WO2022178916A1 - 一种以醇类溶剂为碳源的碳纳米管及其制备方法 - Google Patents

一种以醇类溶剂为碳源的碳纳米管及其制备方法 Download PDF

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WO2022178916A1
WO2022178916A1 PCT/CN2021/079300 CN2021079300W WO2022178916A1 WO 2022178916 A1 WO2022178916 A1 WO 2022178916A1 CN 2021079300 W CN2021079300 W CN 2021079300W WO 2022178916 A1 WO2022178916 A1 WO 2022178916A1
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preparation
carbon nanotubes
carbon
alcohol solvent
ethanol
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顾宏伟
周成燕
耿洪波
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苏州大学
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/30—Purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/13—Energy storage using capacitors

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  • the invention relates to the technical field of carbon nanotubes, in particular to carbon nanotubes using an alcohol solvent as a carbon source and a preparation method thereof.
  • Carbon nanotubes have a high aspect ratio, Young's modulus, and high electrical conductivity, so they play a pivotal role in the fields of composite material preparation, supercapacitors, photocatalysis, microelectronics and nanoelectronic devices.
  • a linear carbon structure material similar to carbon nanotubes was found in the reaction of CO and Fe3O4 at 450 °C.
  • Iijima an electron microscopist at the Basic Research Laboratory of NEC Corporation in Japan, accidentally discovered that polytetrafluoroethylene (C60) was produced by high-resolution transmission microscopy (HRTEM) in the study of the preparation of fullerene (C60) by the graphite arc discharge method in 1991.
  • HRTEM high-resolution transmission microscopy
  • Coaxial tubular new fuller carbons, or CNTs with complete molecular structure composed of layered graphite shells. This material has a nanoscale hollow structure. Because of its excellent physical and chemical properties, researchers have set off a frenzy to study carbon nanomaterials.
  • common techniques for preparing carbon nanotubes include arc discharge method, laser evaporation method, flame method and chemical vapor deposition (CVD).
  • chemical vapor deposition has the potential to produce high-quality carbon nanotubes in large quantities.
  • the traditional chemical vapor deposition method is to introduce hydrocarbons or carbon-containing oxides into a high-temperature tubular furnace containing a catalyst, and form carbon nanotubes after metal catalytic decomposition.
  • the method has high yield, especially it can control the morphology and structure of carbon nanotubes by adjusting the catalyst and synthesis conditions.
  • the metal catalysts used need to be pretreated in multiple steps to have catalytic activity; There are certain limitations; thirdly, in the prepared carbon nanotube products, there are still low proportion of tubular structure, uneven tube diameter, and many crystalline defects, resulting in low degree of graphitization and easy bending of carbon nanotubes. and deformation, etc. For the above reasons, chemical vapor deposition is limited in industrial applications.
  • the purpose of the present invention is to provide a carbon nanotube with an alcohol solvent as a carbon source and a preparation method thereof.
  • the invention adopts the self-made MOF material as the catalyst and the liquid alcohol solvent as the carbon source to obtain the carbon nanotubes by calcination, and further expands the batch production of the functionalized carbon nanotubes by using the functionalized solvent as the carbon source.
  • One of the objects of the present invention is to provide a carbon nanotube preparation method with alcohol solvent as carbon source, comprising the following steps:
  • step (1) the total mole ratio of the metal salt to the urea is 1:5-8.
  • the gold self-metal salt is selected from at least two of cobalt, nickel, manganese, cadmium, iron, copper, zinc, chromium, and lead acetates.
  • the alcohol solvent is one of methanol, ethanol, propanol or isopropanol.
  • the alcohol solvent is one of methanol, ethanol, propanol, octafluoropentanol, trifluoroethanol, tetrafluoropropanol, monoethanolamine, diethanolamine, triethanolamine or several.
  • step (2) before calcining at 700-900° C., the step of calcining at 150-200° C. for 0.5-1.5 h is also included.
  • step (2) calcination is carried out at 700-900° C. for 2-4 hours.
  • the protective atmosphere is an inert gas.
  • the invention uses self-made MOF material catalyst, uses liquid alcohols as solvent and carbon source, makes the catalyst fully disperse in the solvent by ultrasonic wave, and calcines carbon nanotubes under high temperature conditions.
