CN111589443B - 一种石墨烯负载钯纳米颗粒复合材料催化剂的制备方法 - Google Patents
一种石墨烯负载钯纳米颗粒复合材料催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种石墨烯负载钯纳米颗粒复合材料催化剂的制备方法,其步骤包括;(1)浸渍:将氧化石墨烯投入氯化钯溶液中浸渍;(2)喷雾干燥:将步骤(1)的溶液进行喷雾干燥处理,收得含钯的氧化石墨烯粉末;(3)高温还原:将步骤(2)制得含钯氧化石墨烯粉末在H2气氛高温还原收得含钯的石墨烯粉末;(4)再浸渍:称取适量的步骤(3)所制得的含钯石墨烯粉末投入醋酸钯的乙醇‑水溶液中再浸渍;(5)化学还原:再按照一定的摩尔比向(4)的溶液中投入苯硼酸、溴苯、碳酸铯化学还原;(6)分离、干燥收得钯负载量为1.0~2.5wt%石墨烯负载钯纳米颗粒催化剂。本发明工艺流程简单、条件温和,制得的催化剂活性高、且可多次重复利用。
Description
技术领域
本发明属于负载型贵金属催化剂制备技术领域,具体涉及一种石墨烯负载钯纳米颗粒复合材料催化剂的制备方法。
背景技术
钯催化的碳-碳偶联反应在有机合成中的应用范围十分广泛,目前已应用于农药、医药中间体、有机功能材料、液晶材料及生化等领域。根据C-C偶联反应前体的类型,偶联反应可以大致分为自偶联和交叉偶联两种反应类型;交叉偶联反应的主要类型包括:Suzuki-Miyaura、Heck、Hiyama、Sonogashira反应等。其中钯催化芳基硼酸和卤代芳烃之间的Suzuki-Miyaura偶联反应具有反应条件温和、选择性高等优点而备受关注。在Suzuki偶联反应中,催化剂有着至关重要的作用,是Suzuki偶联反应研究的重点。Suzuki偶联反应普遍多利用均相钯催化剂,虽然该催化体系具有分散性好、催化活性高、化学选择性好等优点,但均相催化剂体系也存在催化剂价格昂贵、反应条件苛刻,又因均相催化剂与反应体系在同一相中反应存在分离操作复杂、催化剂难以回收重复利用且残留的钯会对产物造成一定的污染,催化剂在高温下稳定性差等缺点,制约了其大规模使用。而非均相催化剂则不存在此缺陷,且具有易分离、耐高温、寿命长等优点,故越来越多的学者开始关注非均相钯催化剂的研究。
目前用于非均相钯催化剂载体材料包括:碳材料、高分子聚合物、分子筛、金属氧化物、二氧化硅、水滑石以及活性粘土等[5]。其中碳材料由于来源广泛、化学稳定性高、不溶于有机溶剂、廉价易得等优点,是理想的Suzuki反应催化剂的载体而受到广泛关注。常用的碳材料包括活性炭、碳纳米纤维(CNFs)、碳纳米管(CNTs)、有序介孔材料、石墨烯等;其中,石墨烯因具有十分优异的物理和化学性质,已经成为了目前最理想的二维纳米材料。氧化石墨烯是石墨经氧化后得到的一种功能化石墨烯,是石墨烯材料中一类非常重要的衍生物。与石墨烯材料相比,氧化石墨烯具有大量的羧基、羟基和环氧基等含氧基团及良好的离解度和插层性能,这使得氧化石墨烯在生物医学、光电器件和复合材料上具有诱人的应用前景。近年来,氧化石墨烯更是作为一种很有研究和发展前途的催化剂载体材料,受到人们的极大关注。