CN113856758A - 一种金属复合Janus聚合物纳米颗粒催化剂及其制备方法和应用 - Google Patents
一种金属复合Janus聚合物纳米颗粒催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于纳米材料催化剂技术领域,具体为一种纳米尺度金属复合Janus聚合物颗粒催化剂及其制备方法和应用。本发明以含羧基的及可被羧基改性的嵌段聚合物为原料,通过加入小分子无机碱使聚合物链发生电离,使不同高分子链段因静电排斥作用分隔开;再通过加入过渡金属盐使聚合物发生分子内配位交联,原位还原后得到金属复合Janus聚合物纳米颗粒。本发明制备工艺简单,适于大批量生产。所得的纳米催化剂具有高的催化反应活性和重复利用率,能高效地用于均相催化还原芳香硝基化合物,还能在油/水混合乳液环境中用于芳香硝基化合物催化还原。
Description
技术领域
本发明属于纳米材料催化剂技术领域,具体涉及一种纳米尺度金属复合Janus聚合物颗粒催化剂及其制备方法和应用。
背景技术
在现代工业社会中,约百分之九十的工业生产需要使用催化剂来提高反应速率及化学选择性,从而加速目标反应进程(A. Q. Wang, J. Li, T. Zhang, Nat. Rev. Chem.2018, 2, 65-81)。研究发现,减小金属催化剂尺寸到纳米级别时,可有效提高原子利用率,有望获得高催化活性和化学反应选择性的特质(X. F. Yang, A. Q. Wang, B. T. Qiao,T. Zhang, Acc. Chem. Res. 2013, 46, 1740-1748)。Janus材料是一类在形貌结构或化学组成上具有明显分区的不对称材料(F. X. Liang, Z. Z. Yang, Acta PolymericaSinica, 2017, 6, 883-892),其独特的微结构能够用于活性金属组分的负载,在油水混合物体系中表现出远优于各向同性的均质载体的催化性能。其中,纳米尺度的Janus聚合物粒子在药物传递、催化、表面活性剂等方面的潜在应用而受到广泛关注(A. Walther, A. H.E. Muller, Soft Matter 2008, 4, 663-668)。分子内交联技术可用于直接制备小尺寸的Janus聚合物纳米粒子,但是该方法通常要求反应体系中聚合物处于极稀浓度,这限制了它的大批量生产(S. Mavila, O. Eivgi, I. Berkovich, N. G. Lemcoff, Chem. Rev.2016, 116, 878-961)。
如果设计一些具有特定官能团的聚合物,能够在小分子作用下发生电离产生电荷,使得带电链段即使在浓溶液中也能由于静电排斥作用而隔开,之后在金属离子的作用下实现分子内配位交联,原位还原后即得到金属复合Janus聚合物纳米颗粒。该方法一方面能制备尺度小于10 nm的金属粒子,并且聚合物链段形成的交联网络能阻止金属纳米粒子之间的团聚。另一方面还可以实现纳米尺度的金属复合Janus聚合物粒子的批量制备。
发明内容
针对现有技术存在的问题,结合聚合物的组成结构及金属纳米粒子高催化活性的优势,本发明的目的是提供一种纳米尺度可调、产率高的金属复合Janus聚合物纳米颗粒催化剂及其制备方法,和在芳香硝基化合物催化还原反应中的应用。
本发明所述的金属复合Janus聚合物纳米颗粒催化剂,是聚合物经金属离子分子内配位交联并原位还原后形成的纳米颗粒。
本发明提供的金属复合Janus聚合物纳米颗粒催化剂的制备方法,具体步骤为:
(1)将聚合物溶解在有机溶剂中;
(2)将无机碱加入步骤(1)的溶液中,使聚合物链段电离形成电荷排斥;
(3)将金属盐加入步骤(2)的溶液中,使聚合物发生分子内配位交联反应;
(4)加入还原剂使金属离子原位还原,形成金属纳米颗粒;
(5)采用透析和冷冻干燥对步骤(4)的产物进行提纯。
步骤(1)中,所述聚合物为AB型嵌段共聚物;所述A链段为聚苯乙烯、聚甲基苯乙烯、聚苄基氯苯乙烯中的一种;所述B链段为聚丙烯酸、聚甲基丙烯酸、聚异戊二烯、聚丙烯酸叔丁酯、聚甲基丙烯酸叔丁酯、聚丙烯酸甲酯和聚甲基丙烯酸甲酯中的一种。
