CN106582710B - 一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 - Google Patents
一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 Download PDFInfo
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Abstract
本发明公开了一种石墨烯负载钯铜纳米胶囊催化Suzuki偶联反应制备联苯的方法。通过氧化石墨烯和铜盐、钯盐溶液的水热还原，经洗涤、干燥得到石墨烯负载钯铜纳米胶囊催化剂。使用石墨烯负载钯铜胶囊型纳米胶囊催化Suzuki偶联反应制备联苯反应中有良好的催化作用，实现高效催化的同时减少了钯的使用量，并减少了钯中毒。卤代烃化合物转化率超过90%，联苯化合物选择性达到95%，并对多种卤代烃化合物有良好适用性。
Description
技术领域
本发明公开了一种石墨烯负载钯铜纳米胶囊催化剂的制备方法及其在催化Suzuki偶联反应制备联苯中的应用。
背景技术
从2004年，英国曼彻斯特大学的Geim课题组利用非常简单的胶带剥离石墨的方法首次制备出了稳定的高质量的单层和少数几层石墨烯，到现在人们逐渐将其实现生产规模化和实用化，石墨烯的有关技术已经成为了化学材料研究领域中的重要研究课题。石墨烯拥有独特的二维结构和优异的物理、化学性能，这一点引发了全世界范围内对这一材料的理论与实践研究。由于其独特的二维共轭结构，石墨烯展现出诸多突出的物理化学性质。各国学者开始尝试应用化学或者物理等相关方法开发各种可靠的石墨烯制备方法。包括机械剥离法、外延生长法、化学气相沉积法、胶体溶液法以及其它一些方法。其中，化学法制备石墨烯越来越受到人们关注。石墨烯巨大的比表面积可以为金属纳米粒子的负载提供一个优良场所，并且石墨烯的片层结构可以增大与反应物的接触，有效的提高反应速率和效率。
联苯是重要的有机原料，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。联苯存在于煤焦油、原油和天然气中。制备联苯，传统方法是通过各种煤焦油馏分制联苯的分离提取法；联苯在煤焦油中的质量分数为0.20%~0.40%，含量太少，此类方法已使用较少。还有石油化工上，通过苯热解制联苯的化学合成法。随着钯催化偶联反应近50年的发展，通过偶联方法合成联苯类化合物已经成为主要的合成手段。而用钯催化剂通过Suzuki偶联反应制备联苯化合物已是最经济的合成方案。为了开发出更加高效的催化剂，同时也降低钯催化剂的使用量，发展协调匹配的双金属或多金属催化剂，协助钯金属的催化作用，这类含钯复合催化材料的开发变的越来越重要。
发明内容
在本发明的目的在于发展一种石墨烯负载钯铜纳米胶囊催化Suzuki偶联反应制备联苯的方法。通过氧化石墨烯和氯化钯、硫酸铜的水热还原，经洗涤、干燥得到石墨烯负载钯铜胶囊型纳米胶囊催化剂。使用石墨烯负载钯铜纳米胶囊催化剂在 Suzuki偶联反应中有很好的催化作用，可把卤代烃化合物高选择性、高效率地合成联苯化合物。实现高效催化的同时减少了钯的使用量，并且通过钯、铜之间的电子效应，减少了钯中毒的情况发生。卤代烃化合物转化率超过90%，联苯化合物选择性达到95%，对多种卤代烃化合物有优秀的催化适用性。
为实现上述目的，本发明采用下述技术方案：
1、一种石墨烯负载钯铜纳米胶囊催化剂的制备方法，主要是由氧化石墨烯、氯化钯、硫酸铜通过水热还原反应制得，其制备方法包括以下步骤：将氯化钯乙二醇溶液逐滴加入到Hummers法制备的氧化石墨烯乙二醇浆液中，在29 oC下搅拌混合40分钟，加入硫酸铜水溶液、谷氨酸钠后，通过滴加一定浓度的氢氧化钾乙二醇溶液，调节pH至10~13，25~30 oC搅拌一定时间，移入水热釜中，180 oC下水热反应8~16小时，水、乙醇洗涤，干燥得石墨烯负载钯铜纳米胶囊催化剂。
2、石墨烯负载钯铜纳米胶囊催化剂的制备方法，10mg/mL的氧化石墨烯水溶浆液乙二醇配制后氧化石墨烯成浆液浓度为0.5~1.5mg/mL，优选0.8mg/mL~1.2 mg/mL。
3、石墨烯负载钯铜纳米胶囊催化剂的制备方法，氯化钯、硫酸铜的摩尔比为2~7:9~3,优选4~7:7~5。水溶浆液中所含氧化石墨烯质量和L-谷氨酸钠质量之比为3:5。
4、一种石墨烯负载钯铜纳米胶囊催化Suzuki偶联反应制备联苯的方法，包括下述步骤：将卤代烃化合物、苯硼酸、碳酸钾、石墨烯负载钯铜纳米胶囊催化剂置于反应装置中，卤代烃化合物：苯硼酸：碳酸钾摩尔比=1:1~3:1~6；卤代烃化合物与石墨烯负载钯铜纳米胶囊的质量比为20~200:1，优选为50~100:1；以水和乙醇体积比1:1配制溶剂加入到反应体系中，溶剂体积为1~30mL/1mmol（卤代烃化合物），优选4~12mL/1mmol（卤代烃化合物），60~100℃下加热反应4~24小时。
5、石墨烯负载钯铜纳米胶囊催化Suzuki偶联反应制备联苯的方法，卤代烃化合物包括碘苯、溴苯、γ-溴代蒽、间氯溴苯、对氯溴苯、对甲基溴苯、对溴苯甲醛、邻溴苯甲酸、α-溴代萘、β-溴代萘、间溴苯甲酸、3,5-二氯溴苯、氯苯、2-硝基-5-溴吡啶。
与现有技术相比，本发明的有益效果是：
通过氧化石墨烯和氯化钯、硫酸铜通过水热还原把氧化石墨烯和铜离子、钯离子同时原位还原，从而得到纳米尺寸的钯铜纳米胶囊均匀分散在还原石墨烯片上。反应后经水、乙醇洗，冻干得到石墨烯负载的钯铜纳米胶囊催化剂。使用所得复合催化剂在比例为1:1的水和乙醇混合液中进行反应，卤代烃化合物的转化率超过90%，联苯化合物选择性达到95%。反应完成后，回收非均相的石墨烯负载钯铜纳米胶囊催化剂，重复使用五次，卤代烃化合物的转化率仍超过90%，联苯化合物选择性仍达到95%。
