CN115041202A - 非均相Pd催化剂的制备方法及其应用 - Google Patents
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Abstract
本发明涉及一种非均相Pd催化剂的制备方法,将Ti3C2粉末加入到溶剂中,并进行超声处理;然后将钯源,铜源、表面活性剂加入悬浮液中,110℃‑170℃下反应1‑3h;反应结束后,依次加入乙醇和水进行离心清洗;最终通过冷冻干燥获得产品。本发明具有操作过程简单、金属前驱体利用率高等优点;并利用该催化剂合成高收率的阿贝西里药物关键中间体。
Description
技术领域
本发明属于新型非均相催化剂的合成,具体地说是涉及一种非均相Pd催化剂的制备方法及其应用。
背景技术
Suzuki反应是阿贝西里药物合成中关键步骤。均相钯催化剂是该步骤最为广泛使用的催化剂。但均相催化剂难以回收,造成了昂贵的催化剂的浪费。为了克服均相催化剂的缺点,人们对异质催化剂进行了探索。在Pd中添加非贵金属,如Cu、Fe和Ni,形成纳米合金或金属间化合物可以有效地提高了催化性能,并减少贵金属。但对于金属纳米晶体,其高比表面积会导致催化剂啊在催化过程中的聚集并脱落,这影响了纳米催化剂的回收性能。
为了克服这些挑战,人们用载体来负载钯基纳米晶体,以避免纳米晶体的聚集,同时保持高催化效率。二维材料,具有许多优点,如表面有许多官能团以增强结合力,具有独特的电子结构以提高其催化性能。但使用氧化石墨烯作为基底制备C-C偶联反应的催化剂需要进行表面功能化或与其他材料复合以提高其电荷转移能力,这使得催化剂的制备过程更加复杂,效率低下,并造成原材料的损失。因此寻找一种合适的新型二维材料作为合金的负载材料是十分必要的。
发明内容
为了克服现有技术的不足,本发明提供了一种非均相Pd催化剂的制备方法及其应用,所述方法为一步还原法制备Ti3C2负载PdCu合金的方法,在Ti3C2纳米片上一步还原生长Pd及PdCu纳米颗粒(简称PdCu4@Ti3C2)的方法。该方法具有操作过程简单、金属前驱体利用率高等优点;并利用该催化剂合成高收率的阿贝西里药物关键中间体。
本发明采用的技术方案为:
一种非均相Pd催化剂的制备方法,将Ti3C2粉末加入到溶剂中,并进行超声处理;然后将钯源,铜源、表面活性剂加入悬浮液中,110℃-170℃下反应1-3h;反应结束后,依次加入乙醇和水进行离心清洗;最终通过冷冻干燥获得产品。
作为优选,钯源和铜源的摩尔比为1:0-4。
作为优选,所述钯源为醋酸钯,铜源为醋酸铜;所述表面活性剂为聚乙烯吡咯烷酮。
作为优选,所述非均相Pd催化剂为PdCu4@Ti3C2、PdCu@Ti3C2,Pd5@Ti3C2中的任一种。
作为优选,所述溶剂为乙二醇;所述水为去离子水。
作为优选,所述Ti3C2粉末通过下述方法获得:
将Ti3AlC2粉末缓慢加入到HF中,在室温下搅拌24-48h;用去离子水离心洗涤,倒出上清液,在加入蒸馏水洗涤,重复该过程数次,直到溶液pH值达到>6;然后将制得的Ti3C2粉末收集并冷冻干燥。
一种上述非均相Pd催化剂在Suzuki反应中应用。
作为优选,上述非均相Pd催化剂在Suzuki反应中应用具体操作为:在试管中加入将4-碘苯甲醚0.5mmol、苯硼酸0.65mmol、K2CO3 1mmol、PdCu4@Ti3C210mg、5mL H2O,在80℃下搅拌1小时,反应结束后,用乙酸乙酯提取混合物;有机层用硫酸镁干燥,过滤并真空浓缩;残余物经硅胶色谱法和石油醚提纯,得到产品,反应产率达到95%,产物中催化剂Pd的残留小于10ppm。
