CN107008478A - 一种磁性纳米催化剂的制备方法 - Google Patents
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Abstract
本发明提供一种催化活性高，并可回收利用的Pd负载多酸复合磁性纳米催化剂的制备方法，该催化剂是由具有磁性的颗粒包覆介孔TiO2包覆并氨基化后作为载体，采用电化学法还原杂多酸后负载于磁性载体上，利用还原性多酸原位还原并沉积贵金属钯纳米粒子得到的复合型催化剂。本发明制备方法简单，催化还原反应活性高，可以直接通过磁体吸引分离，多次循环利用，有效的解决了多酸催化剂的固载、分离回收及重复利用的技术难题。
Description
技术领域
本发明涉及一种贵金属钯纳米粒子沉积于磁性核壳催化剂的制备方法，尤其涉及贵金属钯纳米粒子是采用还原性多酸制备的。
背景技术
贵金属纳米粒子由于其特殊的化学活性和纳米性能，显示出与大块固体不同的化学、光学、电学、催化和磁学性能，尤其在催化剂的开发领域贵金属纳米粒子及其复合材料受到了广泛的关注。但是贵金属资源有限，贵金属纳米粒子合成条件比较苛刻，以及贵金属纳米粒子作为催化剂实用难以回收利用而造成的催化剂损耗也比较大。
杂多酸是一类具有独特催化性能的多金属含氧酸盐簇合物，然而大多数多酸都易于溶剂，因此常作为均相催化剂应用于催化反应的研究。例如在光催化分解水制氢气和氧气，光催化有机染料降解，催化氧化醇类和汽油脱硫及酸催化酯化反应体系中，多酸作为催化剂都显示除了很好地催化性能，但是催化剂回收利用问题仍是一个难题。多酸可以同时做还原剂、稳定剂和催化剂。近些年，多金属氧酸离子在合成贵金属纳米粒子引起了广泛的兴趣，并成为一个热点研究领域。因为多金属氧酸粒子具有可逆的氧化还原性，利用还原性的多酸还原贵金属纳米粒子前驱体的方法合成贵金属纳米离子的方法，在常温常压下的水溶液中进行不仅合成过程绿色环保，而且合成方法简单实用。
磁性Fe3O4纳米颗粒因具有强磁性，可以利用外磁场快速分离。同时对其表面可以包覆一层其他的材料制备成磁性核壳结构的材料，既可以降低磁性颗粒间的相互团聚，又能赋予磁性颗粒另一种功能材料。以磁性核壳材料作为催化剂载体，负载具有催化活性的贵金属及多酸制备成磁性易回收的非均相催化剂。
发明内容
本发明的目的是提供一种催化活性高，并可回收利用的Pd负载多酸复合磁性纳米催化剂的制备方法。
本发明的实现过程如下：
一种磁性纳米催化剂的制备方法，包括以下步骤：
（1）制备介孔二氧化钛包覆的球型四氧化三铁Fe3O4@mTiO2；
（2）采用电化学法将磷钼酸还原成具有还原性的磷钼酸r-H3PMo12O40；
（3）采用浸渍法将还原性的磷钼酸负载于磁性Fe3O4@mTiO2载体上，得到Fe3O4@mTiO2@r-PMo12；
（4）将Fe3O4@mTiO2@r-PMo12浸渍于氯化钯溶液中，利用磷钼酸还原性将Pd2+还原，原位沉积Pd纳米粒子得到Fe3O4@mTiO2@ PMo12/Pd0催化剂。
上述步骤（1）中，所述Fe3O4@mTiO2中，Fe3O4直径为200-250nm球型颗粒，包覆厚度为10-50nm介孔二氧化钛。
上述步骤（2）中，磷钼酸H3PMo12O40浓度为5.00-15.0mmol/L的水溶液。
上述步骤（2）中，所用电化学还原法采用三电极电解槽，电流为2-8mA，电压为2-8V，电解时间为4-8 h。