这主要是因为与传统的贵金属催化剂载体材料相比,氧化石墨烯具有一些显著的结构特点:(1)氧化石墨烯含有大量的含氧活性基团,如羧基、羟基与环氧基等,这不仅提高了其在水相介质中的分散性,同时有利于化学功能修饰,能与贵金属催化剂的多种配体进行反应,得到各种不同配位形式的负载型钯催化剂,从而提高负载型催化剂的活性;(2)氧化石墨烯具有独特的二维结构,可提高钯纳米粒子在其表面的分散性能,从而提高负载型催化剂的催化活性;(3)氧化石墨烯具有较高的比表面积,可提高氧化石墨烯与钯的作用力,能在很大程度上防止钯在反应过程中发生迁移和浸出;(4)此外,氧化石墨烯尺寸可控制,以其为载体制备的催化剂具有较高的传质速率,这可在很大程度上提高催化反应速率,节省反应时间。由此可见,氧化石墨烯材料具有其它传统载体材料无可比拟的优势,非常适合担当钯催化剂的载体。
负载型钯纳米颗粒催化剂常见制备方式有载体与钯盐溶液浸,后再还原或先制备钯纳米颗粒后再将其与载体浸渍进行负载。整个制备过程常用的方法有物理法和化学法两种,以化学法研究的最多。物理法主要有超声化学法,包括超声和微波法,物理法制备的钯纳米纯度较高,但是纳米颗粒的尺寸和均匀分散性则是物理方法难于控制的。而化学法主要为化学还原法和电化学法化学还原法根据还原剂还原能力的不同,可分为强还原剂和弱还原剂。这些方法存在着成本高、工艺较复杂、重复性差等问题。
发明内容
本发明的一个方面在于避免加入额外还原剂造成多余的环境污染的同时;另一个方面在于提供了一种制备工艺简单、重复性好、钯纳米颗粒均匀分散在载体上的方法。本发明的催化剂中钯的含量为1.0~2.5wt%,钯纳米颗粒平均粒径为10nm;催化Suzuki偶联反应,可重复循环使用至少8次。
为实现上述目的,本发明的技术方案:
步骤1、浸渍:按照载体与钯的质量比为400~1000:1,取适量的氧化石墨烯水溶液,并将其投入一定浓度的氯化钯溶液中,浸渍24~48小时。
步骤2、喷雾干燥:将步骤1所得的混合溶液,使用喷雾干燥设备进行干燥处理,雾化过程液体流量为3.0~8.0ml/min,雾化气压为0.1~0.5MPa,进口温度为170~190℃,热空气气流量为4.0~10.0L/min,收得含钯的氧化石墨烯粉末。
步骤3、高温H2还原:将步骤2所得氧化石墨烯粉末用管式炉在氢气气氛、400~600℃条件下还原1~3小时,收得含钯的石墨烯粉末。
步骤4、再浸渍:称取适量的醋酸钯,使用无水乙醇和去离子水(体积比1:1)进行溶解;然后再称取适量的步骤3中所制得的钯负载量约为0.1wt%的石墨烯投入上述溶液中,保温30~50℃,并持续搅拌3~6h。
步骤5、Suzuki还原:再按照摩尔比0.05(钯):1:1.25:3.0投入苯硼酸、溴苯、碳酸铯;升温至80℃,搅拌反应1~4h,通过TLC跟踪反应情况,反应结束后静置冷却至室温。
步骤6、离心、干燥:使用离心将催化剂进行分离,离心分离参数:5000~8000rpm、5~10min,并使用无水乙醇、去离子水交替清洗固体3~5次。最后,将收集的固体在50~80℃下烘干16~24小时,钯负载量约为1.0~2.5wt%的石墨烯催化剂制成。
本发明通过雾化干燥及化学还原工艺,制备出了可重复利用的高活性的钯纳米颗粒负载石墨烯催化剂,工艺流程简单,易于实施,所的催化剂的钯含量为1.0~2.5wt%,催化Suzuki偶联反应转化率>85%(与传统均相催化剂相当)且可重复利用8次。载体选择石墨烯,贵金属钯易回收,减少了污染和能耗,具有重要的经济效益和环境意义。
附图说明
图1为本发明的工艺流程图。
图2为本发明负载量2.48wt%石墨烯负载钯纳米颗粒催化剂的TEM图。
