CN110642240A - 一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法 - Google Patents
一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法 Download PDFInfo
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Abstract
本发明提供一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法，属于材料制备技术领域。本发明是以化学法或者物理法制备的尺寸小于100nm的Fe‑Sn‑O纳米颗粒为催化剂，并利用简易方式使其堆积接触，后利用所制备催化剂采用热CVD法高效合成的碳纳米线圈。本发明提供的方法工艺简单，成本低，另外本发明揭示了一种新颖的碳纳米线圈生长的机理，使得制备出的用于生长碳纳米线圈的催化剂更高效，并易于工业化宏量生产。
Description
技术领域
本发明属于材料制备技术领域，涉及一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法。
背景技术
具有螺旋形貌的碳纳米线圈(CNC)具备独特的物理、化学性质，在复合材料、储能、应变传感器、电磁吸收材料、MEMS系统中都有广泛的应用前景，因此高效制备CNCs对于拓展其应用领域至关重要，而高效制备的前提是对其合成的机理有全面清晰的认识。
化学气相沉积法(CVD法)是最适合大规模高效制备CNC的生产方法，其中催化剂活性的优劣则是影响合成效率的重中之重。目前对CNC生长用催化剂的合成、应用及机理研究都集中于对单粒催化剂的催化活性的各向异性的研究和应用，即单粒催化剂的形貌、晶面、组分以及尺寸对CNC生长影响的研究和应用[出版物：Liu,Wen-Chih,et al.Acs Nano 4.7(2010):4149-4157；Wang,Guizhen,et al.ACS nano 8.5(2014):5330-5338.]。此外，研究表明尺寸在100-200nm的单粒催化剂适合弹簧状CNC生长[出版物：Qian,Juanjuan,etal.Journal of nanoscience and nanotechnology 10.11(2010):7366-7369.]，其它粒径的催化剂只能生长为其他形态的碳纳米材料；另一方面，Fe/Sn催化剂因其制备成本低廉，原料来源广泛且催化活性高被广泛研究，目前报道的Fe/Sn催化剂通常是利用含Fe/Sn的前驱体溶液利用溶胶凝胶法、热共沉积法制备适合碳纳米线圈生长的催化剂颗粒(100-200nm)，但这些方法制备的催化剂往往粒径分布广、比表面积小、催化剂中有效成分低，严重制约了碳纳米线圈的高效生产。因此，如何高效制备尺寸、组分合适的催化剂成为目前研究和应用的重点以及难点。
发明内容
本发明的目的是针对目前高效合成碳纳米线圈过程中，催化剂合成过程复杂、效率低这一问题，提供一种聚集小尺寸催化剂颗粒的方法，通过多颗小尺寸催化剂之间的复合协同催化高效生长的碳纳米线圈的方法。与之前报道的由单个纳米颗粒作催化剂生长CNC不同，本专利是由两个以上的尺寸为100nm以下催化剂颗粒作为复合催化剂协同生长CNC的方法，通过改变催化剂堆积密度的方式现实多颗粒催化剂复合催化生长，相比大尺寸催化剂(大于100nm),小颗粒催化剂比表面积更大，其与碳源气体接触更充分，从而实现对CNC高效制备。
为了达到上述目的，本发明采用的技术方案为：
一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法，该方法首先制备尺寸小于100nm的Fe-Sn-O纳米颗粒，Fe/Sn催化剂因其制备成本低廉，原料来源广泛且催化活性高被广泛研究。以此为催化剂，并利用简易方式使其堆积接触，再利用所制备催化剂采用热CVD法高效合成的碳纳米线圈。具体包括以下步骤：
(1)制备的碳纳米线圈所用小尺寸催化剂
采用Fe3+盐或铁的氧化物和可溶性Sn4+盐或锡的氧化物为原料，采用化学合成法、物理法或化学合成法与物理法相互组合的方法制备复合催化剂粉末，所述复合催化剂粉末由Fe-Sn-O组成，催化剂中Fe：Sn的摩尔比为5:1-30:1，催化剂颗粒尺寸为10-100nm。
