CN1365946A - 一种直接合成超长连续单壁碳纳米管的工艺方法 - Google Patents
一种直接合成超长连续单壁碳纳米管的工艺方法 Download PDFInfo
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Abstract
一种直接合成超长连续单壁碳纳米管的工艺方法,涉及一种碳纳米材料的制备工艺。本发明采用立式浮动催化裂解法,以正己烷为碳源,二茂铁为催化剂,噻吩为添加剂制成反应溶液,以蒸汽的形式随氢气一同引入反应器进行催化裂解。在特定的工艺参数下,制得的超长绳状单壁碳纳米管产物,管束定向性良好,纯度最高可达85%;管束中的单壁碳纳米管生长连续、平直,长度可达20cm(单根单壁碳纳米管长径比>108)。本发明由于采用立式浮动催化裂解法,仅需一个立式电炉,且不需要石墨基底,二茂铁直接溶解在正己烷溶液中,无需预先在氢气气氛下还原,因此操作简单、方便,可实现超长连续单壁碳纳米管束的低成本批量制备。
Description
技术领域
本发明涉及一种碳纳米材料的制备工艺,尤其涉及一种单壁碳纳米管的合成工艺方法。
背景技术
单壁碳纳米管的发现极大地推动了纳米科技研究及其应用领域的发展。1996年,Smalley研究小组在《科学》杂志(Science,1996,273(5274):483~487)上报道了采用激光蒸发工艺合成高纯度单壁碳纳米管的方法。1997年,Journet等人在《自然》杂志(Nature,1997,388:756~758)报道了采用直流电弧法批量制备单壁碳纳米管的工艺。另外,采用催化裂解工艺制备单壁碳纳米管也成为该研究领域的焦点之一,因为该方法是最可能实现碳纳米管大批量工业化的制备方法。Dai等人在文献(Chemical Physics Letters,1996,260:471~475)中首先采用CO气体为碳源制备了单壁碳纳米管,但其产量及产率很低。该方法制备单壁碳纳米管的工艺条件比较苛刻,参数控制比较严格。后来,乙烯、甲烷、苯等都被作为碳源制备单壁碳纳米管,通过对工艺参数的改进,产量和产率有所提高。目前单壁碳纳米管的批量制备仍是该领域的难点和热点。Cheng等人在文献(Applied Physics Letters,1998,72(25):3282~3284)中介绍了卧式浮动催化裂解工艺制备单壁碳纳米管。虽然以上方法实现了单壁碳纳米管的制备,但所得单壁碳纳米管的长度均为微米量级,且管束间定向性差,单壁碳纳米管纯度低,从而限制了理论及实验上对超长连续单壁碳纳米管的研究。制备超长连续的单壁碳纳米管是一个重点、难点,在理论及应用方面具有重要意义。这里所指的“超长”是指单壁碳纳米管的长度达到十厘米量级;“连续”是指管束中的单壁碳纳米管连续生长,无间断,并且有良好的定向性。
在催化裂解法中,立式浮动催化裂解法(Carbon,2000,38(14):1933~1937)是大批量制备多壁碳纳米管和碳纳米纤维的一种有效方法。现有的立式浮动催化裂解法以苯为碳源,二茂铁(Fe(C5H5)2)为催化剂,噻吩(C4H4S)为添加剂。设备简单,成本低,适于大批量生产。同卧式浮动催化裂解法实验设备相比,立式浮动催化裂解法仅需一个立式电炉,并且不需要石墨基底。二茂铁直接溶解在碳源中,无需预先在氢气气氛下还原,二茂铁随溶液注入蒸发器,操作简单方便。但由于苯含碳量高,仅适用于制备多壁碳纳米管和碳纳米纤维。且苯有毒性,对环境造成污染。要使用立式浮动催化裂解法实现单壁碳纳米管的制备,就需要寻找一种含碳量低且无毒性的碳源。
发明内容
本发明的目的是提供一种直接合成超长连续单壁碳纳米管的工艺方法,实现超长连续单壁碳纳米管束的低成本批量制备,使所制得的单壁碳纳米管束定向性良好,纯度高且长度长。
本发明的目的是通过如下技术方案实现的:一种直接合成超长连续单壁碳纳米管的工艺方法,采用立式浮动催化裂解法,以二茂铁(Fe(C5H5)2)为催化剂,噻吩(C4H4S)为添加剂溶入碳源中制成反应溶液,以蒸汽的形式随氢气一同引入反应器进行催化裂解,其特征在于该方法是以正己烷(C6H14)为碳源。
所述反应溶液是由正己烷、(0.010~0.020g/ml)的二茂铁和(0.2~0.6wt.%)噻吩组成的混合液。反应溶液引入流量为0.2~0.8ml/min,氢气的流量为150~300ml/min。
本发明由于采用立式浮动催化裂解法,该方法仅需一个立式电炉,并且不需要石墨基底,二茂铁直接溶解在正己烷溶液中,无需预先在氢气气氛下还原,且二茂铁随溶液注入蒸发器,因此操作简单、方便,可实现超长连续单壁碳纳米管束的低成本批量制备。制得的超长绳状单壁碳纳米管产物,管束定向性良好,纯度最高可达85%;管束中的单壁碳纳米管生长连续、平直,长度可达20cm(单根单壁碳纳米管长径比>108)。
附图说明
图1:为本发明(立式浮动催化裂解法)所用设备的结构原理示意图。
图2:为利用扫描电子显微镜检测的产物的微观形貌图。
图3:为利用透射电子显微镜检测的产物的微观形貌图。
具体实施方式
下面结合附图1具体说明本发明的工艺过程及实施方式:
立式浮动催化裂解法的设备主体为立式陶瓷反应管1(外径68mm,内径58mm,长度1600mm),该管垂直放置在电阻炉2(额定温度为1200℃,额定功率6KW)中。反应容器的上部是蒸发器3,包括进气口4及反应溶液(正己烷、二茂铁、噻吩的混合溶液)入口5。反应溶液6通过液体微流量泵7引入蒸发器3(蒸发温度150~200℃)随载气(氢气)以蒸汽的形式一同引入反应容器1。反应容器1下面安装产物收集瓶8、过滤器9及尾气出口10。其具体操作步骤如下:
(1)首先通氩气100ml/min并开始升高炉温,至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1100~1200℃),引入反应溶液开始制备产物。反应溶液6为正己烷(C6H14)、二茂铁(Fe(C5H5)2)和噻吩(C4H4S)的混合溶液。其中正己烷为碳源,二茂铁(0.010~0.020g/ml)为催化剂,噻吩(0.2~0.6wt.%)作为添加剂。
(3)反应溶液6引入流量为0.2~0.8ml/min,氢气的流量为150~300ml/min。
(4)保温一段时间后停止升温,通氩气(100ml/min)冷却并停止氢气,温度降至室温后收集产物。
使用扫描电子显微镜(如图2所示)和透射电子显微镜(如图3所示)检测产物的微观形貌。
使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。
检测结果表明,立式浮动催化技术可以实现超长连续的单壁碳纳米管的批量制备。产物由大量密集排列的定向单壁碳纳米管束组成;管束中的单壁碳纳米管长度可达20cm,直径分布在1~2nm之间。单壁碳纳米管的纯度最高可达85%。
实施例1:
(1)首先通氩气100ml/min并开始升温,至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1100℃),引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源,二茂铁(Fe(C5H5)2,0.010g/ml)为催化剂,噻吩(G4H4S,0.6wt.%)作为添加剂。
(3)反应溶液引入流量为0.5ml/min,氢气的流量为200ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气,温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝,由单壁碳纳米管和部分碳纳米管纤维组成,单壁碳纳米管含量为60%。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径20~60nm)组成。管束由直径在1~2nm间的单壁碳纳米管组成。
实施例2:
(1)首先通氩气100ml/min并开始升温,至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1150℃),引入反应溶液开始制备产物。反应溶液采用正己烷(C6H14)为碳源,二茂铁(Fe(C5H5)2,0.020g/ml)为催化剂,噻吩(C4H4S,0.4wt.%)作为添加剂。
(3)反应溶液引入流量为0.5ml/min,氢气的流量为250ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气,温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝,由单壁碳纳米管和少量双壁碳纳米管组成,单壁碳纳米管含量为85%。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径10~50nm)组成。管束由直径在1~2nm间的单壁碳纳米管组成。
实施例3:
(1)首先通氩气100ml/min并开始升温,至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1200℃),引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源,二茂铁(Fe(C5H5)2,0.018g/ml)为催化剂,噻吩(C4H4S,0.4wt.%)作为添加剂。
(3)反应溶液引入流量为0.2ml/min,氢气的流量为250ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气,温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝,由单壁碳纳米管和少量多壁碳纳米管、碳纳米纤维组成,单壁碳纳米管含量为80%。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径10~60nm)组成。管束由直径在1~2nm间的单壁碳纳米管组成。
实施例4:
(1)首先通氩气100ml/min并开始升温,至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1200℃),引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源,二茂铁(Fe(C5H5)2,0.018g/ml)为催化剂,噻吩(C4H4S,0.2wt.%)作为添加剂。
(3)反应溶液引入流量为0.8ml/min,氢气的流量为250ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气,温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝,由单壁碳纳米管和碳纳米纤维组成,单壁碳纳米管含量为70%。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径20~60nm)组成。管束由直径在1~2nm间的单壁碳纳米管组成。
实施例5:
(1)首先通氩气100ml/min并开始升温,至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1200℃),引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源,二茂铁(Fe(C5H5)2,0.018g/ml)为催化剂,噻吩(C4H4S,0.5wt.%)作为添加剂。
(3)反应溶液引入流量为0.5ml/min,氢气的流量为150ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气,温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝,由单壁碳纳米管和多壁碳纳米管、碳纳米纤维组成,单壁碳纳米管含量为70%。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径20~60nm)组成。管束由直径在1~2nm间的单壁碳纳米管组成。
实施例6:
(1)首先通氩气100ml/min并开始升温,至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1200℃),引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源,二茂铁(Fe(C5H5)2,0.018g/ml)为催化剂,噻吩(C4H4S,0.5wt.%)作为添加剂。
(3)反应溶液引入流量为0.5ml/min,氢气的流量为300ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气,温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝,由单壁碳纳米管和少量多壁碳纳米管组成,单壁碳纳米管含量为80%。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径10~50nm)组成。管束由直径在1~2nm间的单壁碳纳米管组成。
Claims (3)
1.一种直接合成超长连续单壁碳纳米管的工艺方法,采用立式浮动催化裂解法,以二茂铁(Fe(C5H5)2)为催化剂,噻吩(C4H4S)为添加剂溶入碳源中制成反应溶液,以蒸汽的形式随氢气一同引入反应器进行催化裂解,其特征在于该方法是以正己烷(C6H14)为碳源。
2.按照权利要求1所述的一种直接合成超长连续单壁碳纳米管的工艺方法,其特征在于所述反应溶液是由正己烷、(0.010~0.020g/ml)的二茂铁和(0.2~0.6wt.%)噻吩组成的混合液。
3.按照权利要求1所述的一种直接合成超长连续单壁碳纳米管的工艺方法,其特征在于反应溶液引入流量为0.2~0.8ml/min,氢气的流量为150~300ml/min。
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US10/370,519 US7615204B2 (en) | 2002-02-22 | 2003-02-24 | Direct synthesis of long single-walled carbon nanotube strands |
AU2003216383A AU2003216383A1 (en) | 2002-02-22 | 2003-02-24 | Direct synthesis of long single-walled carbon nanotube strands |
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CN113562724A (zh) * | 2021-07-06 | 2021-10-29 | 上海大学 | 一种单壁碳纳米管封装超长线性碳链及其制备方法 |
CN113562724B (zh) * | 2021-07-06 | 2024-03-19 | 上海大学 | 一种单壁碳纳米管封装超长线性碳链及其制备方法 |
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