图3为本发明实施例1、2制备的催化剂的性能评价图。
具体实施方式
本发明先后进行过多次试验,现举一部分试验结果作为参考实例对发明进行详细描述及验证其效果。
实施例1
(1)浸渍工艺:移取适量体积的一定浓度的氯化钯溶液,然后按照载体与钯的质量比为400:1取适量的氧化石墨烯水溶液,并将其投入溶液中,浸渍36小时。
(2)喷雾干燥工艺:将(1)所得的混合溶液,使用喷雾干燥机控制液流量为4.0ml/min,雾化气压为0.4MPa,进口温度为180℃,热空气气流量为8.0L/min,进行干燥处理,收得含钯的氧化石墨烯粉末。
(3)高温还原工艺:将(2)所得的含钯氧化石墨烯粉末使用管式炉,在氢气气氛、500℃条件下还原1小时,收得负载钯的石墨烯粉末。
(4)再浸渍工艺:称取适量的醋酸钯,使用无水乙醇、去离子水(体积比1:1)进行溶解;然后再按照石墨烯与钯的质量比为40:1,称取适量的(3)中所制得的负载钯的石墨烯粉末投入上述溶液中,在40℃条件下保温,并持续搅拌4h。
(5)化学还原工艺:再向步骤4中的含钯溶液投入苯硼酸、溴苯、碳酸铯,其摩尔比按照醋酸钯、苯硼酸、溴苯、碳酸铯分别为0.05:1.0:1.25:3.0;升温至80℃,搅拌反应1~4h,通过TLC跟踪反应情况,反应结束后静置冷却至室温。
(6)分离、干燥工艺:使用离心(8000rpm、10min)方式将催化剂分离出来,并使用无水乙醇、去离子水交替清洗分离出的催化剂4次。最后,将收集的催化剂在75℃下烘干24小时,收得钯负载量为2.48wt%的石墨烯催化剂。
实施例2
本发明所述钯纳米颗粒-石墨烯催化剂通过如下工艺制得:
(1)浸渍工艺:移取适量体积的浓度为的氯化钯溶液,然后按照载体与钯的质量比为1000:1,取适量的氧化石墨烯水溶液,并将其投入溶液中,浸渍24小时。
(2)喷雾干燥工艺:将(1)所得的混合溶液,使用喷雾干燥机控制液流量为6.0ml/min,雾化气压为0.3MPa,进口温度为180℃,热空气气流量为8.0L/min,进行干燥处理,收得含钯的氧化石墨烯粉末。
(3)高温还原工艺:将(2)所得的含钯氧化石墨烯粉末使用管式炉,在氢气气氛、500℃条件下还原1小时,收得负载钯的石墨烯粉末。
(4)再浸渍工艺:称取适量的醋酸钯,使用无水乙醇、去离子水(体积比1:1)进行溶解;然后再按照石墨烯与钯的质量比为100:1,称取适量的(3)中所制得的负载钯的石墨烯粉末投入上述溶液中,在40℃条件下保温,并持续搅拌3h。
(5)化学还原工艺:再向步骤4中的含钯溶液投入苯硼酸、溴苯、碳酸铯,其摩尔比按照醋酸钯、苯硼酸、溴苯、碳酸铯分别为0.05:1.0:1.25:3.0;升温至80℃,搅拌反应1~4h,通过TLC跟踪反应情况,反应结束后静置冷却至室温。
(6)分离、干燥工艺:使用离心(8000rpm、10min)方式将催化剂分离出来,并使用无水乙醇、去离子水交替清洗分离出的催化剂3次。最后,将收集的催化剂在75℃下烘干16小时,收得钯负载量为1.05wt%的石墨烯催化剂。
对本发明实施例1、2制备的催化剂性能进行评价:在连接冷凝管的三口烧瓶中加入1mmol苯硼酸,1.25mmol溴苯,3mmol碳酸铯,钯纳米颗粒-石墨烯催化剂(Pd含量为0.005mmol),5mL无水乙醇,5mL去离子水,然后搅拌、升温至80℃,反应1~3小时,通过TLC跟踪反应情况,反应结束后冷却至室温,取样进行HPLC分析,结果见下图3;再采用离心分离方式,以进行催化剂循环反应。
