CN112808314A - 一种具有磁性核壳层结构的光催化剂材料的制备方法及其用途 - Google Patents
一种具有磁性核壳层结构的光催化剂材料的制备方法及其用途 Download PDFInfo
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Abstract
本发明公开了一种具有磁性核壳层结构的光催化剂材料的制备方法及其用途。本发明以磁性Fe3O4@SiO2复合纳米粒子、有机配体1,10‑邻菲罗啉‑2,9‑二羧酸钾、钯盐为原料，通过溶液中自组装反应，制备了具有磁性核壳层结构的光催化剂材料，该材料作为有机偶联反应催化剂催化效率高，结构稳定，能够多次循环使用。本发明制备过程安全易操作，生产效率高、设备投资少，适合批量生产。
Description
技术领域
本发明属于无机纳米材料制备技术领域，具体涉及一种具有磁性核壳层结构的光催化剂材料的制备方法及其用途。
背景技术
铃木反应，也称作Suzuki-Miyaura偶联反应，是一种有机偶联反应，在钯配合物催化下，芳基或烯基硼酸或硼酸酯与卤代代芳烃或烯烃发生交叉偶联。该反应由铃木章在1979年首先报道，在有机合成中的用途很广，具有较强的底物适应性及官能团容忍性，常用于合成多烯烃、苯乙烯和联苯的衍生物，从而广泛应用于众多天然产物、药物、有机材料的合成中，是一种重要的有机合成反应。目前，有机偶联反应多是采用加热使用钯作为催化剂完成的，但其具有催化剂回收利用效率低，污染严重，能源消耗大等不足。
发明内容
本发明所要解决的技术问题是针对现有技术，提供一种制备工艺简单、反应条件温和、无需耗能加热、产率高的具有磁性核壳层结构的光催化剂材料的制备方法。
本发明为解决上述技术问题所采取的技术方案为：一种具有磁性核壳层结构的光催化剂材料的制备方法，所述制备方法以所制备的磁性Fe3O4@SiO2复合纳米粒子、有机配体1,10-邻菲罗啉-2,9-二羧酸钾(phenCOOK)、钯盐为原料，通过自组装反应，得到一种具有磁性核壳层结构的光催化剂材料，具体包括以下步骤：
1)将一定质量的磁性Fe3O4@SiO2复合纳米粒子悬浮于一定体积无水甲醇或乙醇溶剂中，超声分散，添加有机配体1,10-邻菲罗啉-2,9-二羧酸钾(phenCOOK)，然后混合物在氮气氛围下回流适当时间，冷却至室温，离心分离沉淀，用无水甲醇或乙醇洗涤三次后，真空干燥，得到含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子。
2)将一定质量的含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子分散到一定体积的无水甲醇或乙醇中，然后缓慢滴加适量的钯盐溶液，混合物在氮气氛围下回流适当时间，冷却至室温，离心分离沉淀，洗涤，真空干燥，得到含有Pd-phenCOO的磁性Fe3O4@SiO2复合纳米粒子，简写为Fe3O4@SiO2@Pd-phenCOO，即为所述的一种具有磁性核壳层结构的光催化剂材料。
所述phenCOO为失去钾离子的有机配体1,10-邻菲罗啉-2,9-二羧酸钾的简称；
所述钯盐为醋酸钯、二氯化钯或硝酸钯；
反应的溶剂、合成原料均为化学纯。
进一步地，步骤1)和步骤2)的回流时间各自独立选自6～12小时。例如，6小时、8小时、12小时等。
进一步地，所述含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子和所述钯盐的质量比为10:1～5:1。
进一步的，本发明还提供了所述具有磁性核壳层结构的光催化剂材料的用途，该材料作为催化剂，在模拟太阳光的条件下能够高效催化铃木偶联反应。
与现有技术相比，本发明的特点是：
(1)本发明所制备的具有磁性核壳层结构的光催化剂材料的形貌为微球体，微球体的直径为100～200nm；
(2)本发明所制备的具有磁性核壳层结构的光催化剂材料中，含有Pd与有机配体1,10-邻菲罗啉-2,9-二羧酸特定的强的氢键和螯合键作用；
