CN106669840A - 一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂及其制备方法 - Google Patents
一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂及其制备方法 Download PDFInfo
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Abstract
本发明提供一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂及其制备方法，属于金属纳米材料催化技术领域。所述复合催化剂是聚苯胺与纳米钯粒子的复合物，呈网络状结构，且复合物中纳米钯被聚苯胺薄层所包覆。其具体制备过程是：室温下，将氯钯酸钠和聚苯胺、二丙二醇甲醚的N,N二甲基甲酰胺(DMF)溶液混合，搅拌30min后，缓慢滴加抗坏血酸/DMF混合溶液，30∽50℃下回流反应1h后，过滤获得不溶物，经洗涤、干燥后可得纳米钯/聚苯胺网络状复合催化剂。该催化剂制备过程方便、工艺简单；其在催化甲酸分解制氢中表现出良好的催化活性，可用于制氢反应及其它相关催化领域。
Description
技术领域
本发明属于金属纳米材料催化技术领域，具体涉及一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂及其制备方法。
背景技术
Pd基纳米复合催化剂可催化甲酸分解制氢、乙醇电氧化、Heck交叉偶联反应等多类化学与电化学反应，因此在化学、化工、材料等领域具有广泛的应用(张海博，刘一凡,朱轩伯,谭捷,丁连俊.藻土负载钯催化剂、制备方法及其应用，CN105772080A)。探索新颖Pd基复合催化剂及其制备方法，一直是纳米Pd催化领域的研究热点。
聚苯胺是一种应用广泛的导电聚合物，其具合成方便、成本低廉、稳定性好等特点。由于其可提供良好的导电环境，因此近年来常被用来作为贵金属纳米Pd催化剂的载体使用,促进Pd催化活性的提升(马先斌,冯媛媛,李扬,韩运石,鹿国萍,杨海芳,孔德生.聚苯胺对钯催化甲酸电氧化反应的促进作用，催化学报，2015,7,943-951；曾朝霞,杨元法,卢茂玲,蒋静.聚苯胺负载钯催化剂的制备及对Heck反应的催化性能，浙江师范大学学报，2006,29,431-434.)。这些研究的方法一般是先制备聚苯胺固体粉末，而后将贵金属纳米Pd粒子锚定在其表面，从而获得负载型复合催化剂。固然，上述复合型催化剂具有制备简单、适合规模化。然而这类负载时，多数情况只是纳米Pd粒子在聚苯胺上的轻度锚定和接触，因此还存在聚苯胺对纳米Pd金属的催化活性促进能力不高、纳米Pd粒子在催化反应中易团聚、致使催化活性稳定性欠佳等缺陷。
发明内容
本发明针对现有技术存在的以上问题，提供了一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂及其制备方法。
本发明提供了一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂，该复合催化剂是聚苯胺与纳米钯粒子的复合物，呈网络状结构，且复合物中纳米钯被聚苯胺薄层所包覆。
本发明同时提供了上述纳米钯@聚苯胺核/壳纳米粒子复合催化剂的制备方法，具体包括如下步骤：
(1)将经减压蒸馏后的苯胺单体加入1mol/L的盐酸溶液中，搅拌30min后，加入与苯胺单体相同摩尔数的过硫酸铵固体，室温下持续搅拌5h后，产品经过滤、洗涤、烘干后，得盐酸掺杂的聚苯胺固体粉末；所述苯胺单体与盐酸溶液的体积比为1:200。
(2)将步骤(1)制备的盐酸掺杂的聚苯胺固体粉末置于质量分数为2％的氨水溶液，搅拌过滤后再置于3mol/L NaOH水溶液，经大量水洗涤至洗涤液呈中性后干燥，获得处理后的聚苯胺粉末；所述盐酸掺杂的聚苯胺固体粉末与氨水溶液和NaOH水溶液的质量比均为1:20。
