，印染废水已成为我国工业废水主要来源之一。印染废水中含有大量以芳环为母体的有机组分，它们的处理和降解已成为当前环境工作的重点与难点之一。以亚甲基蓝为例，亚甲基蓝(MB)是一种硫氮杂苯染料，广泛应用于化学指示剂、染料、生物染色剂和药物等方面，不易被降解，是印染废水的典型代表，容易引起一系列环境问题。目前，国内外处理印染废水的主要方法包括物理法、化学法、物理化学法、生物化学法等。其中，光催化降解法是近几十年发展起来的处理污水的新方法。光催化降解法能有效降解多种有机污染物并将其矿化为CO2、H2O或毒性更小的有机物，是一种节能、高效、污染物降解彻底的处理方法。常用的光催化降解催化剂包括金属氧化物、硫化物、配合物和分子筛等，其中金属配合物类光催化剂由于本身易形成超分子聚集体，易于过滤，而且其多孔、多层、网状等特殊的结构使其具有较大比表面积，使催化活性的点位有所增加，并使反应中产物或底物具有较快的扩散速度，可有效提高其再生和回收效率，因此研究这类光催化剂的分子结构和光催化活性之间的规律，可以为设计和合成具有高效催化活性的催化剂提供理论借鉴和实际帮助。
发明内容
本发明的目的是提供一种钕配合物及其制备方法，以及该钕配合物在降解亚甲基蓝染料中的应用。
本发明提供的一种钕配合物，结构简式为：[Nd(D-DTTA)3(CH3O)3]n，其中D-H2DTTA为(+)-2,3-二乙酰对甲苯-D-酒石酸，CH3OH为甲醇。其化学结构式为：
该配合物的晶体属于三方晶系，空间群为R3，晶胞参数： α＝β＝90°，γ＝120°。该配合物中钕离子采用九配位模式，与Nd(III)配位的氧原子分别来自六个DTTA2-中的羧基氧原子(O4,O4B,O4D,O5A,O5C,O5E)和三个配位甲醇分子中的氧原子(O9,O9B,O9D)，通过配体两端羧基桥连Nd(III)离子在c方向形成无限的一维链状结构。Nd-O键长的范围为X射线粉末衍射证实晶体样品均一稳定。在室温条件、日光照射下该配合物对亚甲基蓝染料具有很好的降解效果，可以用作降解亚甲基蓝染料的催化剂。
本发明提供的一种钕配合物的制备方法，包括如下步骤：
((1)将摩尔比为1:1～1.5的NdCl3·3H2O和(+)-2,3-二乙酰对甲苯-D-酒石酸分别溶解于水和甲醇中，将二者混合；
(2)室温下搅拌均匀，并加入适量KOH水溶液，调节pH至3.0～4.5，常温搅拌7-10小时，过滤，将滤液于室温条件下静置，直到有淡紫色三棱柱状单晶充分析出，过滤，收集产品。
优选调节pH为3.5，优选NdCl3·3H2O和(+)-2,3-二乙酰对甲苯-D-酒石酸的摩尔比为1:1.5时晶体质量最好，产率最高。
只有溶剂为甲醇和水时才能得到该配合物的晶体。
本发明的优点和效果：
本发明提供的钕配合物是基于(+)-2,3-二乙酰对甲苯-D-酒石酸配体构成的一种新配合物，使用常规化学合成方法，制备方法工艺简单，样品稳定性好，纯度高，成本低，推广应用前景良好。在常温、日光照射条件下可快速催化降解亚甲基蓝染料，40分钟降解率可达78％；120分钟降解率可达85％。
附图说明
图1实施例1制备的钕配合物的不对称结构单元及钕离子配位的单晶结构图。
图2实施例1制备的钕配合物在298K的X射线粉末衍射图(实验及模拟图)。
图3本发明配合物存在下，在室温条件日光照射下亚甲基蓝溶液的紫外吸收光谱。
图4室温条件日光照射下，本发明配合物对亚甲基蓝的催化降解以及不加配合物的对比试验。
具体实施方式
下面结合附图和实例对本发明作进一步说明。
实施例1.将D-H2DTTA(0.1mmol,0.0386g)溶于2.5mL甲醇中，然后加入2.5mLNdCl3·3H2O(0.066mmol,0.0165g)的水溶液，常温搅拌10分钟，再向其中缓慢加入KOH溶液(0.2mol/L,150μL)，常温搅拌7小时，过滤后将得到的澄清溶液置于室温下，2天后有淡紫色三棱柱状单晶析出，过滤收集，产率约为40％。
钕配合物的结构测定：
晶体结构测定采用北京同步辐射1W2B工作线站光源为入射辐射，MAR165CCD探测器，marccd和HKL2000程序收集并还原数据，经过最小二乘法修正得到晶胞参数，从差值Fourier电子密度图利用SHELXL-97直接法解得晶体结构，并经Lorentz和极化效应修正。C原子采用理论加氢。详细的晶体测定数据见表1。结构见图1。