(3)本发明所制备的具有磁性核壳层结构的光催化剂材料作为催化剂，具有高的可见光吸收性能和高的光生载流子效率，能够在模拟太阳光的条件下，高效催化铃木偶联反应，且催化剂能够多次循环重复使用多次。具有减少污染，节约能源等优势，具有重要的社会和经济效益。
附图说明
图1是本发明实施例1所制备的材料的XRD图。
图2是本发明实施例1所制备的材料的SEM图。
具体实施方式
太阳能是廉价的取之不竭的绿色能源，是光化学和光热反应的重要能量来源。过渡金属光催化体系能够吸收太阳能，其作为有机合成反应催化剂能够有效利用太阳能。在光催化技术中，过渡金属化合物的光吸收能力和光激发寿命长短是光物理性能的两个重要指标。因此，席夫碱或一些含有共轭π基元的过渡金属配位化合物能够高效吸收太阳能，其在光催化反应领域具有潜在的应用。将一些具有高效吸收太阳能的过渡金属配位化合物作为催化剂应用于铃木反应，是节约能源实现绿色合成重要途径之一。
基于此，本发明提供一种具有磁性核壳层结构的光催化剂材料的制备方法。该制备方法得到的光催化剂材料能够应用于铃木反应。
以下结合实施例对本发明作进一步详细描述，本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。
磁性Fe3O4@SiO2复合纳米粒子的制备：
将10mmol的FeCl3·6H2O和5mmol的FeCl2·4H2O置于100mL的圆底烧瓶中，加60mL的蒸馏水，搅拌溶解；加热到75℃，边搅拌边滴加氨水至溶液的pH值为8～9，恒温30min，然后，添加0.1g柠檬酸，溶液温度升到85℃，继续搅拌30min，离心分离沉淀，沉淀用蒸馏水洗涤三次后用乙醇洗涤两次，然后50℃恒温干燥，得到磁性Fe3O4纳米粒子；
将环己烷、Triton X-100和正己醇按体积比4:1:1的比例混合，配成微乳液；
取上述微乳液120mL与上述磁性Fe3O4纳米粒子200mg混合，搅拌分散均匀，加2mL氨水，搅拌混合均匀，然后滴加正硅酸乙酯100mL，滴加完毕后继续搅拌3h，得到棕黄色乳液，离心沉淀分离，固体用蒸馏水和无水乙醇交替洗涤三次，然后50℃恒温干燥，得到磁性Fe3O4@SiO2复合纳米粒子。
实施例1
将1.0g的磁性Fe3O4@SiO2复合纳米粒子悬浮于20mL无水甲醇溶剂中，超声20min后，添加0.1g的有机配体1,10-邻菲罗啉-2,9-二羧酸钾(phenCOOK)，然后混合物在氮气氛围下回流12h，冷却至室温，离心分离沉淀，用无水甲醇洗涤三次后，真空干燥，得到含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子。
将1.0g含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子分散到20mL的干燥甲醇中，然后缓慢滴加10mL浓度为0.01g/mL醋酸钯甲醇溶液，混合物在氮气氛围下回流12h，冷却至室温，离心分离沉淀，用无水甲醇洗涤三次后，真空干燥，得到含有Pd-phenCOO的磁性Fe3O4@SiO2复合纳米粒子，简写为Fe3O4@SiO2@Pd-phenCOO，即为所述的一种具有磁性核壳层结构的光催化剂材料。粉末X射线(XRD)测试材料的组成结构(图1)，扫描电镜观测材料的形貌为微球体，直径为100～200nm(图2)。
实施例2
将1.0g的磁性Fe3O4@SiO2复合纳米粒子悬浮于30mL无水乙醇溶剂中，超声30min后，添加0.1g的有机配体1,10-邻菲罗啉-2,9-二羧酸钾(phenCOOK)，然后混合物在氮气氛围下回流8h，冷却至室温，离心分离沉淀，用无水乙醇洗涤三次后，真空干燥，得到含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子。