  • the MOF material synthesized in step (1) of the present invention is used as a catalyst for the growth of carbon nanotubes, and its composition, shape and size play a decisive role in the growth of carbon nanotubes.
  • using liquid alcohols as the carbon source compared with the gas carbon source, the liquid carbon source has a wide range of sources, is cheap, and is convenient to transport, which can reduce the cost of carbon nanotube synthesis. Sex is better.
  • the cracking reduction of the metal catalyst and the growth of carbon nanotubes occur simultaneously, and carbon nanotubes are formed in situ.
  • the second objective of the present invention is to provide a functionalized carbon nanotube prepared by the above preparation method, including a heteroatom-doped carbon nanotube.
  • heteroatom is selected from nitrogen or/and fluorine.
  • the present invention has at least the following advantages:
  • the invention provides a simple controllable synthesis of carbon nanotubes and a preparation method thereof.
  • the self-made MOF material was dissolved in an alcohol solvent atmosphere and calcined to obtain a carbon nanotube product.
  • the method is easy to operate, and uses an alcohol solvent as a carbon source to obtain carbon nanotubes of uniform size after calcination.
  • the method of the invention has certain universality and can be applied to catalyst systems of MOF materials containing different metal salts, and carbon nanotubes are obtained by calcination.
  • the calcination process of the invention is simple, the operability is strong, and it is suitable for industrialized mass production.
  • functional solvents and alcohols containing heteroatoms such as fluorine as carbon sources functionalized carbon nanotubes can also be obtained in one step.
  • Fig. 1 is the TEM image of calcined products in different solvents
  • Fig. 2 is the physical photo of the calcined product obtained by adding ethanol and not adding ethanol;
  • Fig. 3 is the TEM image of the calcined product obtained by adding ethanol and not adding ethanol;
  • Example 4 is a TEM image of the calcined product in Example 3.
  • Fig. 5 is the real photograph comparison diagram before and after CoNi-U calcination
  • Figure 6 is the SEM and TEM images of CoNi-CNTs-1 and CoNi-CNTs-2;
  • Fig. 7 is the SEM, TEM image, HR-TEM image of CoNiMn-CNTs and its element distribution map;
  • Fig. 8 is the XRD comparison chart of CoNi-CNTs-1, CoNi-CNTs-2 and CoNiMn-CNTs;
  • FIG. 9 is the SEM, TEM, HR-TEM and element distribution diagrams of CoCdFe-CNTs.
  • Figures 5a and 5b are physical photographs of CoNi-U before and after calcination. It can be seen that after calcination, the solution in the porcelain ark changed from brown to a fluffy black substance, and SEM and TEM characterizations further found that carbon nanotubes were formed. By comparison, the mass of the sample before calcination (without adding ethanol) is 750 mg, and the mass of the sample after calcination is 1500 mg. It can be seen that the sample has increased in weight, which further proves that the ethanol solvent can be used as the basis for the carbon source, and also shows that this method has the ability to produce carbon in large quantities. The potential of nanotubes for industrial production.
  • Figures 6a and 6c are the SEM and TEM images of CoNi-CNTs-1, respectively;
  • Figures 6b and 6d are the SEM and TEM images of CoNi-CNTs-2, respectively. From the SEM image, it can be seen that the carbon nanotubes are typical fibrous. Further, it can be seen from the TEM image that the carbon nanotubes have obvious hollow tubes, and the ends of the carbon nanotubes are wrapped with granular substances; the diameter of the carbon nanotubes in CoNi-CNTs-1 is about 30 nm, and the thickness of the tube wall is about 10 nm. ; The diameter of carbon nanotubes in CoNi-CNTs-2 is about 40 nm, and the thickness of the tube wall is about 10 nm.
  • Figures 7a and 7b are the SEM and TEM images of CoNiMn-CNTs, respectively,
  • Figure 7c1 is the HR-TEM image of CoNiMn-CNTs, and
  • Figures 7c2-c7 are the distributions of Co, Ni, Mn, C, N, and O elements in sequence.
  • SEM and TEM images it can be seen that CoNiMn-CNTs are similar in structure to CoNi-CNTs-1 and CoNi-CNTs-2.
  • the diameter of the carbon nanotubes is about 30 nm, and the thickness of the tube wall is about 10 nm.
  • the metal elements Co, Ni and Mn as catalysts are mainly distributed at the ends of the carbon nanotubes in the form of particles.
