CN109622037A - 一种Pd@Co4(tpt)2(btb)复合材料及其制备方法和应用 - Google Patents
一种Pd@Co4(tpt)2(btb)复合材料及其制备方法和应用 Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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Abstract
本发明涉及一种Pd@Co4(tpt)2(btb)复合材料及其制备方法和应用。采用的技术方案：将2,4,6‑三(4‑吡啶基)‑1,3,5‑三嗪、1,3,5‑三(4‑羧基苯基)苯、七水硫酸钴和溶剂加入到容器内，搅拌，再加入氟硼酸搅拌至溶解。密封后放入烘箱内，于393K下保持5天；冷却到室温，静置1‑3天后，洗涤，过滤，干燥，得Co4(tpt)2(btb)晶体；将氯钯酸钠的甲醇溶液缓慢滴加到Co4(tpt)2(btb)材料中，用还原剂进行还原，得Pd@Co4(tpt)2(btb)复合材料。本发明所制备的Pd@Co4(tpt)2(btb)复合材料制备方法简单，对Suzuki反应展示出良好的催化性能。
Description
技术领域
本发明属于贵金属催化剂领域，具体涉及的是一种Pd@Co4(tpt)2(btb)复合材料及其制备方法和应用。
背景技术
Suzuki反应是目前在偶联反应中一种十分重要的合成反应，其产物联苯化合物广泛用于医药、农药、染料、液晶材料等领域。可以用来合成增塑剂、防腐剂，还可以用于制造燃料、工程塑料和高能燃料等。因此，提供一种能够提高Suzuki反应效率的催化剂具有十分重要的意义。
钯纳米粒子是一种高效的异相催化剂，具有较高的原子活性。近些年来，钯纳米粒子经常被负载在载体上(氧化铝载体、硅胶载体、活性炭载体及某些天然产物如浮石、硅藻土等)，用来催化各种有机反应。但这些载体循环性能差，催化效率低，并且在催化过程中很难保护催化剂，容易造成活性金属的流失，降低催化性能。金属有机骨架材料是一种很好的载体，其结构稳定，热稳定性好，相比较氧化铝、硅胶等载体有诸多好处。
发明内容
本发明的目的是提供一种Pd@Co4(tpt)2(btb)复合材料及其制备方法，是从含钯的金属化合物氯化钯出发，通过简单的等量浸渍后，将纳米粒子与金属有机骨架有效的结合在一起，再通过还原法将其还原成零价态的钯，形成一种具有孔洞结构的新型复合材料Pd@Co4(tpt)2(btb)。
为实现上述目的，本发明采用如下技术方案，一种Pd@Co4(tpt)2(btb)复合材料，所述的Pd@Co4(tpt)2(btb)复合材料是钯纳米粒子负载在金属有机骨架Co4(tpt)2(btb)上形成的复合材料。
上述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，包括如下步骤：
1)将2,4,6-三(4-吡啶基)-1,3,5-三嗪、1,3,5-三(4-羧基苯基)苯、七水硫酸钴和溶剂，加入到容器内，于常温下，搅拌溶解；
2)加入氟硼酸，搅拌均匀，超声至完全溶解，将容器密封后放入烘箱内，以10K·min-1的升温速率升温至393K并保持5天；
3)以10K·min-1的降温速率冷却到室温，静置1-3天后，得晶体，用N,N-二甲基乙酰胺、乙醇洗涤，过滤，干燥，得Co4(tpt)2(btb)晶体；
4)取氯化钯用溶剂进行溶解，加入中性盐与其反应，得氯钯酸的盐溶液；
5)将氯钯酸的盐溶液缓慢滴加到Co4(tpt)2(btb)材料中，得Pd2+@Co4(tpt)2(btb)复合材料。
6)将Pd2+@Co4(tpt)2(btb)复合材料用还原剂进行还原，得Pd@Co4(tpt)2(btb)复合材料。
优选的，上述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，步骤1)中，按摩尔比，2,4,6-三(4-吡啶基)-1,3,5-三嗪:1,3,5-三(4-羧基苯基)苯:七水硫酸钴＝61:48:103。
优选的，上述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，步骤1)中所述的溶剂为N,N-二甲基乙酰胺、甲醇和1,4-二氧六环的混合物。