一种上述非均相Pd催化剂在制备阿贝西里药物关键中间体中的应用具体操作为:在50mL圆底烧瓶中分别加入硼酸酯2.5mmol,2,4-二氯-5-氟嘧啶2.5mmol,碳酸钾5mmol,15mL甲苯,15mL水,50mg PdCu4@Ti3C2,滴加完毕后在80℃下继续反应8个小时,反应用TLC检测;待反应完成后,反应结束后,用乙酸乙酯提取混合物;有机层用硫酸镁干燥,过滤并真空浓缩;残余物经硅胶色谱法和石油醚提纯,得到阿贝西里关键中间体,产物收率达到90%,产物中催化剂Pd的残留小于10ppm。。
作为优选,上述非均相Pd催化剂在制备阿贝西里药物关键中间体中的应用本发明的有益效果在于:
(1)首次将Ti3C2用于制备Suzuki反应的非均相催化剂的基底材料,基于Ti3C2优异的性能,相比于其他二维材料,如氧化石墨烯,该催化剂制备过程简单,通过一步还原法就能制备得到,原料利用率高,并且催化性能优异;
(2)该催化剂在Suzuki偶联反应中可多次循环,目标产物保持良好的产率,表明催化剂具有反应体系产业化的可能;
(3)该催化剂可以应用于阿贝西里药物关键中间体的合成,并且目标产物的收率可以高达90%以上;
(4)产物中金属残留小于10ppm,好于现有文献水平。
附图说明
图1为合成的PdCu4@Ti3C2的XRD图;
图2为合成的PdCu4@Ti3C2的透射电子显微镜图;
图3为阿贝西里关键中间体的核磁氢谱图;
图4为催化剂循环使用的效果图。
具体实施方式
下面结合具体实施例对本发明做出进一步的说明,这些实施例并非对本发明的限定,依照本领域现有的技术,本发明的实施方式并不限于此,凡依照本发明公开内容所做出的本领域的等同替换,均属本发明的保护内容。
实施例1
PdCu4@Ti3C2的制备
对Ti3AlC2进行化学蚀刻制备Ti3C2。将2g的Ti3AlC2粉末缓慢加入到20ml的HF中,为避免由于反应放热导致温度升高,可在冰水浴中放置5分钟,然后取出在室温下搅拌24h。用去离子水离心(3500rpm)洗涤,倒出上清液,在加入蒸馏水洗涤,重复该过程数次,直到溶液pH值达到>6。然后将制得的Ti3C2粉末收集并冷冻干燥24h。
向20ml的EG中加入300mg制成的Ti3C2粉末,并进行超声处理6h。然后将22mg的Pd(Ac)2,72mg的Cu(Ac)2和300mg的PVP加入溶液中,在170℃的油浴中反应2h。反应结束后,依次加入乙醇和去离子水进行离心清洗。最终通过冷冻干燥24h获得产品PdCu4@Ti3C2。
为了进行比较,还按照相同的方案制备了PdCu@Ti3C2,Pd5@Ti3C2、Cu@Ti3C2和PdCu4,其中PdCu@Ti3C2的金属源为22mg Pd(Ac)2,18mg Cu(Ac)2,Pd5@Ti3C2和Cu@Ti3C2的金属源分别为110毫克Pd(Ac)2和90毫克Cu(Ac)2,而其他原料保持不变。PdCu4为制备过程中不加入Ti3C2载体。
经X射线衍射分析(图1)、透射电子显微镜(图2)以及电感耦合等离子体质谱表征,衬底为Ti3C2,负载的颗粒为PdCu合金,Pd和Cu的摩尔比为1:4,并且原料利用率较高。PdCu@Ti3C2,Pd5@Ti3C2和Cu@Ti3C2经ICP-MS分析,均有负载。
实施例2
阿贝西里关键中间体的合成
在50mL圆底烧瓶中分别加入硼酸酯(2.5mmol),2,4-二氯-5-氟嘧啶(2.5mmol),碳酸钾(5mmol),15mL甲苯,15mL水,50mg PdCu4@Ti3C2,滴加完毕后在80℃下继续反应8个小时,反应用TLC检测。待反应完成后,反应结束后,用乙酸乙酯提取混合物。有机层用硫酸镁干燥,过滤并真空浓缩。残余物经硅胶色谱法和石油醚提纯,得到产品。晾干后得到阿贝西里关键中间体反应产率达到90%。
阿贝西里关键中间体结构表征核磁共振数据如图3所示:1H NMR(500MHz,DMSO-d6)δ8.97(d,J=3.4Hz,1H),8.16(s,1H),7.63(d,J=11.8Hz,1H),4.89–4.84(m,1H),2.65(s,3H),1.60(d,J=6.9Hz,6H).