  • O is also mainly distributed at the ends of the carbon nanotubes
  • C and N are mainly distributed in the tube walls of the carbon nanotubes.
  • Figure 8 is the XRD comparison of CoNi-CNTs-1, CoNi-CNTs-2 and CoNiMn-CNTs.
  • the metallic Co and Ni in CoNi-CNTs-1 and CoNi-CNTs-2 mainly exist in the form of metal elements, and in CoNiMn-CNTs Metals Co and Ni also mainly exist in the form of metal elements, and Mn mainly exists in the form of MnO.
  • Figures 9a and 9b are the SEM and TEM images of CoCdFe-CNTs, respectively,
  • Figure 9c1 is the HR-TEM of CoCdFe-CNTs, and
  • Figures 9c2-c7 are the distributions of Co, Cd, Fe, C, N, and O elements in sequence.
  • SEM and TEM images it can be seen that CoCdFe-CNTs have a structure similar to CoNiMn-CNTs, and the diameter of the carbon nanotubes is about 100 nm, and the thickness of the tube wall is about 20 nm.
  • the metal elements Co, Cd and Fe as catalysts are mainly distributed at the ends of the carbon nanotubes in the form of particles.
  • O is also mainly distributed at the ends of the carbon nanotubes
  • C and N are mainly distributed in the tube walls of the carbon nanotubes.

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Abstract

本发明是一种以醇类溶剂为碳源的碳纳米管及其制备方法。将金属盐和尿素溶于醇类溶剂中，并回流反应，反应完全后得到金属有机框架（MOF）材料；然后在惰性气体氛围下，以醇类溶剂为碳源，700-900℃下煅烧，得到碳纳米管。由此延伸，利用功能性溶剂，以含氟等杂原子的醇为碳源，一步法得到功能化的碳纳米管。

Description

一种以醇类溶剂为碳源的碳纳米管及其制备方法 技术领域
本发明涉及碳纳米管技术领域，尤其涉及以醇类溶剂为碳源的碳纳米管及其制备方法。
背景技术
碳纳米管具有高长径比、杨氏模量和高导电性，因此在复合材料制备、超级电容器、光催化、微电子和纳电子器件等领域都占有举足轻重的地位。早在1953年，就有人在450℃下进行的CO与Fe 3O 4反应中发现了与碳纳米管类似的线状碳结构材料。几十年后，日本NEC公司基础研究实验室的电镜学家Iijima，于1991年在采用石墨电弧放电法制备富勒烯(C60)的研究中通过高分辨透射显微镜(HRTEM)意外发现了由多层石墨壳组成的、具有完整分子结构的同轴管状新型富勒碳，即CNTs。这种材料具有纳米量级尺寸的中空结构，因其优异的理化性能，掀起了科研人员研究碳纳米材料的狂潮。