上述步骤（3）中，负载时 Fe3O4@mTiO2的质量浓度为0.50-1.50g/L，负载时间为6-12h。
上述步骤（4）中，PdCl2浓度为1.0-5.0 mmol/L 水溶液。
上述制备方法制备得到的磁性纳米催化剂在催化降解水中的硝基苯酚中的应用。
本发明的优点与积极效果：本发明利用杂多酸多酸水溶液作为还原剂，常温下还原氯化钯制备贵金属钯纳米粒子，制备条件温和； 贵金属钯纳米粒子沉积于磁性核壳载体上得到复合型催化剂，能够有效解决多酸和贵金属纳米粒子的回收困难的问题；同时各个组分间的协同效应可以提高原材料的催化性能。
附图说明
图1 是Pd纳米粒子原位沉积于多酸负载的磁性纳米核壳催化剂的制备流程图；
图2 是Pd纳米粒子原位沉积于多酸负载的磁性纳米核壳催化剂的红外光谱图；
图3 是Pd纳米粒子原位沉积于多酸负载的磁性纳米核壳催化剂的X射线衍射图；
图4 是Pd纳米粒子原位沉积于多酸负载的磁性纳米核壳催化剂的扫描电镜图；
图5 是Pd纳米粒子原位沉积于多酸负载的磁性纳米核壳催化剂的X-射线能谱图；
图6 是Pd纳米粒子原位沉积于多酸负载的磁性纳米核壳催化剂的催化活性图；
图7 是Pd纳米粒子原位沉积于多酸负载的磁性纳米核壳催化剂的循环使用效果图。
具体实施方式
下面通过实施例详细叙述本发明，但并不对本发明做任何形式限定。
如图1所示，本发明所述磁性纳米催化剂的制备，首先将磷钼酸(H3PMo12O40)采用电化学法还原成r-H3PMo12O40，并负载于磁性Fe3O4@mTiO2载体上，然后利用还原性多酸还原氯化钯并原位沉积贵金属钯纳米粒子于磁性核壳载体上，最后将催化剂应用于催化降解4-硝基苯酚的反应体系中研究催化活性和回收利用性能。
实施例1 介孔TiO2包覆磁性Fe3O4微粒的合成
参考文献[J. Mater. Chem. A, 2015, 3, 6492–6500]制备Fe3O4磁性微粒：氯化铁(2.70 g)，聚乙二醇(3.00g)和无水乙酸钠(7.2 0g)溶解于乙二醇(80 mL)中，加热搅拌至均相后转移至聚四氟乙烯内衬的不锈钢高压釜(100mL)，于200°C下保持8 h。结束后磁铁收集产物。
Fe3O4@mTiO2磁性核壳制备：Fe3O4（0.15g）分散于乙醇（90ml）中，加入氨水（0.4ml）调节至碱性，加入钛酸四丁酯的乙醇溶液（0.75g溶于10ml），45℃下搅拌24h后，磁铁分离并分散于水中（50ml），于20℃回流水下恒温超声4h，磁铁分离乙醇洗涤并室温干燥。于N2条件下，600℃处理2h。用磁铁将得到的磁性纳米颗粒分离。再将固体分散于APTES的甲苯溶液（1mL溶于50mL）氨基化得到Fe3O4@mTiO2。
实施例2磷钼酸的电化学还原
将磷钼酸H3PMo12O40配置成10mM溶液，在电解槽中通入直流电源，在(5V，10mA)条件下电解6h，多酸溶液逐渐变成蓝色并密封保存，记为r-H3PMo12O40。
实施例3还原多酸负载于磁性载体
取0.1g Fe3O4@mTiO2加入100ml r-H3PMo12O40，室温下搅拌12h，用磁铁将得到的磁性纳米颗粒分离并洗涤干燥。如图2所示，曲线 (d)上出现了磷钼酸的特征峰，表明多酸成功负载。
实施例4 Pd纳米粒子原位沉积于多酸负载的磁性纳米核壳