(2)采用合成的复合催化剂利用化学气相沉积技术复合催化高效生长碳纳米线圈
将制备得到的复合催化剂粉末分散至水或乙醇等溶剂中，其中分散液浓度为0.01mg-1mg/ml，清洗担载衬底。将催化剂分散液滴涂、旋涂或喷涂至衬底表面，其中催化剂在衬底表面密度范围在1×109/cm-2—5×1010/cm-2，实现催化剂颗粒在基板上的均匀担载及相互堆积接触。将干燥后将其放至于CVD系统中利用化学气相沉积技术合成高纯度(纯度大于95％)碳纳米线圈。
进一步的，步骤(1)中所述的制备过程中使用的可溶性Fe3+盐包括但不限于氯化铁、硝酸铁、硫酸铁等；可溶性Sn4+盐包括氯化锡；Sn4+盐与Fe3+盐可以任意组合；步骤(1)中所述的铁的氧化物为Fe2O3，锡的氧化物为SnO2。
进一步的，步骤(1)中所述的化学合成法包括水热法、溶剂热法等；物理法包括热蒸镀、磁控溅射、高速球磨法等。
进一步的，步骤(2)中所述的衬底包括石英片、硅片、SiO2片、石墨基板、不锈钢或氧化铝基板等。
本发明方法可以高效制备碳纳米线圈的原理可总结为：所述催化剂合成碳纳米线圈的机理是利用各催化剂纳米粒子的催化活性不同而造成整个复合催化剂的催化活性的各向异性。具体为：小尺寸的Fe-Sn催化剂相互堆积接触，在高温下当碳源气体在催化剂表面裂解、渗碳和析碳的过程中，附近数颗催化剂自然团聚并通过碳相互结合，形成复合催化剂，其中从不同催化剂小颗粒生长出的形貌不同的纤维(管)状碳纳米线相互粘连，同时不同催化剂小颗粒因其尺寸、形貌、组分差异导致碳源气体裂解、渗碳和析碳的速度产生差异，使得长出的复合碳纳米线为螺旋结构，即碳纳米线圈。
本发明的有益效果：小尺寸的催化剂具有较高的比表面积，使得其催化活性更高，效率更好，产物纯度更高。
附图说明
图1为实施实例1制备的催化剂粉末的EDS元素分析测试图谱。
图2为实施实例1中a、b两步制备催化剂粉末的透射电镜图。
图3为实施实例1中催化剂分散液旋涂30次后制备的CNC宏观SEM图像(a)以及单根CNC顶部催化剂SEM图(b)。
图4为实施实例1中催化剂旋涂30次后典型产物的TEM图。
图5为实施实例2中a、b两步制备催化剂粉末的透射电镜图。
图6为实施实例2中催化剂分散液喷涂20次后制备的CNC宏观SEM图像(a)以及单根CNC顶部催化剂SEM图(b)。
图7为实施实例3中a、b两步制备催化剂粉末的扫描电镜图。
图8为实施实例3中催化剂分散液滴涂10次后制备的CNC宏观SEM图像(a)以及单根CNC顶部催化剂SEM图(b)。
具体实施方式
通过参考以下对实施方案、对照实施方案和附图的详细描述可以更容易地理解本发明。然而，本发明可以有许多不同的形式实施，不应被解释为限于本文所阐述的实施方案。这些实施例旨在使本发明的公开内容完整并且告知本发明所属领域的技术人员本发明的范围。本发明仅由权利要求的范围限定。在整个说明书中相同的附图标记表示相同的元件。
在下文中，将参照附图详细描述本发明的优选实施方案，即小颗粒催化剂协同催化高效合成碳纳米线圈。下文所述实例中，CVD合成碳纳米线圈的过程为，以乙炔(C2H2)为碳源，流速为15sccm，氩气(Ar)为保护气，流量为245sccm，反应温度为710℃，反应时间为30min。待反应结束后自然降温。
实施实例1：
(1)水热法(化学法)制备小尺寸催化剂
本实例合成步骤分为a、b两步：(a)将1.2g Fe(NO3)3·9H2O和溶于20ml去离子水中，超声至混合溶液完全溶解后15ml氨水(质量分数15％)，超声溶解均匀，将混合分散均匀后的混合溶液转移至高压反应釜内，反应温度在140℃，反应时间为12小时，自然冷却到室温，将所得的红色沉淀过滤，洗涤，干燥，得到单一红色粉末。
(b)取上步制备的红色粉末20mg超声分散在30ml水中，加入0.2g SnCl4·5H2O待充分溶解后逐滴滴加1mol/L的NaOH溶液调整PH至10，将混合分散均匀后的混合溶液转移至高压反应釜内，反应温度在200℃，反应时间为1.5小时，得到的产物Fe、Sn摩尔比为20:1，自然冷却到室温，将所得的红色沉淀过滤，洗涤，干燥，得到单一红色粉末。
附图1为催化剂粉末的以及EDS元素分析测试，结果表明红色粉末主要由Fe、Sn、O三种元素组成；附图2是制备催化剂粉末的透射电镜图(TEM)，图中可见催化剂颗粒分布范围为70-100nm之间。
(2)使用上述催化剂制备碳纳米线圈