(3)室温下，将步骤(2)处理后的聚苯胺粉末0.5g溶于100ml DMF中，于25～90℃溶解12h，过滤除去不溶物，获得质量分数为0.005～0.02％的聚苯胺/DMF溶液，而后加入二丙二醇甲醚，得到混合溶液；所述二丙二醇甲醚在混合溶液中的质量分数为0.001％。
(4)称取一定量的氯钯酸钠溶于步骤(3)制备的混合溶液，搅拌得到A溶液；所述氯钯酸钠在A溶液中的质量分数为0.025～0.2％。
(5)按一定体积比，将抗坏血酸/DMF溶液缓慢滴加至A溶液，30～50℃下，反应1h后，过滤获得不溶物，经蒸馏水、乙醇洗涤，干燥后得到纳米钯@聚苯胺核/壳纳米粒子复合催化剂；所述抗坏血酸/DMF溶液质量分数为10～15％，所述抗坏血酸/DMF溶液和A溶液的体积比为1:15。
本发明一方面利用了导电聚苯胺高分子的结构指引作用，促使生成的复合材料具有特殊的网络结构；另一方面，在复合材料的形成过程中，利用聚苯胺大分子和钯的相互作用使其在纳米钯表面形成了薄层包覆，因而能充分发挥聚苯胺对纳米钯(核层)催化活性的促进作用，使复合材料展现优良的催化性能。
与现有技术相比，本发明具有以下技术效果：
1、所述复合催化剂催化性能优良，在64℃下，其催化甲酸分解制氢速率是商业化Pd/C催化剂(Aldrich公司，Pd含量为10％)的1.8-2.5倍。
2、该催化剂制备过程方便、工艺简单，可用于制氢反应及其它相关催化。
附图说明
图1为本发明实施例1制备的一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂透射电镜图片(放大倍数：1万倍)；
从图1中可以看出，复合催化剂呈网络状。
图2为本发明实施例1制备的一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂透射电镜图片(放大倍数：10万倍)；
图2确认了复合催化剂的网络状结构，可看出其由许多纳米粒子复合而成。
图3为本发明实施例1制备的一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂透射电镜图片(放大倍数：30万倍)；
从图3中可以看出，复合物中纳米钯(黑色)被聚苯胺薄层(浅色，约0.5～2.5nm)所包覆，形成了特殊的纳米钯(核)/聚苯胺(壳)结构。
具体实施方式
以下结合具体实施例详述本发明，但本发明不局限于下述实施例。
实施例1
1、将经减压蒸馏后的苯胺单体加入1mol/L的盐酸溶液中，搅拌30min后，加入与苯胺单体相同摩尔数的过硫酸铵固体，室温下持续搅拌5h后，产品经过滤、蒸馏水洗涤，并于60℃烘干后，得盐酸掺杂的聚苯胺固体粉末；所述苯胺单体与盐酸溶液的体积比为1:200。
2、将盐酸掺杂的聚苯胺固体粉末置于2％的氨水溶液，搅拌30min过滤后再置于3mol/L NaOH水溶液，经大量水洗涤至洗涤液呈中性，于60℃下干燥，获得处理后的聚苯胺粉末；所述盐酸掺杂的聚苯胺固体粉末与氨水溶液和NaOH水溶液的质量比均为1:20。
3、室温下，将处理后的聚苯胺粉末0.5g溶于100ml N,N二甲基甲酰胺(DMF)中，于25℃溶解12h,过滤除去不溶物，获得质量分数为0.005％的聚苯胺/DMF溶液，而后加入二丙二醇甲醚，得到混合溶液；所述二丙二醇甲醚在混合溶液中的质量分数为0.001％。
4、称取一定量的氯钯酸钠溶于步骤3制备的混合溶液，搅拌30min,得到A溶液。所述氯钯酸钠在A溶液中的质量分数为0.025％。
5、按一定体积比，将抗坏血酸/DMF溶液缓慢滴加至A溶液，30℃下，反应1h后，过滤获得不溶物，经大量蒸馏水、乙醇洗涤，干燥后得到纳米钯/聚苯胺网络状复合催化剂。所述抗坏血酸/DMF溶液质量分数为10％，所述抗坏血酸/DMF溶液和A溶液的体积比为1:15。
所得纳米钯/聚苯胺网络状复合催化剂在64℃下，其催化甲酸分解制氢速率是商业化Pd/C催化剂(Aldrich公司，Pd含量为10％)的2.5倍(通过气相色谱法测试，下同)。
