CN107899598A - 一种钴、氮共掺杂的纳米粒子‑碳纳米管复合材料的制备方法 - Google Patents
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Abstract
本发明涉及一种钴、氮共掺杂的纳米粒子‑碳纳米管复合材料的制备方法，属于纳米复合材料制备技术领域。解决现有制备方法过程复杂，成本较高，需要特殊的贵重仪器，不利于大规模生产的问题。本发明提供的钴、氮共掺杂的纳米粒子‑碳纳米管复合材料的制备方法主要是以CdS纳米线、多巴胺和硝酸钴作为原料，在硝酸钴存在的条件下，在CdS纳米线外面包覆多巴胺，所得样品经过高温煅烧即可得到。通过控制CdS纳米线和硝酸钴的质量比，可以调节所得材料的形貌。该制备方法过程简单，成本低。所得复合材料具有较大的比表面积和丰富的介孔结构，使得材料具有很好的氧还原电催化性能，在燃料电池、生物传感、金属‑空气电池、超级电容器等领域有广泛的应用前景。
Description
技术领域
本发明属于纳米复合材料制备技术领域，具体涉及一种钴、氮共掺杂的纳米粒子-碳纳米管复合材料的制备方法。该方法简单便捷，便于大批量的制备、成本低。所制备的复合材料具有良好的电催化性能，在燃料电池、金属-空气电池、生物传感、超级电容器等领域有广泛的应用前景。
背景技术
碳纳米管具有比表面积大、导电性好和一维的孔结构等特点，被认为是一种非常理想的纳米载体及良好的催化剂载体。杂原子共掺杂的纳米粒子-碳纳米管复合材料，具有较大的比表面积、丰富的孔结构和良好的导电性等，在燃料电池、生物传感、超级电容器等方面具有独特的优势和良好的发展潜力。将零维的金属纳米粒子修饰到碳纳米管的表面可以获得性能优越的功能性纳米复合材料，可使活性金属的前驱体得到充分的分散，防止金属粒子烧结，由于碳纳米管与活性金属间的强相互作用，可以极大地促进催化剂的活性、选择性和稳定性。
目前，制备纳米粒子-碳纳米管复合材料的方法，比较局限，主要包括以下几种：1.化学镀法:是在无外加电流的情况下借助合适的还原剂，使镀液中金属离子还原成金属，并沉积到材料上的过程。如Guo等利用化学镀法将Pd纳米粒子沉积到碳纳米管上，并且探究了碳纳米管直径对于沉积结果的影响[Guo Y,Fhayli K,Li Song,Yang Y,RSC Advances2013,3,17693-17695.]；2.电化学沉积法：电化学沉积是指金属或合金或金属化合物在电场作用下从其化合物水溶液、非水溶液或熔盐中在电极表面沉积出来的电化学过程。如Quinn等利用电化学沉积方法合成了Au(Pt,Pd)-多壁碳纳米管复合材料[Quinn B,DekkerC,Lemay S，Journal of the American Chemical Society 2005,127,6146-6147.]；3.物理方法：包括溅射沉积、离子和电子束辐射沉积、气相蒸发沉积等，其优势在于可以有效调控金属纳米粒子的尺寸、形貌和在碳纳米管表面的分散性。如Soin等通过磁控溅射方法在垂直排列的碳纳米管表面获得均匀分散的粒径介于3～5nm的Pt纳米粒子[Soin N,Roy SS,Karlsson L,Diamond and Related Materials 2010,19,595-598.]。但是上述这些制备方法过程复杂，成本较高，需要特殊的贵重仪器、工艺复杂，不利于大规模生产。
发明内容