所述B链段为聚异戊二烯时,需用巯基乙酸对其进行羧基改性;当B链段为聚丙烯酸叔丁酯、聚甲基丙烯酸叔丁酯、聚丙烯酸甲酯和聚甲基丙烯酸甲酯中的一种时,需用三氟乙酸对酯进行水解转化为羧基。
所述有机溶剂为N,N-二甲基甲酰胺(DMF)、四氢呋喃(THF)、二甲基亚砜(DMSO)、二氧六环中的一种。
所述聚合物的浓度为0.01~50 mg/mL,优选在0.05~30 mg/mL。
步骤(2)中,所述无机碱为氢氧化钠和氢氧化钾中的一种。
所述无机碱中氢氧根基团与聚合物中羧基的摩尔比为0.1:1~1:1。
步骤(2)反应条件为:温度25~40℃,反应时间6~24小时。
步骤(3)中,所述金属化合物为过渡金属化合物,作为优选,为钯、钴和镍的金属化合物中的一种。
进一步,作为优选,所述钯、钴和镍的金属化合物为氯化钯,硝酸钴、氯化钴、硝酸镍、氯化镍中的一种。
步骤(3)中,金属盐的用量为金属盐与聚合物中羧基的摩尔比为0.1:1~0.5:1。
步骤(3)中,反应条件为温度20~40℃,反应时间6~24小时。
步骤(4)中,所述还原剂为壳聚糖、抗坏血酸、硼烷衍生物中的一种。
所述还原剂的用量为金属化合物的2~8倍当量。
步骤(5)中,所述透析相对去离子水,透析时间为12~48h。冷冻干燥时间为24~72h。
本发明所制备的金属复合Janus聚合物纳米颗粒催化剂,其颗粒尺寸小(<10 nm),具有高的金属原子利用率和高的催化反应活性。该纳米催化剂兼具Janus聚合物纳米颗粒的两亲性,可高效地用于均相催化还原芳香硝基化合物反应中,还可用于油/水混合乳液环境中高效催化还原芳香硝基化合物的反应中。
与现有技术相比,本发明具有如下优点:制备工艺简单,适于大批量生产。所得的纳米催化剂,其纳米尺度可调,合成产率高,具有高的催化反应活性和高的重复利用率,具有工业化推广前景。
附图说明
图1为本发明金属钯复合Janus聚合物纳米颗粒的TEM图。
图2为本发明金属钴复合Janus聚合物纳米颗粒催化还原硝基苯酚的转化率-循环次数图。
图3为本发明金属镍复合Janus聚合物纳米颗粒均相催化还原硝基苯的转化率-时间图。
图4为本发明金属钯复合Janus聚合物纳米颗粒乳液界面催化还原硝基苯的转化率-时间图。
具体实施方式
下面结合具体实施例,进一步阐述本发明,应理解这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明做各种改动或修改,这些等价形式同样落于本申请所附的权利要求书限定的范围内。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述是实例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1,金属钴复合Janus聚合物纳米颗粒的制备。
取30 mg PVBC20k-b-PAA5k固体溶解于2 mL THF中,按与羧基摩尔比0.8﹕1的比例加入氢氧化钾,25℃恒温快速搅拌6小时;在上述体系中,按与羧基摩尔比0.4﹕1的比例将加入氯化钴(CoCl2),25℃恒温快速搅拌24小时;往上述溶液中加入5倍金属当量的NaBH4,25℃恒温快速搅拌24小时。将反应液透析24小时后冷冻干燥得到金属钴复合Janus聚合物纳米颗粒。图1是实施例中金属钴复合Janus聚合物纳米颗粒的TEM图。
实施例2,金属镍复合Janus聚合物纳米颗粒的制备。
取30 mg PS5.2k-b-PAA4k固体溶解于1 mL DMF中,按与羧基摩尔比0.6﹕1的比例加入氢氧化钠,25℃恒温快速搅拌6小时;在上述体系中,按与羧基摩尔比0.2﹕1的比例加入硝酸镍(Ni(NO3)2),25℃恒温快速搅拌24小时;往上述溶液中加入5倍金属当量的NaBH4,25℃恒温快速搅拌24小时。将反应液透析24小时后冷冻干燥得到金属镍复合Janus聚合物纳米颗粒。
实施例3,金属钯复合Janus聚合物纳米颗粒的制备
PS20k-b-PI20k先用巯基乙酸对侧链双键进行羧基改性并提纯。取30 mg改性后的聚合物溶于2 mL DMF,按与羧基摩尔比1﹕1的比例加入氢氧化钠,25℃恒温快速搅拌6小时;在上述体系中,按与羧基摩尔比0.3﹕1的比例加入氯化钯(PdCl2);往上述溶液中加入5倍金属当量的抗坏血酸,25℃恒温快速搅拌24小时。将反应液透析24小时后冷冻干燥得到金属钯复合Janus聚合物纳米颗粒。