实施例2
1、将经减压蒸馏后的苯胺单体加入1mol/L的盐酸溶液中，搅拌30min后，加入与苯胺单体相同摩尔数的过硫酸铵固体，室温下持续搅拌5h后，产品经过滤、蒸馏水洗涤，并于60℃烘干后，得盐酸掺杂的聚苯胺固体粉末；所述苯胺单体与盐酸溶液的体积比为1:200。
2、将盐酸掺杂的聚苯胺固体粉末置于2％的氨水溶液，搅拌30min过滤后再置于3mol/L NaOH水溶液，经大量水洗涤至洗涤液呈中性，于60℃下干燥，获得处理后的聚苯胺粉末；所述盐酸掺杂的聚苯胺固体粉末与氨水溶液和NaOH水溶液的质量比均为1:20。
3、室温下，将处理后的聚苯胺粉末0.5g溶于100ml N,N二甲基甲酰胺(DMF)中，于90℃溶解12h,过滤除去不溶物，获得质量分数为0.02％的聚苯胺/DMF溶液，而后加入二丙二醇甲醚，得到混合溶液；所述二丙二醇甲醚在混合溶液中的质量分数为0.001％。
4、称取一定量的氯钯酸钠溶于步骤3制备的混合溶液，搅拌30min,得到A溶液。所述氯钯酸钠在A溶液中的质量分数为0.2％。
5、按一定体积比，将抗坏血酸/DMF溶液缓慢滴加至A溶液，50℃下，反应1h后，过滤获得不溶物，经大量蒸馏水、乙醇洗涤，干燥后得到纳米钯/聚苯胺网络状复合催化剂。所述抗坏血酸/DMF溶液质量分数为15％，所述抗坏血酸/DMF溶液和A溶液的体积比为1:15。
所得纳米钯/聚苯胺网络状复合催化剂在64℃下，其催化甲酸分解制氢速率是商业化Pd/C催化剂(Aldrich公司，Pd含量为10％)的1.8倍。
实施例3
1、将经减压蒸馏后的苯胺单体加入1mol/L的盐酸溶液中，搅拌30min后，加入与苯胺单体相同摩尔数的过硫酸铵固体，室温下持续搅拌5h后，产品经过滤、蒸馏水洗涤，并于60℃烘干后，得盐酸掺杂的聚苯胺固体粉末；所述苯胺单体与盐酸溶液的体积比为1:200。
2、将盐酸掺杂的聚苯胺固体粉末置于2％的氨水溶液，搅拌30min过滤后再置于3mol/L NaOH水溶液，经大量水洗涤至洗涤液呈中性，于60℃下干燥，获得处理后的聚苯胺粉末；所述盐酸掺杂的聚苯胺固体粉末与氨水溶液和NaOH水溶液的质量比均为1:20。
3、室温下，将处理后的聚苯胺粉末0.5g溶于100ml N,N二甲基甲酰胺(DMF)中，于50℃溶解12h,过滤除去不溶物，获得质量分数为0.01％的聚苯胺/DMF溶液，而后加入二丙二醇甲醚，得到混合溶液；所述二丙二醇甲醚在混合溶液中的质量分数为0.001％。
4、称取一定量的氯钯酸钠溶于步骤3制备的混合溶液，搅拌30min,得到A溶液。所述氯钯酸钠在A溶液中的质量分数为0.1％。
5、按一定体积比，将抗坏血酸/DMF溶液缓慢滴加至A溶液，35℃下，反应1h后，过滤获得不溶物，经大量蒸馏水、乙醇洗涤，干燥后得到纳米钯/聚苯胺网络状复合催化剂。所述抗坏血酸/DMF溶液质量分数为10％，所述抗坏血酸/DMF溶液和A溶液的体积比为1:15。
所得纳米钯/聚苯胺网络状复合催化剂在64℃下，其催化甲酸分解制氢速率是商业化Pd/C催化剂(Aldrich公司，Pd含量为10％)的2倍。
实施例4
1、将经减压蒸馏后的苯胺单体加入1mol/L的盐酸溶液中，搅拌30min后，加入与苯胺单体相同摩尔数的过硫酸铵固体，室温下持续搅拌5h后，产品经过滤、蒸馏水洗涤，并于60℃烘干后，得盐酸掺杂的聚苯胺固体粉末；所述苯胺单体与盐酸溶液的体积比为1:200。
2、将盐酸掺杂的聚苯胺固体粉末置于2％的氨水溶液，搅拌30min过滤后再置于3mol/L NaOH水溶液，经大量水洗涤至洗涤液呈中性，于60℃下干燥，获得处理后的聚苯胺粉末；所述盐酸掺杂的聚苯胺固体粉末与氨水溶液和NaOH水溶液的质量比均为1:20。
3、室温下，将处理后的聚苯胺粉末0.5g溶于100ml N,N二甲基甲酰胺(DMF)中，于70℃溶解12h,过滤除去不溶物，获得质量分数为0.015％的聚苯胺/DMF溶液，而后加入二丙二醇甲醚，得到混合溶液；所述二丙二醇甲醚在混合溶液中的质量分数为0.001％。