本发明要解决现有技术中的技术问题，提供一种钴、氮共掺杂的纳米粒子-碳纳米管复合材料的制备方法。该制备方法是以CdS纳米线作为牺牲模板，在其外表面包覆一层多巴胺，包覆的同时，向反应液中加入一定量的硝酸钴，将所得产物经过高温煅烧，就可以得到钴、氮共掺杂的纳米粒子-碳纳米管的复合材料，并且通过控制与调节CdS纳米线与硝酸钴的质量比，可以得到性能更加优异的钴、氮共掺杂的纳米粒子-碳纳米管复合材料。该制备方法简便可行，成本低，制得的复合材料表现出优异的氧还原电化学催化性能。该复合材料在燃料电池、生物传感、金属-空气电池、超级电容器等领域有广泛的应用前景。
为了解决上述技术问题，本发明的技术方案具体如下：
一种钴、氮共掺杂的纳米粒子-碳纳米管复合材料的制备方法，包括以下步骤：
步骤1、首先制备50～200mg嵌段共聚物聚(乙二醇)-聚(丙二醇)-聚(乙二醇)(P123)和120mg三(羟甲基)氨基甲烷(Tris)的混合水溶液，向该混合水溶液中加入0.01～1.00g硝酸钴，再将0.10～0.30g CdS纳米线加入到上述混合水溶液中，室温下搅拌；
步骤2、称取0.10～0.50g多巴胺溶于去离子水中，加入到步骤1得到的混合溶液中，室温下搅拌反应；
步骤3、将反应后的溶液，通过离心，洗涤，干燥后得到产物；
步骤4、将所得产物放在石英舟中，氮气保护下程序升温至900℃，热处理1～3h后即得到钴、氮共掺杂的纳米粒子-碳纳米管复合材料。
在上述技术方案中，所述CdS纳米线与硝酸钴的质量比为10:1、1:1、1:2或1:5。
本发明的有益效果是：
本发明提供的钴、氮共掺杂的纳米粒子-碳纳米管复合材料的制备方法，主要是以CdS纳米线、多巴胺和硝酸钴作为原料，在硝酸钴存在的条件下，在CdS纳米线外面包覆多巴胺，所得样品经过高温煅烧即可得到钴、氮共掺杂的纳米粒子-碳纳米管复合材料。通过控制CdS纳米线和硝酸钴的质量比，可以调节所得材料的形貌，只有在最佳比例下，才能得到形貌均一的钴、氮共掺杂的纳米粒子-碳纳米管复合材料。该制备方法过程简单，成本低。此外，所得到的复合材料，由于具有较大的比表面积和丰富的介孔结构，使得材料具有很好的氧还原电催化性能，可以广泛适用于氧还原、氧析出、燃料电池以及氢气析出等方面。该制备方法制备的复合材料在燃料电池、生物传感、金属-空气电池、超级电容器等领域有广泛的应用前景。
附图说明
下面结合附图和具体实施方式对本发明作进一步详细说明。
图1是本发明实施例1方法制备的复合材料的透射电镜(TEM)图；
图2是本发明实施例2方法制备的复合材料的TEM图；
图3是本发明实施例3方法制备的复合材料的TEM图；
图4是本发明实施例4方法制备的复合材料的TEM图；
图5是本发明实施例2方法制备的复合材料的X射线衍射图(XRD)图；
图6是在N2、O2下测试本发明实施例2方法制备的复合材料的电催化氧还原过程的循环伏安曲线。
具体实施方式
下面结合附图对本发明做以详细说明。
所用原料多巴胺(购于阿拉丁试剂)、硝酸钴(购于国药试剂)。
实施例1
原料比例：CdS纳米线和硝酸钴的质量比10:1，形貌见附图1。
1)将50mg P123、120mg Tris和0.01g硝酸钴溶解于100mL去离子水中，再将0.10gCdS纳米线加入到上述溶液中，室温下搅拌；
2)称取0.10g多巴胺溶解到50mL去离子水中，加入到上述溶液中，室温下搅拌反应；
3)将反应后的溶液，进行离心，用乙醇洗涤数次，之后在烘箱内进行干燥，得到产物；
4)将所得产物放入石英舟中，氮气保护下程序升温至900℃，热处理2h，即得到钴、氮共掺杂的纳米粒子-碳纳米管复合材料。
实施例2
原料比例，CdS纳米线和硝酸钴的质量比1:1，形貌见附图2。
1)将100mg P123、120mg Tris和0.10g硝酸钴溶解于100mL去离子水中，再将0.10gCdS纳米线加入到上述溶液中，室温下搅拌；
2)称取0.20g多巴胺溶解到50mL去离子水中，加入到上述溶液中，室温下搅拌反应；
