CN108479769B - 一种制备Pd纳米粒子的方法 - Google Patents
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Abstract
本发明提供了一种制备Pd纳米粒子的方法，属于有机合成技术领域。其包括如下步骤：以廉价的苯胺为起始原料，配制苯胺与四氟硼酸的乙醇溶液，冰浴条件下向该溶液中滴加亚硝酸叔丁酯，得到苯基重氮四氟硼酸盐；将苯基重氮四氟硼酸盐与醋酸Pd混合成均匀的溶液，室温下搅拌反应，冰浴条件下再滴加硼氢化钠的甲醇溶液，反应后得到Pd纳米粒子。本发明以苯胺做起始底物，操作简便、安全，成本低廉，并且得到的Pd纳米粒子具有反应活性高、不易失活的特点。
Description
技术领域
本发明涉及一种制备Pd纳米粒子的方法及其应用，属于有机合成技术领域。
背景技术
过渡金属Pd(钯)具有优异的催化性能，作为催化剂，被广泛地应用于催化氧化、还原和偶联等反应中。尽管Pd是过渡金属催化剂中较常用的一种，但是不同Pd催化剂的催化过程不尽相同，对于底物的适应性也有较大差别。并且，传统的均相催化剂不利于回收和重复使用，不但浪费资源，也容易污染环境，因此，对于可重复利用的Pd催化剂的研究十分必要。传统的提高Pd催化效率的方法是改变配体和Pd的化合态，然而近年来的研究表明制成Pd纳米粒子同样是提高Pd催化性能的一个非常有效的途径，这是因为纳米粒子的比表面积大，表面活化中心多，使得分子接触发生碰撞的机率增加，并且纳米粒子具有便于活化和重复使用的优点。
Pd纳米粒子很早就有相关研究，特别是在催化加氢领域中，Pd纳米粒子表现出优异的催化性能，并具有催化过程简单，不涉及配体制备等问题，同时又具有易于回收重复使用的优点。随着不同类型Pd纳米粒子研究的发展，其制备的方法也较为多样。因此，研发一种操作简便、只需使用简单易得的反应底物就能实现高催化性能的Pd纳米粒子的合成方法，仍然具有十分重要的意义。
发明内容
本发明的目的在于提供一种操作简便、简单易得的Pd纳米粒子合成新方法，并探究该Pd纳米粒子的催化应用。
为实现本发明目的，本发明以廉价的苯胺为起始原料，通过以下技术方案实现：
所述制备Pd纳米粒子的方法包括如下步骤：
(1)将苯胺与四氟硼酸溶于乙醇溶液中，混合均匀，冰浴条件下向该溶液中滴加亚硝酸叔丁酯，室温下搅拌反应，过滤得到苯基重氮四氟硼酸盐；苯胺、四氟硼酸与亚硝酸叔丁酯的摩尔比优选1:2.5:2.5。
(2)将苯基重氮四氟硼酸盐用四氢呋喃溶解，醋酸钯用甲醇溶解，混合成均匀的溶液，室温下搅拌反应，冰浴条件下再滴加硼氢化钠的甲醇溶液，滴加完室温下反应至反应充分；苯基重氮四氟硼酸盐、醋酸钯与硼氢化钠的摩尔比优选4:1:5。
(3)将反应液旋干、洗涤、干燥后得到Pd纳米粒子。
探究该Pd纳米粒子的催化应用，利用Pd纳米粒子对硝基的还原加氢，具体实施如下：
本发明优点：以廉价的苯胺为起始原料，制备过程安全高效、操作简便。而且本发明制备的Pd纳米粒子反应活性高、不易失活，催化性能优异，催化过程高效简单、催化剂用量低。在催化还原加氢反应中，可以在常温常压下进行，且用水作溶剂，环保清洁无污染，符合当前化工发展的方向。
附图说明
图1是本发明制备的Pd纳米粒子的TEM照片，由图可知，本发明合成的Pd为纳米级。