优选的，上述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，步骤4)中，所述的溶剂为甲醇，所述的中性盐为氯化钠。
优选的，上述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，按摩尔比，氯化钠：氯化钯＝19:17。
优选的，上述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，步骤6)中，所述的还原剂为硼氢化钠，还原温度为室温，还原时间为15min。
上述的一种Pd@Co4(tpt)2(btb)复合材料在催化Suzuki反应中的应用。
优选的，上述的应用，取碘苯，苯硼酸，碳酸钾，乙醇和催化剂于容器中，通入氮气，搅拌，343K下反应0.5h；所述的催化剂是Pd@Co4(tpt)2(btb)复合材料。反应式如下：
上述的应用，按质量比，Pd@Co4(tpt)2(btb)复合材料：碘苯＝1:4。
本发明的有益效果是：
1.本发明所述的催化剂与传统的催化剂相比，本发明所制备的Pd@Co4(tpt)2(btb)复合材料对Suzuki反应具有优异的催化活性，反应时间只需半小时并且产率可以达到100％。而且合成方法简单，具有应用前景。
2.本发明采用Co4(tpt)2(btb)晶体作为负载贵金属钯纳米粒子的金属有机骨架，形成新型的复合材料。Co4(tpt)2(btb)晶体的孔洞适中，有优异的化学稳定性和热稳定性。可以保证负载在其中的金属钯纳米粒子的分散，又可以避免由于团聚、氧化等因素引起的催化剂失活。
3.本发明合成的Pd@Co4(tpt)2(btb)复合材料，具有良好的重复利用能力，易与反应物分离，对整个反应体系不存在干扰。
附图说明
图1是本发明Pd@Co4(tpt)2(btb)复合材料与Co4(tpt)2(btb)的XRD图。
图2是本发明Pd@Co4(tpt)2(btb)复合材料的透射电子显微镜图。
图3是本发明Pd@Co4(tpt)2(btb)复合材料五次循环催化反应的催化活性。
具体实施方式
为了更好的理解本发明，下面通过实施例对本发明做进一步说明，应理解以下实施目的在于更好的解释本发明的内容，而不是对本发明的保护范围产生任何限制。
实施例1 Pd@Co4(tpt)2(btb)复合材料
(一)、制备
准确称取2,4,6-三(4-吡啶基)-1,3,5-三嗪0.019g(0.061mmol)、1,3,5-三(4-羧基苯基)苯0.021g(0.048mmol)、七水硫酸钴0.029g(0.103mmol)于容器中，加入溶剂N,N-二甲基乙酰胺5mL、甲醇5mL、1,4-二氧六环1mL，搅拌溶解，再加入100μL氟硼酸(40％水溶液)，超声30分钟至完全溶解。将容器密封后放入烘箱内，以10K·min-1的升温速率升温至393K并保持5天；以10K·min-1的降温速率冷却到室温，静置1天后，得到褐色纺锤体状晶体；用N,N-二甲基乙酰胺、乙醇洗涤，过滤，干燥，得Co4(tpt)2(btb)晶体。
准确称取氯化钯晶体0.12g(0.68mmol)于容器中，加入4mL甲醇，同时加入0.044g(0.76mmol)氯化钠，超声30分钟，搅拌过夜，得到棕褐色的0.17mol/L的氯钯酸钠溶液。移取80μL氯钯酸钠溶液缓慢滴加到50mg的Co4(tpt)2(btb)复合材料中加入搅拌子在磁力搅拌器上搅拌，使氯钯酸钠溶液充分进入到Co4(tpt)2(btb)孔洞中，得Pd2+@Co4(tpt)2(btb)复合材料。然后用2mL 0.6mol/L的硼氢化钠的甲醇溶液在室温下进行还原，在磁力搅拌器上搅拌15分钟，离心并用新鲜的甲醇溶液洗涤晶体三次，干燥，得目标产物Pd@Co4(tpt)2(btb)复合材料。
(二)、检测
图1为Pd@Co4(tpt)2(btb)复合材料的粉末X-射线衍射(PXRD)图，表明Pd@Co4(tpt)2(btb)复合材料在制备过程中Co4(tpt)2(btb)的晶体结构没有被破坏，依旧完整。图2为Pd@Co4(tpt)2(btb)复合材料的透射电子显微镜(TEM)图，可以看到钯纳米粒子被很好的负载到Co4(tpt)2(btb)的孔洞中，并且钯纳米粒子大小均匀，分散较好。
实施例2 Pd@Co4(tpt)2(btb)复合材料对Suzuki反应的催化功能