准确称取步骤(1)制备的催化剂粉末分散至酒精中(浓度为：0.1mg/ml)，取反应担载衬底硅片分别用丙酮、酒精、去离子水清洗后干燥待用。量取0.2ml催化剂分散液旋涂至衬底表面(转速:2000/分钟)，上述过程重复30次，附图3(a)为旋涂30次催化剂的基板CVD反应后的产物SEM照片，CNC纯度高于95％，附图3(b)CNC的顶部催化剂的SEM照片，从图中可以看到CNC顶端的催化剂为多颗小颗粒聚集状态，与之前公开的单一颗粒的催化剂的生长机理有显著不同。附图4为典型产物的TEM图，图中可见催化剂是由大小不等的4颗催化剂组成，各个催化剂的形貌尺寸等特性的不同导致其催化活性有差异从而引起CNC的各项异性生长。
实施实例2：
(1)溶剂热法(化学法)制备所用小尺寸催化剂
本实例合成步骤分为a、b两步：(a)将0.526gFe2(SO4)3·7H2O加入35mlN，N-二甲基甲酰胺中，超声至混合溶液完全溶解，最后加入0.8g聚乙烯吡咯烷酮(PVP)待完全溶解后，转移至反应釜内，在溶剂热体系中控制反应温度在180℃，反应时间为6小时，自然冷却到室温，将所得的红色沉淀过滤，洗涤，干燥，得到单一红色粉末。
(b)取上步制备的红色粉末20mg超声分散在30ml水中，加入0.2g SnCl4·5H2O待充分溶解后逐滴滴加1mol/L的NaOH溶液调整PH至10，将混合分散均匀后的混合溶液转移至高压反应釜内，反应温度在200℃，反应时间为2小时，得到的产物Fe、Sn摩尔比为10:1，自然冷却到室温，将所得的红色沉淀过滤，洗涤，干燥，得到单一红色粉末。附图5是a、b两步制备催化剂粉末的透射电镜图(TEM)，图中可见催化剂颗粒分布范围为30-50nm之间。
(2)使用上述催化剂高效制备碳纳米线圈
准确称取步骤(1)制备的催化剂粉末分散至酒精中(浓度为：0.1mg/ml)，取反应担载衬底硅片分别用丙酮、酒精、去离子水清洗后干燥待用。量取0.1ml催化剂分散液喷涂至衬底表面，上述过程重复20次，待干燥后将担载催化剂的衬底至于CVD系统中反应，附图6(a)为旋涂30次催化剂的基板CVD反应后的产物SEM照片，CNC纯度高于95％，附图3(b)CNC的顶部催化剂的SEM照片，从图中可以看到CNC顶端的催化剂为多颗小颗粒聚集状态，说明该碳纳米线圈的催化剂是由多颗小尺寸的催化剂堆叠而成。
实施实例3：
(1)物理溅射法(化学-物理法结合)制备碳纳米线圈所用小尺寸催化剂
本实例合成步骤分为a、b两步：(a)将0.270gFeCl3·6H2O加入35mlN，N-二甲基甲酰胺中，超声至混合溶液完全溶解，最后加入0.8g聚乙烯吡咯烷酮(PVP)待完全溶解后，转移至反应釜内，在溶剂热体系中控制反应温度在180℃，反应时间为6小时，自然冷却到室温，将所得的红色沉淀过滤，洗涤，干燥，得到单一红色粉末。
(b)准确称取步骤(a)制备的催化剂粉末分散至酒精中(浓度为：0.1mg/ml)，取反应担载衬底硅片分别用丙酮、酒精、去离子水清洗后干燥待用。量取0.1ml催化剂分散液滴涂至衬底表面，干燥后将衬底放入磁控溅射仪中复合SnO2，具体参数为：工作电流为60mA、工作电压为40mV、工作功率为20W、沉积时间为3min。铁锡原子摩尔比为30:1，附图8是a、b两步制备催化剂粉末的扫描电镜图，图中可见催化剂颗粒分布范围为30-50nm之间。
(2)使用上述催化剂制备高纯度碳纳米线圈
上述步骤b重复10次，待干燥后将担载催化剂的衬底至于CVD系统中反应，附图3(a)为旋涂30次催化剂的基板CVD反应后的产物SEM照片，CNC纯度高于95％，附图3(b)CNC的顶部催化剂的SEM照片，从图中可以看到CNC顶端的催化剂为多颗小颗粒聚集状态，说明该碳纳米线圈的催化剂是由多颗小尺寸的催化剂堆叠而成。
实施实例4：
(1)物理球磨(物理法)制备的碳纳米线圈所用小尺寸催化剂
将α-Fe2O3(20-50nm)以及SnO2(10-20nm)按铁锡摩尔比5：1混合之后放入高速球磨机，具体参数为：转速1000r/min、时间为2H，球磨结束后取出催化剂粉末，清洗待用。
(2)使用上述催化剂制备,碳纳米线圈
准确称取一定量步骤(1)制备的催化剂粉末分散至水或有机溶液中超声待用(浓度为：1mg/ml)，取反应担载衬底硅片分别用丙酮、酒精、去离子水清洗后干燥待用。量取1ml催化剂分散液涂布至衬底表面；待干燥后将担载催化剂的衬底至于CVD系统中反应，待反应结束后自然降温。产物即为碳纳米线圈。