目前，常见的制备碳纳米管技术包括：电弧放电法、激光蒸发法、火焰法和化学气相沉积法(CVD)。与前三种方法相比，化学气相沉积法具有大批量生产优质碳纳米管的潜力。传统的化学气相沉积法是将烃类或含碳氧化物引入到含有催化剂的高温管式炉中，经过金属催化分解后形成碳纳米管。该法产率高，特别是它可以通过调整催化剂及合成条件来达到控制碳纳米管的形貌和结构。但目前仍存在以下缺点：其一，使用的金属催化剂需通过多步预处理才具有催化活性；其二，作为碳源的气体烃类物质或气体碳氧化物，在实际操作和储存运输上都存在一定的局限性；其三，制得的碳纳米管产物中，仍然存在管状结构比例低、管径不均匀、较多结晶缺陷等情况，导致其石墨化程度低、碳纳米管易发生弯曲和变形等缺点。以上原因致使化学气相沉积法在工业应用方面受到一定的限制。
近年来众多的科研工作者为解决以上问题也提出了许多新的策略。Kenji Hata等人的研究表明，水的存在可优化碳纳米管的形貌并提高其纯度(Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes.Science,2004,306:1362-1364.)。该研究以乙烯为碳源，添加一定量的水，通过化学气相沉积法，在不同催化剂的作用下成功地制备出高质量的单壁碳纳米管。这证明在煅烧过程中加入少量的水可去除无定形碳，提高催化剂的活性和寿命，同时也有利于解决碳纳米管在生长过程中遇到的前面所述的问题。由此可见，水辅助碳纳米管生长方法适用于大规模生产碳纳米管，同时可解决诸如扩展性、纯度和成本等关键问题，这为碳纳米管合成方法提供了一个新的方向。随着碳纳米管被广泛用作 催化剂材料及人们对更高效能源的进一步需求，研发更优质的碳纳米管催化剂已成趋势，现阶段主要通过掺杂杂原子来提高碳纳米管的质量品质。例如Hou等人以聚吡咯为氮源，乙炔为碳源，Fe 3O 4为铁源，在低温退火条件下，采用自催化CVD法制备了Fe 3C/N掺杂的碳纳米管，通过实验结果和理论计算证明杂原子掺杂的协同作用可提高碳纳米管的储锂性能(A facile self-catalyzed CVD method to synthesize Fe 3C/N-doped carbon nanofibers as lithium storage anode with improved rate capability and cyclability.Journal of Materials Science&Technology,2020,44:229–236.)。当今，如何简便地将杂原子掺杂于碳纳米管中和降低其生产成本，以实现碳纳米管的工业级大规模生产已成为人们关注的另一焦点。
发明内容
为解决上述技术问题，本发明的目的是提供一种以醇类溶剂为碳源的碳纳米管及其制备方法。本发明采用自制的MOF材料作为催化剂，液态的醇类溶剂作为碳源，煅烧得到碳纳米管，此外还扩展了利用功能化溶剂作为碳源实现功能化碳纳米管的批量生产。
本发明的目的之一是提供以醇类溶剂为碳源的碳纳米管制备方法，包括以下步骤：
(1)将金属盐和尿素溶于醇类溶剂中，将得到的混合溶液在50-80℃下回流反应，反应完全后得到MOF材料；
(2)将所述MOF材料作为催化剂，醇类溶剂作为碳源，在700-900℃下煅烧，得到所述碳纳米管。
进一步地，在步骤(1)中，所述金属盐的总摩尔数和尿素的摩尔比为1:5-8。
进一步地，在步骤(1)中，所述金自金属盐选自钴、镍、锰、镉、铁、铜、锌、铬、铅的乙酸盐中的至少两种。
进一步地，在步骤(1)中，所述醇类溶剂为甲醇、乙醇、丙醇或异丙醇的一种。
进一步地，在步骤(2)中，所述醇类溶剂为甲醇、乙醇、丙醇、八氟戊醇、三氟乙醇、四氟丙醇、一乙醇胺、二乙醇胺、三乙醇胺中的一种或几种。
进一步地，在步骤(2)中，在700-900℃下煅烧之前，还包括在150-200℃下煅烧0.5-1.5h的步骤。
进一步地，在步骤(2)中，在700-900℃下煅烧2-4h。
进一步地，在步骤(2)中，保护气氛为惰性气体。
本发明以自制MOF材料催化剂，以液体醇类为溶剂和碳源，通过超声使催化剂充分分散在溶剂里，在高温条件下煅烧生成碳纳米管。本发明步骤(1)合成的MOF材料作为碳纳米管生长的催化剂，其组分、形状以及尺寸的大小对碳纳米管的生长起着决定性作用。另外， 以液体醇类为碳源，相比较于气体碳源，液体碳源来源广泛，价格便宜，运输方便，可降低碳纳米管合成成本，且在煅烧时，装置搭建要求不高，可控性更好。最后，在高温条件下，金属催化剂的裂解还原和碳纳米管的生长同时发生，原位形成了碳纳米管。