具体实施方式
石墨烯负载钯铜纳米胶囊催化剂制备实例：
1、取一100mL烧杯，量取3.0mL10.0mg/mL的氧化石墨烯水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取2.8mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取0.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入50.0mg谷氨酸钠固体，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
2、取一100mL烧杯，量取1.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取3.7mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取0.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入25.0mg谷氨酸钠固体，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至13，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
3、取一100mL烧杯，量取4.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取3.7mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取0.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入75.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至13，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
4、取一100mL烧杯，量取3.0mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取2.6mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入50.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至12，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
5、取一100mL烧杯，量取1.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取2.6mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入25.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至13，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
6、取一100mL烧杯，量取4.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取2.6mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入75.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
7、取一100mL烧杯，量取3.0mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取0.5mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入50.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
8、取一100mL烧杯，量取1.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取0.5mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入25.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
9、取一100mL烧杯，量取4.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取0.5mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入75.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
石墨烯负载钯铜纳米胶囊催化氢气还原硝基芳烃化合物制备芳基胺化合物的方法实施例：
1、取一38mL的密封管，加入94.7mg溴苯、80.8mg苯硼酸、110.0mg碳酸钾和1.4mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应8h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，碘苯的转化率为100.0%，联苯化合物的选择性为100.0%。
2、取一38mL的密封管，加入61.9mg碘苯、40.7mg苯硼酸、106.0mg碳酸钾和1.0mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，碘苯的转化率为100.0%，联苯化合物的选择性为100.0%。
3、取一38mL的密封管，加入100.6mg邻溴苯甲醛、73.0mg苯硼酸、106.0mg碳酸钾和2.0mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应8h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，邻溴苯甲醛的转化率为99.5%，联苯化合物的选择性为99.8%。
4、取一38mL的密封管，加入51.1mg间溴苯甲酸、59.3mg苯硼酸、112.0mg碳酸钾和1.0mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应10h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，间溴苯甲酸的转化率为99.6%，联苯化合物的选择性为80%。
5、取一38mL的密封管，加入98.9mg γ-溴代蒽、34.6mg苯硼酸、81.7mg碳酸钾和1.3mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，γ-溴代蒽的转化率为91.6%，联苯化合物的选择性为98.6%。
6、取一38mL的密封管，加入105.5mg间氯溴苯、85.3mg苯硼酸、157.8mg碳酸钾和1.7mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，间氯溴苯的转化率为99.9%，联苯化合物的选择性为100.0%。
7、取一38mL的密封管，加入77.2mg对溴碘苯、108.0mg苯硼酸、180.0mg碳酸钾和1.2mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，对溴碘苯的转化率为98.9%，联苯化合物的选择性为99.1%。
8、取一38mL的密封管，加入94.9mg对氯溴苯、71.0mg苯硼酸、103.2mg碳酸钾和1.1mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，碘苯的转化率为96.3%，联苯化合物的选择性为99.0%。
9、取一38mL的密封管，加入126.9mg对甲氧基溴苯、95.4mg苯硼酸、146.0mg碳酸钾和1.5mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应10h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，碘苯的转化率为98.7%，联苯化合物的选择性为99.0%。
10、取一100mL的密封管，加入1.25g溴苯、0.897g苯硼酸、1.86g碳酸钾和20mg石墨烯负载钯铜纳米胶囊催化剂，量取30mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应8h后，停止加热，自然冷却至室温。过滤，将滤出固体用乙醇和水洗涤，离心，干燥，收集固体催化剂。然后称取1.25g溴苯、0.90g苯硼酸、1.86g碳酸钾、回收的固体催化剂和30.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应8h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，并用液相色谱和气相色谱分析，溴苯的转化率为96.0%，联苯化合物的选择性为96.5%。重复套用石墨烯负载钯铜纳米胶囊催化剂，按此方法。
上述虽然结合实施例对本发明的具体实施方式进行了描述，但并非对本发明实施方式的限定。对所属领域技术人员来说，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
Claims (3)
1.一种石墨烯负载钯铜纳米胶囊催化剂的制备方法，其特征在于，主要是由氧化石墨烯、氯化钯、硫酸铜通过水热还原法制得，其制备方法包括以下步骤：将氯化钯乙二醇溶液逐滴加入到Hummers法制备的氧化石墨烯乙二醇浆液中，在29 ℃下搅拌混合40分钟，加入硫酸铜水溶液、谷氨酸钠后，通过滴加一定浓度的氢氧化钾乙二醇溶液，调节pH至10-13，25-30 ℃搅拌一定时间，移入水热釜中，180 ℃下水热反应8-16小时，水、乙醇洗涤，干燥得石墨烯负载钯铜纳米胶囊催化剂。
2.根据权利要求1所述的一种石墨烯负载钯铜纳米胶囊催化剂的制备方法，Hummers法制备的氧化石墨烯水溶浆液浓度为10mg/mL，乙二醇配制后的氧化石墨烯浓度为0.5-1.5mg/mL。
3.根据权利要求2所述的一种石墨烯负载钯铜纳米胶囊催化剂的制备方法，其特征在于，氯化钯：硫酸铜的摩尔比为2~7:9~3，氧化石墨烯水溶浆液中所含氧化石墨烯质量与谷氨酸钠的质量比为3:5。
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