具体实施方式
下面结合具体的实施例对本发明作进一步详细的说明。
实施例1：
Pd纳米粒子的制备方法
(1)向10ml反应瓶中先加入2ml乙醇溶剂，再加入5mmol苯胺、12.5mmol四氟硼酸混合均匀，冰浴条件下向该混合溶液中滴加12.5mmol亚硝酸叔丁酯，恢复室温，反应0.5h，往反应液加少量乙醚，有白色沉淀生成，过滤、干燥得到苯基重氮四氟硼酸盐0.92g(4.8mmol)，收率为96％；
(2)向250ml反应瓶中加入4mmol苯基重氮四氟硼酸盐(用50ml四氢呋喃溶解)，再加入1mmol醋酸Pd(用50ml甲醇溶解)，室温下搅拌10min～15min，反应液成桔红色，冰浴条件下再滴加5mmol硼氢化钠(50ml甲醇溶解)溶液，滴加完室温下反应1h至反应充分；将反应液旋干、洗涤、干燥后得到Pd纳米粒子。
实施例2：
Pd纳米粒子对硝基苯的催化加氢
向25ml反应瓶中加入2mmol硝基苯，10ml水做溶剂，2.4mg本发明制备的Pd纳米粒子，常温常压下通入H2，反应12h后，TLC检测反应完全，反应液用二氯甲烷萃取，有机相用无水Na2SO4干燥，减压蒸去溶剂，经过柱层析纯化得到相应的目标化合物苯胺0.18g(1.94mmol)，收率为97％。分析数据：1H NMR(400MHz,CDCl3)δ＝7.11(t,J＝8.0Hz,2H),6.72(t,J＝8.0Hz,21H),6.59(d,J＝8.0Hz,2H),3.53(s,br,2H)；GC-MS,m/z,93[M+]。
实施例3：
Pd纳米粒子对氯硝基苯的催化加氢
向25ml反应瓶中加入2mmol对氯硝基苯，10ml水做溶剂，3mg本发明制备的Pd纳米粒子，常温常压下通入H2，反应12h后，TLC检测反应完全，反应液用二氯甲烷萃取，有机相用无水Na2SO4干燥，减压蒸去溶剂，经过柱层析纯化得到相应的目标化合物对氯苯胺0.25g(1.96mmol)，收率为98％。分析数据为:1H NMR(400MHz,CDCl3)δ＝7.07(d,J＝8.0Hz,2H),6.54(d,J＝8.0Hz,2H),3.62(s,2H)；GC-MS,m/z,127[M+]。
实施例4:
Pd纳米粒子循环催化活性的验证试验
以对氯硝基苯为催化底物，第一次取8mg Pd纳米粒子，每次取5mmol对氯硝基苯，平行做六次Pd纳米粒子循环催化反应，每次用的Pd纳米粒子为上次回收的Pd纳米粒子。
因此，本发明制备的Pd纳米粒子重复利用性好能，重复使用6次后，产品收率仍可达94％。
Claims (1)
1.一种制备Pd纳米粒子的方法，其特征在于，包括如下步骤：
（1）将苯胺与四氟硼酸溶于乙醇溶液中，混合均匀，冰浴条件下向该溶液中滴加亚硝酸叔丁酯，室温下搅拌反应，过滤得到苯基重氮四氟硼酸盐；
（2）将苯基重氮四氟硼酸盐用四氢呋喃溶解，醋酸钯用甲醇溶解，混合成均匀的溶液，室温下搅拌反应，冰浴条件下再滴加硼氢化钠的甲醇溶液，滴加完室温下反应至反应充分；
（3）将反应液旋干、洗涤、干燥后得到Pd纳米粒子；
所述苯胺、四氟硼酸与亚硝酸叔丁酯的摩尔比为1:2.5:2.5；
所述苯基重氮四氟硼酸盐、醋酸钯与硼氢化钠的摩尔比为4:1:5。
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