本发明目的之二是提供一种采用上述制备方法所制备的功能化碳纳米管，包括杂原子掺杂的碳纳米管。
进一步地，杂原子选自氮或/和氟。
借由上述方案，本发明至少具有以下优点：
本发明提供了一种简单的可控合成碳纳米管及其制备方法。将自制MOF材料溶于醇类溶剂氛围中煅烧得到碳纳米管产物。此方法操作简便，利用醇类溶剂作为碳源，煅烧后得到碳纳米管尺寸均一。
本发明的方法具有一定的普适性，可适用于含不同金属盐的MOF材料的催化剂体系，通过煅烧得到碳纳米管。本发明煅烧工艺简便，可操作性强，适用于工业化大批量生产。利用功能性溶剂，以含氟等杂原子的醇为碳源，还能一步法得到功能化的碳纳米管。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下为本发明的较佳实施例并配合详细的附图说明。
附图说明
图1是不同溶剂中煅烧产物的TEM图；
图2是添加乙醇和不添加乙醇所得煅烧产物的实物照片；
图3是添加乙醇和不添加乙醇所得煅烧产物的TEM图；
图4是实施例3中的煅烧后产物的TEM图；
图5是CoNi-U煅烧前后的实物照片对比图；
图6是CoNi-CNTs-1和CoNi-CNTs-2的SEM和TEM图；
图7是CoNiMn-CNTs的SEM、TEM图、HR-TEM及其元素分布图；
图8是CoNi-CNTs-1、CoNi-CNTs-2和CoNiMn-CNTs的XRD对比图；
图9是CoCdFe-CNTs的SEM、TEM图、HR-TEM及其元素分布图。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1
为了证明乙醇对碳纳米管生长有优化作用，以下进行如下实验进行验证：
(1)将Co(OAc) 2·4H 2O(1.0mmol)和尿素(5.0mmol)溶解于50mL乙醇中，50℃回流反应8h。冷却后，离心收集产品，70℃真空干燥12h，得到MOF材料Co-U-1。
(2)取Co-U-1(50mg)各两份，放在离心管中，分别加入3mL正己烷和3mL乙醇，超声30min后在相同条件下煅烧。煅烧条件：在氮气氛围下，煅烧第一阶段升温速率为2℃min -1，保温温度为150℃，保温时间1.5h；接着煅烧第二阶段，升温速率为2℃min -1，保温温度为700℃，保温时间4h。
如图1所示，通过TEM的对比图发现：在不含醇羟基的正己烷中煅烧得到的碳纳米管(图1a)比在乙醇中煅烧得到的碳纳米管(图1b)的管壁表面粗糙且杂质多；而在乙醇中生成的碳纳米管，管壁表面光滑，且杂质少。这是因为乙醇溶剂在高温条件下，其C-O键断解产生水，水有利于阻止碳与金属颗粒团聚，保证了更多的金属催化剂的活性，同时碳源可以充分地在催化剂表面扩散，这一效应也进一步促进水作为保护剂的作用，减少非晶态的碳纳米管形成，可以得到更为纯净的碳纳米管。
实施例2
为验证乙醇是否能够对碳纳米管生长有一定的影响，进行如下实验进行验证：
(1)将Co(OAc) 2·4H 2O(1.0mmol)和尿素(7.0mmol)溶解于60mL乙醇中，60℃回流反应7h。冷却后，离心收集产品，70℃真空干燥12h，得到MOF材料Co-U-2。
(2)取Co-U-2(100mg)各两份，放在离心管中，一份加入5mL乙醇超声30min，另一份不加入乙醇。两份样品在相同条件下煅烧。煅烧条件：在氮气氛围下，煅烧第一阶段升温速率为2℃min -1，保温温度为160℃，保温时间1h；接着煅烧第二阶段，升温速率为2℃min -1，保温温度为800℃，保温时间3h。
如图2(实物照片)所示，有乙醇和无乙醇样品的煅烧产物有明显不同。通过称重比较，有乙醇煅烧后的样品净重150mg，无乙醇煅烧后的样品净重80mg，对比发现在乙醇的存在下煅烧后产物的产率更高。考虑到煅烧是在惰性气氛(N 2)下进行，不参与碳纳米管的生长，无外来的碳源提供，且和无乙醇煅烧对比，碳纳米管收率有明显差距，由此我们可以证明乙醇不仅作为溶剂介质使催化剂和金属盐均匀分散，也可以作为碳纳米管生长的碳源。进一步的，通过TEM表征看到，添加乙醇后煅烧生成了碳纳米管(图3a)，而不添加乙醇直接煅烧的产物多是块状团聚物(图3b)。由此可再说明，作为溶剂的乙醇也是调控碳纳米管生长的至关因素。
