CN108126757A - 一种银修饰磷钨氧簇催化剂的制备方法及用途 - Google Patents
一种银修饰磷钨氧簇催化剂的制备方法及用途 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 20
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 3
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Abstract
本发明公开了银修饰磷钨氧簇催化剂的制备方法，该种方法将硝酸银、有机配体4,6‑二(吡啶‑2‑基)嘧啶‑2‑胺、磷钨酸、二甲基亚砜置于烧杯中反应，反应完毕后，过滤、滤液缓慢挥发，得到银修饰磷钨氧簇催化剂的晶体。本发明方法具有反应速度快、反应过程简单，得到的产品纯度高，后处理简单等特点。并且在催化苯乙炔、甲醛与六氢吡啶一锅法反应中，转化率高达99%，选择性高达100%。
Description
技术领域
本发明属于催化剂材料制备技术领域，其中涉及到银修饰磷钨氧簇催化剂的制备方法及用途。
背景技术
无机-有机杂化材料最近成为科学家们研究的热点领域，尤其是金属-氧簇合物与有机配体结合得到的杂化材料，它们不仅具有多样的结构，而且在很多领域都具有潜在的应用前景，例如催化、储氢、分子吸附、磁性和光化学等领域。多金属氧簇（Polyoxometalates，简写为POMs）由于其卓越的催化性能以及其化学稳定性，包括氧化稳定性、热稳定性和水解稳定性等使其成为一个众所周知的无机构筑快。作为POMs的一个重要分支，磷钨酸盐由于结构的多样性成为构筑基于POMs杂化材料的非常重要的选项。而过渡金属杂化的磷钨酸盐由于过渡金属单元和磷钨氧簇之间的协同作用使得这类材料在很多性质和功能的改良方面有很好的应用前景。POMs是一种环境友好并且经济可行的固体催化剂。同时过渡金属银具有独特的物理及化学性质，但是很多银化合物因其的稳定性、活性较低、易分解、无法重复利用等在催化方面受到限制。因此将过渡金属银结合有机配体引入到POMs中，因其兼具过渡金属离子特有的d轨道和d电子的授受性质和开放式的一维链状、二维或三维多孔结构，可望获得具有较高活性和选择性的催化材料。
Mannich反应在有机合成及工业生产中占有十分重要的地位, Schiff base它不仅在药物、农药、染料、调料、涂料、炸药等方面有着广泛的用途, 而且是有机化学中合成天然生物活性分子的重要中间体。传统的催化剂是在质子酸或者路易斯酸的催化下进行的，催化效率差、有毒、价格昂贵、对环境污染严重等问题，因此寻找一种经济、高效、反应条件温和、对环境友好且易于回收利用的催化剂仍然是目前十分重要的课题.尤其是在设计合成结构新颖、催化效能更好且能广泛应用于Mannich 反应的有机催化剂将成为今后的发展趋势.
通过检索，尚未未发现与本发明申请相关的公开专利文献。
发明内容
本项发明的目的是解决单纯的多金属氧簇催化剂在Mannich反应过程中催化活性有待提高的问题。提供一种合成银修饰磷钨氧簇催化剂的制备方法，以期在苯乙炔、甲醛与六氢吡啶合成中起到催化的作用。
这类催化剂的晶体结构信息通过如下方法获得的：
通过常规的溶液反应合成得到银修饰磷钨氧簇的晶体，具体的描述实验方法如下：
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺、 二甲基亚砜，在室温下电磁搅拌15~30 min，加入硝酸银，电磁搅拌15~30分钟，然后加入H3PW12O40反应3~5h，反应完毕后，过滤，滤液在室温下缓慢蒸发，一周左右得到块状单晶。产率约25~45%。
优选的方案，4,6-二(吡啶-2-基)嘧啶-2-胺：硝酸银：磷钨酸的物质的量之比为1~3：1~3：1~3。
优选的方案，所用溶剂为二甲基亚砜，所述4,6-二(吡啶-2-基)嘧啶-2-胺与二甲基亚砜的质量体积比（g/ml）为0.0025~0.005。
产品通过单晶X衍射图1，粉末X射线衍射图2进行表征，以及晶体学数据表1中可以得到关于晶体结构的准确信息。具体的结果如下：
晶体的分子式为[Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO, 其中阳离子部分为Ag+阳离子，阴离子为POM多阴离子，二者通过弱电作用相互结合在一起。在晶体结构图1中，其中Ag1，Ag4空间占有率各占0.5， Ag2，Ag3空间占有率为1，所以在化合物1中一共有三个Ag+，一个PW12O40 3-阴离子。
通过结构分析我们发现此催化剂含有两个活性中心，一个是过渡金属位点，一个是POMs位点，二者对于Mannich反应都有贡献，我们期望能够起到协同催化的作用。
从图2可以看出，合成的样品与测试的样品谱图能够较好地符合，说明合成的样品纯度较高，从而可以直接用来催化Mannich反应。
表1. 化合物1的晶体学数据
从晶体学数据表1可以得出结论，此化合物分子式为C40H58Ag3N10O4PS6W12；和化合物1的结构式正好相符，此化合物的晶体结晶属于三斜晶系，空间群为P-1，分子量为4168.10。
这项发明主要是合成了一个银修饰磷钨氧簇催化剂，已经将其应用于一锅法合成Mannich反应。这项发明涉及了银修饰磷钨氧簇催化剂的制备方法。这类催化剂可以较温和的反应条件下实现催化取代苯乙炔、甲醛与六氢吡啶反应，转化率高达99%，选择性高达100%。该类催化剂的制备方法反应过程简单。