对比实验:在氩气保护下,投入1mmol苯硼酸,1.25mmol溴苯,3mmol碳酸铯,醋酸钯(含钯为0.05mmol),5mL无水乙醇,5mL去离子水,然后搅拌、升温至80℃,反应1小时,通过TLC跟踪反应情况,反应结束后冷却至室温,取样进行HPLC分析;与实施例1、2中的对比结果如下表所示:
项目 | 催化剂用量 | 时间 | 温度 | 气氛 | 溶剂 | 转化率 | TON | TOF |
实施例1 | 0.5mol% | 1h | 80℃ | 空气 | EtOH:H<sub>2</sub>O=(1:1) | 100% | 200 | 200 |
实施例2 | 0.5mol% | 1h | 80℃ | 空气 | EtOH:H<sub>2</sub>O=(1:1) | 100% | 200 | 200 |
对比实验 | 5mol% | 1h | 80℃ | 氩气 | EtOH:H<sub>2</sub>O=(1:1) | 95% | 19 | 19 |
Claims (4)
1.一种石墨烯负载钯纳米颗粒复合材料催化剂的制备方法,所述催化剂由石墨烯载体和负载于载体上的钯纳米颗粒组成,其中钯的含量为催化剂的1.0~2.5wt%;其特征在于:所述制备方法包含以下步骤:
(1)步骤1、浸渍:按照载体与钯的质量比为400~1000:1,取适量的氧化石墨烯水溶液,并将其投入一定浓度的氯化钯溶液中,浸渍24~48小时;
(2)步骤2、喷雾干燥:将步骤1所得的混合溶液,使用喷雾干燥设备进行干燥处理,雾化过程液体流量为3.0~8.0ml/min,雾化气压为0.1~0.5MPa,进口温度为170~190℃,热空气气流量为4.0~10.0L/min,收得含钯的氧化石墨烯粉末;
(3)步骤3、高温还原:将步骤2所得含钯氧化石墨烯粉末用管式炉在H2气氛进行高温还原;
(4)步骤4、再浸渍:称取适量的醋酸钯,用体积比1:1的无水乙醇和去离子水进行溶解;然后再称取适量的步骤3中所制得的含钯的石墨烯粉末投入上述溶液中,保温30-50℃,并持续搅拌3~6h;
(5)步骤5、化学还原:再向步骤4中的含钯溶液投入苯硼酸、溴苯、碳酸铯,其摩尔比按照醋酸钯、苯硼酸、溴苯、碳酸铯分别为0.05:1.0:1.25:3.0;升温至80℃,搅拌反应1~4h,通过TLC跟踪反应情况,反应结束后静置冷却至室温;
(6)步骤6、分离干燥:使用离心分离方式将催化剂溶液中分离出,并使用无水乙醇、去离子水交替清洗所收集的固体3~5次;最后,将固体在50~80℃下烘干16~24小时。
2.根据权利要求1所述的石墨烯负载钯纳米颗粒复合材料催化剂的制备方法,其特征在于:
步骤3中的高温还原的温度为400~600℃、还原时间为1~3h。
3.根据权利要求1所述的一种石墨烯负载钯纳米颗粒复合材料催化剂的制备方法,其特征在于:
步骤4中的所述的含钯的石墨烯、醋酸钯的称取量根据石墨烯与钯的质量比决定,比例为40~100:1。
4.根据权利要求1所述的一种石墨烯负载钯纳米颗粒复合材料催化剂的制备方法,其特征在于:
步骤6中所述的离心分离参数为转速5000~8000rpm、持续时间5~10min。
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