方法：以实施例1制备的Pd@Co4(tpt)2(btb)复合材料作为催化剂对Suzuki反应进行催化。
反应式如下：
取一只洁净干燥的10mL的三口烧瓶，将左右两个支口用翻口橡胶塞塞好，加入反应物碘苯0.204g(1.0mmol)、苯硼酸0.1828g(1.5mmol)，无机碱K2CO3 0.4146g(3.0mmol)，溶剂乙醇5mL，制备好的Pd@Co4(tpt)2(btb)复合材料50mg，连接好反应装置，反应在温度为343K磁力搅拌器中反应半小时。反应完成后通过离心除去催化剂Pd@Co4(tpt)2(btb)复合材料，取上层清液用气相色谱监测反应进程，得到联苯，产率为100％。
催化剂的回收：反应结束后，过滤，将催化剂与反应混合物分离，用N,N-二甲基乙酰胺、乙醇洗涤，滤出，烘干。
循环实验的具体操作：利用回收的催化剂(50mg)催化1.0mmol的碘苯，1.5mmol的苯硼酸和3.0mmol的K2CO3反应，在343K下反应半小时，得到联苯，对催化剂进行回收。循环实验5轮。
如图3所示，循环实验进行到第5轮，催化剂的活性仍然没有下降。说明该Pd@Co4(tpt)2(btb)复合材料作为Suzuki反应催化剂可循环利用。
Claims (10)
1.一种Pd@Co4(tpt)2(btb)复合材料，其特征在于，所述的Pd@Co4(tpt)2(btb)复合材料是钯纳米粒子负载在金属有机骨架Co4(tpt)2(btb)上形成的复合材料。
2.权利要求1所述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，其特征在于，包括如下步骤：
1)将2,4,6-三(4-吡啶基)-1,3,5-三嗪、1,3,5-三(4-羧基苯基)苯、七水硫酸钴和溶剂，加入到容器内，于常温下，搅拌溶解；
2)加入氟硼酸，搅拌均匀，超声至完全溶解，将容器密封后放入烘箱内，以10K·min-1的升温速率升温至393K并保持5天；
3)以10K·min-1的降温速率冷却到室温，静置1-3天后，得晶体，用N,N-二甲基乙酰胺、乙醇洗涤，过滤，干燥，得Co4(tpt)2(btb)晶体；
4)取氯化钯用溶剂进行溶解，加入中性盐与其反应，得氯钯酸的盐溶液；
5)将氯钯酸的盐溶液缓慢滴加到Co4(tpt)2(btb)材料中，得Pd2+@Co4(tpt)2(btb)复合材料；
6)将Pd2+@Co4(tpt)2(btb)复合材料用还原剂进行还原，得Pd@Co4(tpt)2(btb)复合材料。
3.根据权利要求2所述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，其特征在于，步骤1)中，按摩尔比，2,4,6-三(4-吡啶基)-1,3,5-三嗪:1,3,5-三(4-羧基苯基)苯:七水硫酸钴＝61:48:103。
4.根据权利要求2所述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，其特征在于，步骤1)中所述的溶剂为N,N-二甲基乙酰胺、甲醇和1,4-二氧六环的混合物。
5.根据权利要求2所述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，其特征在于，步骤4)中，所述的溶剂为甲醇，所述的中性盐为氯化钠。
6.根据权利要求5所述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，其特征在于，按摩尔比，氯化钠：氯化钯＝19:17。
7.根据权利要求2所述的一种Pd@Co4(tpt)2(btb)复合材料的制备方法，其特征在于，步骤6)中，所述的还原剂为硼氢化钠，还原温度为室温，还原时间为15min。
8.权利要求1所述的一种Pd@Co4(tpt)2(btb)复合材料在催化Suzuki反应中的应用。
9.根据权利要求8所述的应用，其特征在于，取碘苯，苯硼酸，碳酸钾，乙醇和催化剂于容器中，通入氮气，搅拌，343K下反应0.5h；所述的催化剂是权利要求1所述的Pd@Co4(tpt)2(btb)复合材料。
10.根据权利要求9所述的应用，其特征在于，按质量比，Pd@Co4(tpt)2(btb)复合材料：碘苯＝1:4。
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