本发明的目的是通过如下技术方案实现的：
化合物1分子式为：[Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO
上述取代炔烃为苯乙炔、对甲基苯乙炔、对乙基苯乙炔、对丙基基苯乙炔等，溶剂选用乙腈等，转化率，选择性通过气相色谱检测。
本发明提供银修饰磷钨氧簇催化剂具有以下特点：
1.制备方法简单、并且催化剂都具有明确的分子结构，利于研究反应机理；
2.催化剂具有过渡金属、多金属氧簇活性中心，能对Mannich反应起协同催化作用。
催化剂便于容易分离，经处理后可以多次使用，并且仍能保持良好的催化活性，有利于工业化生产。
附图说明
图1. 化合物1 [Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO的晶体结构（DMSO, 为二甲基亚砜，为了结构清晰，氢原子省去）；
图2. 化合物1 [Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO的RXRD表征，上面灰线为合成的样品，下面黑线为模拟的样品。
具体实施方式
实施例1：化合物[Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.2mmol)、10mL 二甲基亚砜，在室温下搅拌30 min，加入硝酸银（0.1mmol），电磁搅拌30分钟，然后加入H3PW12O40 (0.1mmol）反应3h，反应完毕后，冷却至室温，过滤，滤液在室温下缓慢蒸发，一周左右得到块状单晶。产率约26%。
实施例2：化合物[Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.2mmol)、15mL 二甲基亚砜，在室温下搅拌30 min，加入硝酸银（0.2mmol），电磁搅拌15分钟，然后加入H3PW12O40 (0.1mmol）反应3h，反应完毕后，过滤，滤液在室温下缓慢蒸发，一周左右得到块状单晶。产率约35%。
实施例3：化合物[Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.2mmol)、10mL 二甲基亚砜，在室温下搅拌30 min，加入硝酸银（0.2mmol），电磁搅拌20分钟，然后加入H3PW12O40 (0.1mmol）反应4h，反应完毕后，过滤，滤液在室温下缓慢蒸发，一周左右得到块状单晶。产率约45%。
实施例4：化合物[Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.2mmol)、20mL 二甲基亚砜，在室温下搅拌30 min，加入硝酸银（0.2mmol），电磁搅拌20分钟，然后加入H3PW12O40 (0.3mmol）反应5h，反应完毕后，过滤，滤液在室温下缓慢蒸发，一周左右得到块状单晶。产率约32%。
实施例5：化合物[Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.2mmol)、30mL 二甲基亚砜，在室温下搅拌20 min，加入硝酸银（0.3mmol），电磁搅拌30分钟，然后加入H3PW12O40 (0.2mmol）反应5h，反应完毕后，过滤，滤液在室温下缓慢蒸发，一周左右得到块状单晶。产率约31%。
试验例1：催化取代苯乙炔、甲醛与六氢吡啶反应
取取代苯乙炔（0.25~0.5mmol）、六氢吡啶（0.7 ~1.0mmol）、甲醛水溶液（1.4~2.0mmol），加入乙腈溶剂（2~5ml），并加入催化剂（10~20 mg）,保持室温搅拌，反应8~12h后，用气相色谱检测，具体化数据见表2：
表2. 化合物1对取代苯乙炔、甲醛、六氢吡啶催化的结果列表
通过表2可以看出：此催化剂能够较好地催化取代苯乙炔的Mannich 反应，苯乙炔无论是否带有取代基，催化效果良好，转化率高达99%。
Claims (5)
1.一种银修饰磷钨氧簇催化剂的制备方法，其特征在于：其合成步骤为：
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺、二甲基亚砜，在室温下电磁搅拌15~30 min，加入硝酸银，电磁搅拌15~30分钟，然后加入H3PW12O40反应3~5h，反应完毕后，过滤，滤液在室温下缓慢蒸发，一周左右得到块状单晶。
2.根据权利要求1所述的银修饰磷钨氧簇催化剂的制备方法，其特征在于：银修饰磷钨氧簇催化剂1的分子式：[Ag3(C14H11N5)2(DMSO)4][PW12O40]·2DMSO。
3.根据权利要求1所述的银修饰磷钨氧簇催化剂的制备方法，其特征在于：4,6-二(吡啶-2-基)嘧啶-2-胺：硝酸银：磷钨酸的物质的量之比为1~3：1~3：1~3。
4.根据权利要求1所述的银修饰磷钨氧簇催化剂的制备方法，其特征在于：所用溶剂为二甲基亚砜，所述4,6-二(吡啶-2-基)嘧啶-2-胺与二甲基亚砜的质量体积比（g/ml）为0.0025~0.005。
5.一种银修饰磷钨氧簇催化剂可直接用来催化Mannich反应。
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