实施实例5：
(1)热蒸发法(化学-物理法)制备的碳纳米线圈所用小尺寸催化剂
本实例合成步骤分为a、b两步：
(a)将0.404gFe(NO3)3·9H2O加入35mlN，N-二甲基甲酰胺中，超声至混合溶液完全溶解，最后加入0.8g聚乙烯吡咯烷酮(PVP)待完全溶解后，转移至反应釜内，在溶剂热体系中控制反应温度在180℃，反应时间为6小时，自然冷却到室温，将所得的红色沉淀过滤，洗涤，干燥，得到单一红色粉末。
(b)准确称取步骤(a)制备的催化剂粉末分散至酒精中(浓度为：0.1mg/ml)，取反应担载衬底硅片分别用丙酮、酒精、去离子水清洗后干燥待用。量取0.1ml催化剂分散液旋涂至衬底表面，干燥后将衬底放入热蒸发仪中复合Sn，具体参数为：工作电流为1A、温度1000℃、,沉积时间为10min。铁锡原子摩尔比为30:1。
(2)使用上述催化剂制备高纯度碳纳米线圈
上述步骤b重复10次，待干燥后将担载催化剂的衬底至于CVD系统中反应，产物即为高纯度碳纳米线圈。
上述实例证明：采用本文提出的使用小尺寸Fe-S-O催化剂可以高效制备碳纳米线圈，同时本专利提出的。同时上述对实例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于这里的实施例子，本领域技术人员根据本发明的揭示，对于本发明做出的改进和修改都应该在本发明的保护范围之内。
Claims (5)
1.一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法，其特征在于，该方法首先制备尺寸小于100nm的Fe-Sn-O纳米颗粒，并以此为催化剂，再利用所制备催化剂采用热CVD法高效合成的碳纳米线圈；包括以下步骤：
(1)制备的碳纳米线圈所用小尺寸催化剂
采用Fe3+盐或铁的氧化物和可溶性Sn4+盐或锡的氧化物为原料，采用化学合成法、物理法或化学合成法与物理法相互组合的方法制备复合催化剂粉末，所述复合催化剂粉末由Fe-Sn-O组成，催化剂中Fe：Sn的摩尔比为5:1-30:1，催化剂颗粒尺寸为10-100nm；
(2)采用合成的复合催化剂利用化学气相沉积技术复合催化高效生长碳纳米线圈
将制备得到的复合催化剂粉末分散至水或乙醇等溶剂中，其中分散液浓度为0.01mg-1mg/ml，清洗担载衬底；将催化剂分散液滴涂、旋涂或喷涂至衬底表面，其中催化剂在衬底表面密度范围在1×109/cm-2—5×1010/cm-2，实现催化剂颗粒在基板上的均匀担载及相互堆积接触；将干燥后将其放至于CVD系统中利用化学气相沉积技术合成高纯度碳纳米线圈，其中碳纳米线圈纯度大于95％。
2.根据权利要求1所述的一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法，其特征在于，步骤(1)中所述的制备过程中使用的可溶性Fe3+盐包括但不限于氯化铁、硝酸铁、硫酸铁等；可溶性Sn4+盐包括氯化锡；Sn4+盐与Fe3+盐可以任意组合；步骤(1)中所述的铁的氧化物为Fe2O3，锡的氧化物为SnO2。
3.根据权利要求1或2所述的一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法，其特征在于，步骤(1)中所述的化学合成法包括水热法、溶剂热法；物理法包括热蒸镀、磁控溅射、高速球磨法。
4.根据权利要求1或2所述的一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法，其特征在于，步骤(2)中所述的衬底包括石英片、硅片、SiO2片、石墨基板、不锈钢或氧化铝基板。
5.根据权利要求3所述的一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法，其特征在于，步骤(2)中所述的衬底包括石英片、硅片、SiO2片、石墨基板、不锈钢或氧化铝基板。
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| WO2021057104A1 (zh) * | 2019-09-23 | 2021-04-01 | 大连理工大学 | 一种基于多颗小尺寸催化剂形成的复合催化剂合成高纯度碳纳米线圈的方法 |
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