实施例3
为了得到功能化碳纳米管，也进一步证明溶剂作为碳源参与了碳纳米管的生长，我们将 煅烧加入的溶剂换成八氟戊醇。实验步骤如下：
(1)将Co(OAc) 2·4H 2O(1.0mmol)和尿素(8.0mmol)溶解于60mL乙醇中，70℃回流反应5h。冷却后，离心收集产品，70℃真空干燥12h，得到MOF材料Co-U-3。
(2)将Co-U-3(150mg)放在离心管中加入4mL八氟戊醇和4mL乙醇中超声30min后，煅烧。煅烧条件：在氮气氛围下，煅烧第一阶段升温速率为2℃min -1，保温温度为180℃，保温时间0.5h；接着煅烧第二阶段，升温速率为2℃min -1，保温温度为900℃，保温时间2h。
如图4的TEM表征图所示，使用八氟戊醇溶剂，煅烧条件不变，依旧可以得到碳纳米管，且管壁表面光滑，进一步证明醇类溶剂可以调节碳纳米管表面粗糙度，碳纳米管直径尺寸为50nm左右，管壁的厚度15nm左右。同时EDS元素分析发现氟的存在，证明了此方法可适用于功能化的碳源溶剂，可合成功能化碳纳米管(表1)。
表1：产物的EDS图
元素 wt％ At％
C K 59.08 69.49
Co K 7.58 3.33
N K 9.34 8.75
O K 14.27 11.71
F K 9.73 6.72
总量 100.00 100.00
实施例4
(1)将Co(OAc) 2·4H 2O(0.5mmol)、Ni(OAc) 2·4H 2O(0.5mmol)和尿素(8mmol)溶解于70mL乙醇中，80℃回流反应4h。冷却后，离心收集产品，70℃真空干燥12h，得到MOF材料CoNi-U-1。
(2)取CoNi-U-1(500mg)放在离心管中，加入15mL无水乙醇，超声30min后，煅烧。煅烧条件如下：在氮气氛围下，煅烧第一阶段升温速率为2℃min -1，保温温度为200℃，保温时间0.5h；接着煅烧第二阶段，升温速率为2℃min -1，保温温度为700℃，保温时间4h。最后得到产物CoNi-CNTs-1。
实施例5
(1)将Co(OAc) 2·4H 2O(0.2mmol)、Ni(OAc) 2·4H 2O(0.8mmol)和尿素(5mmol)溶解于50mL乙醇中，80℃回流反应4h。冷却后，离心收集产品，70℃真空干燥12h，得到MOF材料CoNi-U-2。
(2)取CoNi-U(125mg)放在离心管中，加入5mL无水乙醇，超声30min后，煅烧。煅烧条件如下：在氮气氛围下，煅烧第一阶段升温速率为2℃min -1，保温温度为180℃，保温时间1h；接着煅烧第二阶段，升温速率为2℃min -1，保温温度为800℃，保温时间3h。最后得到产物CoNi-CNTs-2。
图5a和5b是CoNi-U在煅烧前后的实物照片图。可见煅烧后，瓷方舟中溶液由棕色变为了蓬松的黑色物质，SEM和TEM表征也进一步发现生成了碳纳米管。通过对比，煅烧前(未加入乙醇)样品的质量为750mg，煅烧后样品的质量为1500mg，可见样品增重，这进一步证明乙醇溶剂可作为碳源的依据，也说明此方法具有大批量生产碳纳米管的潜力，可用于工业生产。
图6a和6c分别是CoNi-CNTs-1的SEM和TEM图；图6b和6d分别是CoNi-CNTs-2的SEM和TEM图。从SEM图中可以看到碳纳米管呈典型的纤维状。进一步，从TEM图可以看到碳纳米管有明显的中空管道，碳纳米管端头包裹着颗粒状的物质；CoNi-CNTs-1中碳纳米管的直径为30nm左右，管壁厚度为10nm左右；CoNi-CNTs-2中碳纳米管的直径为40nm左右，管壁厚度为10nm左右。
实施例6
(1)将Co(OAc) 2·4H 2O(0.3mmol)、Ni(OAc) 2·4H 2O(0.3mmol)、Mn(OAc) 2·4H 2O(0.4mmol)和尿素(7mmol)溶解于70mL乙醇中，70℃回流反应5h。冷却后，离心收集产品，70℃真空干燥12h，得到MOF材料CoNiMn-U。
(2)取CoNiMn-U(175mg)放到离心管中，加入6mL无水乙醇，超声30min后，煅烧。煅烧条件如下：在氮气氛围下，煅烧第一阶段升温速率为2℃min -1，保温温度为160℃，保温时间1.5h；接着煅烧第二阶段，升温速率为2℃min -1，保温温度为700℃，保温时间3.5h。最后得到产物CoNiMn-CNTs。