实施例4,均相催化还原对硝基苯酚
取实施例1中的金属钴复合Janus聚合物纳米颗粒3 mg超声分散于10 mL无水乙醇中,依次加入 0.2 mmol对硝基苯酚和 4 mmol NaBH4,置于25℃恒温反应。每隔一段时间离心分离并测量离心液的UV曲线,用以监测对硝基苯酚的还原程度。金属钯复合Janus聚合物纳米颗粒催化还原硝基苯酚的转化率随时间变化图,见图2所示。
实施例5,均相催化还原硝基苯
取实施例2中的金属镍复合Janus聚合物纳米颗粒3 mg超声分散于10 mL无水乙醇中,依次加入 0.2 mmol硝基苯和 4 mmol NaBH4,每隔一段时间离心分离并利用气相色谱监测硝基苯的还原程度。金属镍复合Janus聚合物纳米颗粒催化还原硝基苯的转化率-循环次数,见图3所示。
实施例6,乳液界面催化还原硝基苯
取实施例3中的金属钯复合Janus聚合物纳米颗粒3 mg超声分散于1 mL正癸烷/甲苯的混合液中(v/v=1:1),加入0.2 mmol硝基苯;再加入含有4 mmol NaBH4的10 mL水溶液,剧烈摇晃形成水包油乳液。每隔一段时间离心分离并利用气相色谱监测硝基苯的还原程度。金属钯复合Janus聚合物纳米颗粒催化还原硝基苯的转化率时间变化图,见图4所示。
Claims (10)
1.一种金属复合Janus聚合物纳米颗粒催化剂的制备方法,其特征在于,具体步骤为:
(1)将聚合物溶解在有机溶剂中;
(2)将无机碱加入步骤(1)的溶液中,使聚合物链段电离形成电荷排斥;
(3)将金属盐加入步骤(2)的溶液中,使聚合物发生分子内配位交联反应;
(4)加入还原剂使金属离子原位还原,形成金属纳米颗粒;
(5)采用透析和冷冻干燥对步骤(4)的产物进行提纯;
步骤(1)中,所述聚合物为AB型嵌段共聚物;所述A链段为聚苯乙烯、聚甲基苯乙烯、聚苄基氯苯乙烯中的一种;所述B链段为聚丙烯酸、聚甲基丙烯酸、聚异戊二烯、聚丙烯酸叔丁酯、聚甲基丙烯酸叔丁酯、聚丙烯酸甲酯和聚甲基丙烯酸甲酯中的一种;
所述聚合物的浓度为0.01~50 mg/mL;
步骤(2)中,所述无机碱为氢氧化钠和氢氧化钾中的一种;所述无机碱中氢氧根基团与聚合物中羧基的摩尔比为0.1:1~1:1;
步骤(3)中,所述金属化合物为过渡金属化合物,选自钯、钴和镍的金属化合物中的一种;
步骤(4)中,所述还原剂为壳聚糖、抗坏血酸、硼烷衍生物中的一种。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,当所述B链段为聚异戊二烯时,用巯基乙酸对其进行羧基改性;当所述B链段为聚丙烯酸叔丁酯、聚甲基丙烯酸叔丁酯、聚丙烯酸甲酯和聚甲基丙烯酸甲酯中的一种时,用三氟乙酸对酯进行水解转化为羧基。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述有机溶剂为N,N-二甲基甲酰胺、四氢呋喃、二甲基亚砜、二氧六环中的一种。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,反应条件为:温度25~40℃,反应时间6~24小时。
5.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,所述钯、钴和镍的金属化合物为氯化钯,硝酸钴、氯化钴、硝酸镍、氯化镍中的一种。
6.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,反应条件为:温度20~40℃,反应时间6~24小时。
7.根据权利要求1所述的制备方法,其特征在于,步骤(4)中,所述还原剂的用量为金属化合物的2~8倍当量。
8.根据权利要求1所述的制备方法,其特征在于,步骤(5)中,所述透析相对去离子水,透析时间为12~48h。冷冻干燥时间为24~72h。
9. 由权利要求1-8之一所述制备方法得到的金属复合Janus聚合物纳米颗粒催化剂,其颗粒尺寸小于10 nm。
10.如权利要求9所述的金属复合Janus聚合物纳米颗粒催化剂在均相催化还原芳香硝基化合物反应中的应用,或在油/水混合乳液环境中催化还原芳香硝基化合物反应中的应用。
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