将PdCl2配置成浓度为1.0 mmol/L的溶液，将0.10g的Fe3O4@mTiO2@r-PMo12加入100mlPdCl2溶液中，手摇震荡还原反应数分钟。如图3所示，出现了钯单质纳米粒子的特征峰，表明氯化钯被还原成了单质形式的钯纳米粒子沉积于载体。如图4所示，扫描电镜图片显示催化剂为250nm左右球型，表面有钯纳米颗粒沉积于球形磁性颗粒上。如图5所示，X-射线能谱显示了Fe3O4@mTiO2@ PMo12/Pd0催化剂所有组分的元素。
实施例5 催化剂催化硼氢化钠还原降解对硝基苯酚
石英试管中加入0.0020 mg的催化剂，加入3 mL浓度为0.01 mM的4-硝基苯酚4-NP溶液，超声数秒使催化剂分散，然后加入3 mL浓度为0.0250 M 的NaBH4溶液作为还原剂开始计时，手动摇动使反应进行，每隔30秒取样，用磁铁分离催化剂，取上清液测定UV-Vis吸收光谱。并用最大吸收波长处的吸光度A测定浓度变化，并以此来评价催化剂的催化活性。如图6所示，结果表明随着反应时间的进行，4-硝基苯酚逐渐被还原降解，当反应进行到3分钟硝基苯酚降解完全，催化活性很好，反应结束后，用磁铁可快速将催化剂收集在反应器底部。
将上述实例中的催化剂用磁铁富集在石英管壁，重新加入3mL浓度为0.01 mM的4-硝基苯酚4-NP溶液，超声数秒使催化剂分散，然后加入3mL浓度为0.0250M 的NaBH4溶液作为还原剂开始计时，3分钟后用磁铁分离催化剂，取上清液测定UV-Vis吸收光谱。并用最大吸收波长处的吸光度A测定浓度变化，并以此来评价催化剂的催化回收利用性能。并反复进行此操作。如图7所示，结果表明催化剂可以连续的被重复使用9次仍可以保持很高的催化活性，降解4-硝基苯酚效果基本保持不变。此催化剂活性高，易回收且循环利用能力很好。
Claims (7)
1.一种磁性纳米催化剂的制备方法，其特征在于包括以下步骤：
（1）制备介孔二氧化钛包覆的球型四氧化三铁Fe3O4@mTiO2；
（2）采用电化学法将磷钼酸还原成具有还原性的磷钼酸r-H3PMo12O40；
（3）采用浸渍法将还原性的磷钼酸负载于磁性Fe3O4@mTiO2载体上，得到Fe3O4@mTiO2@r-PMo12；
（4）将Fe3O4@mTiO2@r-PMo12浸渍于氯化钯溶液中，利用磷钼酸还原性将Pd2+还原，原位沉积Pd纳米粒子得到Fe3O4@mTiO2@ PMo12/Pd0催化剂。
2.根据权利要求1所述催化剂的制备方法，其特征在于：步骤（1）中，所述Fe3O4@mTiO2中，Fe3O4直径为200-250nm球型颗粒，包覆厚度为10-50nm介孔二氧化钛。
3.根据权利要求1所述催化剂的制备方法，其特征在于：步骤（2）中，磷钼酸H3PMo12O40浓度为5.00-15.0mmol/L的水溶液。
4.根据权利要求1所述催化剂的制备方法，其特征在于：步骤（2）中，所用电化学还原法采用三电极电解槽，电流为2-8mA，电压为2-8V，电解时间为4-8 h。
5.根据权利要求1所述催化剂的制备方法，其特征在于：步骤（3）中，负载时 Fe3O4@mTiO2的质量浓度为0.50-1.50g/L，负载时间为6-12h。
6.根据权利要求1所述催化剂的制备方法，其特征在于：步骤（4）中，PdCl2浓度为1.0-5.0 mmol/L 水溶液。
7.权利要求1所述制备方法制备得到的磁性纳米催化剂在催化降解水中的硝基苯酚中的应用。
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