分析结果表明,获得的目标产物正确。产物经ICP-MS测定催化剂Pd的残留小于10ppm。
实施例3
苯硼酸与对碘苯甲醚的Suzuki反应
在试管中加入将4-碘苯甲醚(0.5mmol)、苯硼酸(0.65mmol)、K2CO3(1mmol)、PdCu4@Ti3C2(10mg)、5mL H2O,在80℃下搅拌1小时,反应结束后,用乙酸乙酯提取混合物。有机层用硫酸镁干燥,过滤并真空浓缩。残余物经硅胶色谱法和石油醚提纯,得到产品。反应产率达到95%。
产物结构表征核磁共振数据:1H NMR(500MHz,CDCl3)δ7.54(d,J=7.5Hz,2H),7.52(d,J=8.8Hz,2H),7.40(t,J=7.7Hz,2H),7.29(t,J=7.4Hz,1H),6.97(d,J=8.7Hz,2H),3.83(s,3H).
分析结果表明,获得的目标产物正确。产物经ICP-MS测定催化剂Pd的残留小于10ppm。
实施例4
苯硼酸与溴苯的Suzuki反应
在试管中加入将溴苯(0.5mmol)、苯硼酸(0.65mmol)、K2CO3(1mmol)、PdCu4@Ti3C2(10mg)、5mL H2O,在80℃下搅拌1小时,反应结束后,用乙酸乙酯提取混合物。有机层用硫酸镁干燥,过滤并真空浓缩。残余物经硅胶色谱法和石油醚提纯,得到产品。反应产率达到95%。
产物结构表征核磁共振数据1H NMR(500MHz,CDCl3)δ7.56(d,J=7.1Hz,4H),7.40(t,J=7.7Hz,4H),7.31(t,J=7.4Hz,2H).
分析结果表明,获得的目标产物正确。
实施例5
不同催化剂的比较
与实施例3原料相同,分别用PdCu@Ti3C2,Pd5@Ti3C2、Cu@Ti3C2和PdCu4,替代PdCu4@Ti3C2,反应产率分别为80%,92%,33%,82%。其中,虽然Pd5@Ti3C2催化剂也有较高产率,但是Pd5@Ti3C2催化剂中钯的使用量是PdCu4@Ti3C2的5倍。
实施例6
PdCu4@Ti3C2的循环使用
将4-碘苯甲醚(2.5mmol)、苯硼酸(3.25mmol)、K2CO3(5mmol)、PdCu4@Ti3C2(50mg)、25mL H2O置于反应瓶中,在80℃下搅拌。反应结束后,依次加入乙酸乙酯、乙醇和去离子水进行离心清洗。残留的催化剂经冷冻干燥后回收。将烘干的催化剂在相同催化条件下使用,循环使用10次后催化效果没有明显下降,具体如图4所示,可以看出,PdCu4@Ti3C2催化剂在上述反应条件下循环10次,催化效果没有明显的下降。
上述实施例仅例示性说明本发明的较佳方案,而非用于限制本发明。任何熟悉此技术的人士皆可在不超出记载的技术方案的范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变,仍应由本发明的权利要求所涵盖。
Claims (10)
1.一种非均相Pd催化剂的制备方法,其特征在于:将Ti3C2粉末加入到溶剂中,并进行超声处理;然后将钯源,铜源、表面活性剂加入悬浮液中,110℃-170℃下反应1-3h;反应结束后,依次加入乙醇和水进行离心清洗;最终通过冷冻干燥获得产品。
2.根据权利要求1所述非均相Pd催化剂的制备方法,其特征在于:钯源和铜源的摩尔比为1:0-4。
3.根据权利要求1所述非均相Pd催化剂的制备方法,其特征在于:所述钯源为醋酸钯,铜源为醋酸铜;所述表面活性剂为聚乙烯吡咯烷酮。
4.根据权利要求1所述非均相Pd催化剂的制备方法,其特征在于:所述非均相Pd催化剂为PdCu4@Ti3C2、PdCu@Ti3C2,Pd5@Ti3C2中的任一种。
5.根据权利要求1所述非均相Pd催化剂的制备方法,其特征在于:所述溶剂为乙二醇;所述水为去离子水。
6.根据权利要求1所述非均相Pd催化剂的制备方法,其特征在于:所述Ti3C2粉末通过下述方法获得:
将Ti3AlC2粉末缓慢加入到HF中,在室温下搅拌24-48h;用去离子水离心洗涤,倒出上清液,在加入蒸馏水洗涤,重复该过程数次,直到溶液pH值达到>6;然后将制得的Ti3C2粉末收集并冷冻干燥。
7.一种权利要求1所述非均相Pd催化剂在Suzuki反应中应用。