图7a和7b分别是CoNiMn-CNTs的SEM和TEM图，图7c1是CoNiMn-CNTs的HR-TEM图，图7c2-c7依次为Co、Ni、Mn、C、N、O元素分布图。通过SEM和TEM图，可以看到CoNiMn-CNTs类似CoNi-CNTs-1和CoNi-CNTs-2的结构，其碳纳米管的直径约为30nm左右，管壁厚度约为10nm左右。同时元素分析图可以看出，作为催化剂的金属元素Co、Ni和Mn主要以颗粒状分布于碳纳米管的端头处。此外还可见，O也主要分布于碳纳米管的端头处，C和N主要分布于碳纳米管的管壁中。
图8是CoNi-CNTs-1、CoNi-CNTs-2和CoNiMn-CNTs的XRD对比图，CoNi-CNTs-1和CoNi-CNTs-2中金属Co和Ni主要以金属单质形式存在，CoNiMn-CNTs中金属Co和Ni也主要以金属单质形式存在，Mn主要是MnO形式存在。
实施例7
(1)将Co(OAc) 2·4H 2O(0.3mmol)、Cd(OAc) 2·4H 2O(0.3mmol)、Fe(OAc) 2·4H 2O(0.3mmol)和尿素(8mmol)溶解于50mL乙醇中，80℃回流反应5h。冷却后，离心收集产品，70℃真空干燥12h，得到MOF材料CoCdFe-U。
(2)取CoCdFe-U(150mg)放入离心管中，加入3mL无水乙醇，超声30min后，煅烧。煅烧条件如下：在氮气氛围下，煅烧第一阶段升温速率为2℃min -1，保温温度为200℃，保温时间0.5h；接着煅烧第二阶段，升温速率为2℃min -1，保温温度为800℃，保温时间3h。最后得到产物CoCdFe-CNTs。
图9a和9b分别是CoCdFe-CNTs的SEM和TEM图，图9c1是CoCdFe-CNTs的HR-TEM，图9c2-c7依次为Co、Cd、Fe、C、N、O元素分布图。通过SEM和TEM图，可以看到CoCdFe-CNTs类似CoNiMn-CNTs的结构，其碳纳米管的直径为100nm左右，管壁厚度为20nm左右。同时元素分析图可以看出，作为催化剂的金属元素Co、Cd和Fe主要以颗粒状分布于碳纳米管的端头处。此外还可见，O也主要分布于碳纳米管的端头处，C和N主要分布于碳纳米管的管壁中。
以上所述仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (9)

  1. 一种以醇类溶剂为碳源的碳纳米管及其制备方法，其特征在于，包括以下步骤：
    (1)将金属盐和尿素溶于醇类溶剂中，将得到的混合溶液在50-80℃下回流反应，反应完全后得到MOF材料；
    (2)将所述MOF材料在醇类溶剂氛围下，在700-900℃下煅烧，得到所述碳纳米管。
  2. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，所述金属盐的总摩尔数和尿素的摩尔比为1:5-8。
  3. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，所述金属盐选自钴、镍、锰、镉、铁、铜、锌、铬和铅的乙酸盐中的一种或几种。
  4. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，所述醇类溶剂为甲醇、乙醇、丙醇或异丙醇中的一种。
  5. 根据权利要求1所述的制备方法，其特征在于：在步骤(2)中，所述醇类溶剂为甲醇、乙醇、丙醇、八氟戊醇、三氟乙醇、四氟丙醇、一乙醇胺、二乙醇胺、三乙醇胺中的一种或几种。
  6. 根据权利要求1所述的制备方法，其特征在于：在步骤(2)中，在700-900℃下煅烧之前，还包括在150-200℃下煅烧0.5-1.5h的步骤。
  7. 根据权利要求1所述的制备方法，其特征在于：在步骤(2)中，在700-900℃下煅烧2-5h。
  8. 一种权利要求1-6中任一项所述的制备方法所制备的碳纳米管。
  9. 根据权利要求8所述的碳纳米管，其特征在于：所述碳纳米管中掺杂有杂原子，所述杂原子选自氮或/和氟。
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