表1配合物的晶体学数据
实施例2：本发明配合物在室温、日光照射条件下对亚甲基蓝染料的催化降解。
室温条件下，将15ml 0.03mmol/L的亚甲基蓝溶液在黑暗处机械搅拌10分钟，测其吸光度，再将2.0mg本发明配合物分散到亚甲基蓝溶液中得到悬浊液。将悬浊液置于普通日光下照射，并不停进行搅拌，每20分钟取1次样品，测试其吸收曲线。如图3所示，120分钟后配合物对亚甲基蓝的催化降解达到85％。相比之下，在同样的条件下，如果体系中不使用配合物，则120分钟后，亚甲基蓝基本不降解，如图4所示。结果表明，本发明配合物对亚甲基蓝染料的降解具有很好的催化效果。
Claims (6)
1.一种钕配合物，其特征在于，结构简式为：[Nd(D-DTTA)3(CH3O)3]n，其中D-H2DTTA为(+)-2,3-二乙酰对甲苯-D-酒石酸，CH3OH为甲醇，其化学结构式为：
其中配体由(+)-2,3-二乙酰对甲苯-D-酒石酸和甲醇形成；
该配合物的晶体属于三方晶系，空间群为R3，晶胞参数： α＝β＝90°，γ＝120°。
2.如权利要求1所述的一种钕配合物的制备方法，其特征在于，包括如下步骤：
(1)将摩尔比为1:1～1.5的NdCl3·3H2O和(+)-2,3-二乙酰对甲苯-D-酒石酸分别溶解于水和甲醇中，将二者混合；
(2)室温下搅拌均匀，并加入适量KOH水溶液，调节pH至3.0～4.5，常温搅拌7～10小时，过滤，将滤液于室温条件下静置，直到有淡紫色三棱柱状单晶充分析出，过滤，收集产品。
3.如权利要求2所述的一种钕配合物的制备方法，其特征在于，所述NdCl3·3H2O和(+)-2,3-二乙酰对甲苯-D-酒石酸的摩尔比为1:1.5。
4.如权利要求2所述的一种钕配合物的制备方法，其特征在于，所述常温搅拌7小时。
5.如权利要求2所述的一种钕配合物的制备方法，其特征在于，所述调节pH至3.5。
6.如权利要求1所述的一种钕配合物在降解亚甲基蓝染料中的应用。
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| CN109485606B (zh) * | 2018-10-19 | 2021-10-19 | 江苏理工学院 | 纳米管结构的吡唑啉酮锌配合物及其制备方法和应用 |
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| CN101921187A (zh) * | 2009-06-15 | 2010-12-22 | 浙江师范大学 | 溶剂热合成l-酒石酸稀土配合物的方法 |
| CN103949261A (zh) * | 2014-04-10 | 2014-07-30 | 西安工程大学 | 稀土钕掺杂纳米三氧化二铁改性空心玻璃微珠的制备方法 |
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| CN101921285A (zh) * | 2009-06-15 | 2010-12-22 | 浙江师范大学 | 溶剂热合成d-酒石酸稀土配合物的方法 |
| CN101921187A (zh) * | 2009-06-15 | 2010-12-22 | 浙江师范大学 | 溶剂热合成l-酒石酸稀土配合物的方法 |
| CN103949261A (zh) * | 2014-04-10 | 2014-07-30 | 西安工程大学 | 稀土钕掺杂纳米三氧化二铁改性空心玻璃微珠的制备方法 |
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| D-H2DBTA稀土配合物的合成及荧光性能研究;韩忠华;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20131215;B014-117 * |
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