4、称取一定量的氯钯酸钠溶于步骤3制备的混合溶液，搅拌30min,得到A溶液。所述氯钯酸钠在A溶液中的质量分数为0.15％。
5、按一定体积比，将抗坏血酸/DMF溶液缓慢滴加至A溶液，45℃下，反应1h后，过滤获得不溶物，经大量蒸馏水、乙醇洗涤，干燥后得到纳米钯/聚苯胺网络状复合催化剂。所述抗坏血酸/DMF溶液质量分数为12％，所述抗坏血酸/DMF溶液和A溶液的体积比为1:15。
所得纳米钯/聚苯胺网络状复合催化剂在64℃下，其催化甲酸分解制氢速率是商业化Pd/C催化剂(Aldrich公司，Pd含量为10％)的1.95倍。
实施例5
1、将经减压蒸馏后的苯胺单体加入1mol/L的盐酸溶液中，搅拌30min后，加入与苯胺单体相同摩尔数的过硫酸铵固体，室温下持续搅拌5h后，产品经过滤、蒸馏水洗涤，并于60℃烘干后，得盐酸掺杂的聚苯胺固体粉末；所述苯胺单体与盐酸溶液的体积比为1:200。
2、将盐酸掺杂的聚苯胺固体粉末置于2％的氨水溶液，搅拌30min过滤后再置于3mol/L NaOH水溶液，经大量水洗涤至洗涤液呈中性，于60℃下干燥，获得处理后的聚苯胺粉末；所述盐酸掺杂的聚苯胺固体粉末与氨水溶液和NaOH水溶液的质量比均为1:20。
3、室温下，将处理后的聚苯胺粉末0.5g溶于100ml N,N二甲基甲酰胺(DMF)中，于80℃溶解12h,过滤除去不溶物，获得质量分数为0.018％的聚苯胺/DMF溶液，而后加入二丙二醇甲醚，得到混合溶液；所述二丙二醇甲醚在混合溶液中的质量分数为0.001％。
4、称取一定量的氯钯酸钠溶于步骤3制备的混合溶液，搅拌30min,得到A溶液。所述氯钯酸钠在A溶液中的质量分数为0.2％。
5、按一定体积比，将抗坏血酸/DMF溶液缓慢滴加至A溶液，30℃下，反应1h后，过滤获得不溶物，经大量蒸馏水、乙醇洗涤，干燥后得到纳米钯/聚苯胺网络状复合催化剂。所述抗坏血酸/DMF溶液质量分数为15％，所述抗坏血酸/DMF溶液和A溶液的体积比为1:15。
所得纳米钯/聚苯胺网络状复合催化剂在64℃下，其催化甲酸分解制氢速率是商业化Pd/C催化剂(Aldrich公司，Pd含量为10％)的1.9倍。
Claims (2)
1.一种纳米钯@聚苯胺核/壳纳米粒子复合催化剂，其特征在于，所述复合催化剂是聚苯胺与纳米钯粒子的复合物，呈网络状结构，且复合物中纳米钯被聚苯胺薄层所包覆。
2.如权利要求1所述的纳米钯@聚苯胺核/壳纳米粒子复合催化剂的制备方法，其特征在于包括如下步骤：
(1)将经减压蒸馏后的苯胺单体加入1mol/L的盐酸溶液中，搅拌30min后，加入与苯胺单体相同摩尔数的过硫酸铵固体，室温下持续搅拌5h后，产品经过滤、洗涤、烘干后，得盐酸掺杂的聚苯胺固体粉末；
所述苯胺单体与盐酸溶液的体积比为1:200；
(2)将步骤(1)制备的盐酸掺杂的聚苯胺固体粉末置于质量分数为2％的氨水溶液，搅拌过滤后再置于3mol/L NaOH水溶液，经大量水洗涤至洗涤液呈中性后干燥，获得处理后的聚苯胺粉末；
所述盐酸掺杂的聚苯胺固体粉末与氨水溶液和NaOH水溶液的质量比均为1:20；
(3)室温下，将步骤(2)处理后的聚苯胺粉末0.5g溶于100ml DMF中，于25～90℃溶解12h，过滤除去不溶物，获得质量分数为0.005～0.02％的聚苯胺/DMF溶液，而后加入二丙二醇甲醚，得到混合溶液；
所述二丙二醇甲醚在混合溶液中的质量分数为0.001％；
(4)称取一定量的氯钯酸钠溶于步骤(3)制备的混合溶液，搅拌得到A溶液；
所述氯钯酸钠在A溶液中的质量分数为0.025～0.2％；
(5)按一定体积比，将抗坏血酸/DMF溶液缓慢滴加至A溶液，30～50℃下，反应1h后，过滤获得不溶物，经蒸馏水、乙醇洗涤，干燥后得到纳米钯@聚苯胺核/壳纳米粒子复合催化剂；
所述抗坏血酸/DMF溶液质量分数为10～15％，所述抗坏血酸/DMF溶液和A溶液的体积比为1:15。
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