将1.0g含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子分散到30mL的干燥乙醇中，然后缓慢滴加15mL浓度为0.01g/mL二氯化钯乙醇溶液，混合物在氮气氛围下回流8h，冷却至室温，离心分离沉淀，用无水乙醇洗涤三次后，真空干燥，得到含有Pd-phenCOO的磁性Fe3O4@SiO2复合纳米粒子，简写为Fe3O4@SiO2@Pd-phenCOO，即为所述的一种具有磁性核壳层结构的光催化剂材料。粉末X射线(XRD)测试材料的组成结构，扫描电镜观测材料的形貌。
实施例3
将1.0g的磁性Fe3O4@SiO2复合纳米粒子悬浮于30mL无水甲醇溶剂中，超声30min后，添加0.1g的有机配体1,10-邻菲罗啉-2,9-二羧酸钾(phenCOOK)，然后混合物在氮气氛围下回流6h，冷却至室温，离心分离沉淀，用无水甲醇洗涤三次后，真空干燥，得到含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子。
将1.0g含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子分散到20mL的干燥甲醇中，然后缓慢滴加20mL浓度为0.01g/mL硝酸钯甲醇溶液，混合物在氮气氛围下回流6h，冷却至室温，离心分离沉淀，用无水甲醇洗涤三次后，真空干燥，得到含有Pd-phenCOO的磁性Fe3O4@SiO2复合纳米粒子，简写为Fe3O4@SiO2@Pd-phenCOO，即为所述的一种具有磁性核壳层结构的光催化剂材料。粉末X射线(XRD)测试材料的组成结构，扫描电镜观测材料的形貌。
1,10-邻菲罗啉-2,9-二羧酸钾(简称为phenCOOK)配体的结构简式如下：
将上述实施案例1-3所制备的材料作为催化剂，在模拟太阳光的条件下进行光催化偶联反应实验：称取1.0mmol的4-Br-甲苯，1.5mmol的苯硼酸，5.0mmol的K2CO3，置于100mL的圆底烧瓶中，添加5mL乙醇和5mL蒸馏水作为溶剂，添加0.002g的所制备的具有磁性核壳层结构的光催化剂材料作为催化剂，在功率为300W的Xe灯(λ>420nm)光源照射下，反应8h后，反应结束，冷却至室温，磁铁分离催化剂，减压蒸馏除去溶剂得粗产品，随后柱色谱纯化分离，产率为98％；回收的催化剂在同样条件下，重复循环使用10次，产品产率仍能达到85％以上。
Claims (4)
1.一种具有磁性核壳层结构的光催化剂材料的制备方法，其特征在于，所述制备方法包括如下步骤：
1)将一定质量的磁性Fe3O4@SiO2复合纳米粒子悬浮于一定体积无水甲醇或乙醇溶剂中，超声分散，添加适量的1,10-邻菲罗啉-2,9-二羧酸钾(phenCOOK)，然后混合物在氮气氛围下回流，冷却至室温，离心分离沉淀，用无水甲醇或乙醇洗涤三次后，真空干燥，得到含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子；
2)将一定质量的含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子分散到一定体积的无水甲醇或乙醇中，然后缓慢滴加钯盐溶液，混合物在氮气氛围下回流，冷却至室温，离心分离沉淀，洗涤，真空干燥，得到含有Pd-phenCOO的磁性Fe3O4@SiO2复合纳米粒子，简写为Fe3O4@SiO2@Pd-phenCOO，即为所述的一种具有磁性核壳层结构的光催化剂材料；
所述钯盐为醋酸钯、二氯化钯或硝酸钯。
2.根据权利要求1所述的制备方法，其特征在于，步骤1)和步骤2)的回流时间各自独立选自6～12小时。
3.根据权利要求1所述的制备方法，其特征在于，所述含有phenCOO的磁性Fe3O4@SiO2复合纳米粒子和所述钯盐的质量比为10:1～5:1。
4.一种如权利要求1～3任一项所述制备方法得到的具有磁性核壳层结构的光催化剂材料的用途，其特征在于，该材料作为光催化剂，在模拟太阳光条件下能够高效催化铃木偶联反应，重复循环使用十次，偶联反应的产物产率仍能达到85％以上。
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