3)将反应完的溶液，进行离心，用乙醇洗涤数次，之后在烘箱内进行干燥，得到产物；
4)将所得产物放入石英舟中，氮气保护下程序升温至900℃，热处理2h，即得到钴、氮共掺杂的纳米粒子-碳纳米管复合材料。
通过测试发现，本实施例所制备的复合材料的比表面积为661.2m2g-1，而且存在大量的介孔结构。图5是本实施例得到的复合材料的X射线衍射(XRD)图谱，由XRD图，我们可以发现，图中出现了明显的金属硫化物的特征峰以及明显的石墨化的碳的特征峰，这表明通过该方法成功地制备出了共掺杂的纳米粒子-碳纳米管的复合材料，位于26°的特征峰对应于石墨化的碳的(002)的衍射峰，其他峰为金属硫化物的衍射峰。图6是本实施例得到的复合材料的电催化氧还原过程的循环伏安曲线，该图表明该复合材料均有良好的电催化氧还原催化性能，表现出很好的氧还原峰电位以及较大的峰电流密度。
实施例3
原料比例，CdS纳米线和硝酸钴的质量比1:2，形貌见附图3。
1)将160mg P123、120mg Tris和0.60g硝酸钴溶解于100mL去离子水中，再将0.30gCdS纳米线加入到上述溶液中，室温下搅拌；
2)称取0.30g多巴胺溶解到50mL去离子水中，加入到上述溶液中，室温下搅拌反应；
3)将反应完的溶液，进行离心，用乙醇洗涤数次，之后在烘箱内进行干燥，得到产物；
4)将所得产物放入石英舟中，氮气保护下程序升温至900℃，热处理1h，即得到钴、氮共掺杂的纳米粒子-碳纳米管复合材料。
实施例4
原料比例，CdS纳米线和硝酸钴的质量比1:5，形貌见附图4。
1)将200mg P123、120mg Tris和1.00g硝酸钴溶解于100mL去离子水中，再将0.20gCdS纳米线加入到上述溶液中，室温下搅拌；
2)称取0.50g多巴胺溶解到50mL去离子水中，加入到上述溶液中，室温下搅拌反应；
3)将反应完的溶液，进行离心，用乙醇洗涤数次，之后在烘箱内进行干燥，得到产物；
4)将所得产物放入石英舟中，氮气保护下程序升温至900℃，热处理3h，即得到钴、氮共掺杂的纳米粒子-碳纳米管复合材料。
由图1-4，我们可以发现，适当控制CdS纳米线和硝酸钴的质量比，可以有效控制所制备的复合材料的形貌。当CdS纳米线和硝酸钴的质量比为10:1时，碳纳米管外面只生长了很少的纳米粒子；当CdS纳米线和硝酸钴的质量比为1:1时，适量的纳米粒子均匀分布在碳纳米管外面；当CdS纳米线和硝酸钴的质量比继续增加到1:2和1:5时，大量纳米粒子分布在碳纳米管外部。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (2)
1.一种钴、氮共掺杂的纳米粒子-碳纳米管复合材料的制备方法，其特征在于，包括以下步骤：
步骤1、首先制备50～200mg嵌段共聚物聚(乙二醇)-聚(丙二醇)-聚(乙二醇)(P123)和120mg三(羟甲基)氨基甲烷(Tris)的混合水溶液，向该混合水溶液中加入0.01～1.00g硝酸钴，再将0.10～0.30g CdS纳米线加入到上述混合水溶液中，室温下搅拌；
步骤2、称取0.10～0.50g多巴胺溶于去离子水中，加入到步骤1得到的混合溶液中，室温下搅拌反应；
步骤3、将反应后的溶液，通过离心，洗涤，干燥后得到产物；
步骤4、将所得产物放在石英舟中，氮气保护下程序升温至900℃，热处理1～3h后即得到钴、氮共掺杂的纳米粒子-碳纳米管复合材料。
2.根据权利要求1所述的制备方法，其特征在于，所述CdS纳米线与硝酸钴的质量比为10:1、1:1、1:2或1:5。
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