8.根据权利要求7所述的应用,其特征在于具体操作为:在试管中加入将4-碘苯甲醚0.5mmol、苯硼酸0.65mmol、K2CO3 1mmol、PdCu4@Ti3C2 10mg、5mL H2O,在80℃下搅拌1小时,反应结束后,用乙酸乙酯提取混合物;有机层用硫酸镁干燥,过滤并真空浓缩;残余物经硅胶色谱法和石油醚提纯,得到产品,反应产率达到95%,产物中催化剂Pd的残留小于10ppm。
9.一种权利要求1所述非均相Pd催化剂在制备阿贝西里药物关键中间体中的应用。
10.根据权利要求9所述的应用,其特征在于具体操作为:在50mL圆底烧瓶中分别加入硼酸酯2.5mmol,2,4-二氯-5-氟嘧啶2.5mmol,碳酸钾5mmol,15mL甲苯,15mL水,50mgPdCu4@Ti3C2,滴加完毕后在80℃下继续反应8个小时,反应用TLC检测;待反应完成后,反应结束后,用乙酸乙酯提取混合物;有机层用硫酸镁干燥,过滤并真空浓缩;残余物经硅胶色谱法和石油醚提纯,得到阿贝西里关键中间体,产物收率达到90%,产物中催化剂Pd的残留小于10ppm。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107537540A (zh) * | 2017-08-28 | 2018-01-05 | 浙江工业大学 | 一种MXene(Ti3C2)负载钯催化剂及其制备方法和应用 |
CN112553646A (zh) * | 2020-12-08 | 2021-03-26 | 湖南省益思迪科技有限公司 | 一种MXene负载纳米合金催化剂、制备方法及其应用 |
US10967363B1 (en) * | 2017-10-16 | 2021-04-06 | Iowa State University Research Foundation, Inc. | Two-dimensional metal carbide catalyst |
CN113318753A (zh) * | 2021-06-22 | 2021-08-31 | 黄山学院 | 一种负载型CuPd双金属催化剂的制备及其在氧化偶联反应中的应用 |
CN114517304A (zh) * | 2022-03-16 | 2022-05-20 | 杭州师范大学 | 具有PdCu合金颗粒负载的NiFe-LDH金属纳米片材料电催化剂制备方法 |
-
2022
- 2022-07-11 CN CN202210812429.5A patent/CN115041202A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107537540A (zh) * | 2017-08-28 | 2018-01-05 | 浙江工业大学 | 一种MXene(Ti3C2)负载钯催化剂及其制备方法和应用 |
US10967363B1 (en) * | 2017-10-16 | 2021-04-06 | Iowa State University Research Foundation, Inc. | Two-dimensional metal carbide catalyst |
CN112553646A (zh) * | 2020-12-08 | 2021-03-26 | 湖南省益思迪科技有限公司 | 一种MXene负载纳米合金催化剂、制备方法及其应用 |
CN113318753A (zh) * | 2021-06-22 | 2021-08-31 | 黄山学院 | 一种负载型CuPd双金属催化剂的制备及其在氧化偶联反应中的应用 |
CN114517304A (zh) * | 2022-03-16 | 2022-05-20 | 杭州师范大学 | 具有PdCu合金颗粒负载的NiFe-LDH金属纳米片材料电催化剂制备方法 |
Non-Patent Citations (1)
Title |
---|
DANCHENG ZHU ET AL.: "One-step synthesis of PdCu@Ti3C2 with high catalytic activity in the Suzuki-Miyaura coupling reaction", 《NANOSCALE ADVANCES》, vol. 4, pages 3362 - 3369 * |
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