WO2019113993A1 - Carbon nanotube and method for fabrication thereof - Google Patents

Carbon nanotube and method for fabrication thereof Download PDF

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WO2019113993A1
WO2019113993A1 PCT/CN2017/117054 CN2017117054W WO2019113993A1 WO 2019113993 A1 WO2019113993 A1 WO 2019113993A1 CN 2017117054 W CN2017117054 W CN 2017117054W WO 2019113993 A1 WO2019113993 A1 WO 2019113993A1
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carbon nanotube
nanotube according
metal
preparing
carbon nanotubes
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孙公权
许新龙
王素力
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中国科学院大连化学物理研究所
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C01B32/166—Preparation in liquid phase
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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
    • C01B2202/36—Diameter
    • 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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to the field of preparation and application of carbon materials, in particular to the preparation and application of carbon nanotubes.
  • Carbon nanotubes are a new type of carbon nanomaterial composed of carbon atoms. Their unique one-dimensional structure, high degree of graphitization and excellent electrical and mechanical properties have attracted wide interest of researchers, especially in electrochemical energy storage and The field of conversion is considered to have broad application prospects.
  • diameter is an important structural parameter of carbon nanotubes, and studies have shown that the electrochemical properties can be significantly affected by changing the diameter of carbon nanotubes.
  • the commonly used carbon nanotube preparation methods include arc discharge method, laser evaporation method, CVD, solid phase pyrolysis method and the like.
  • arc discharge method In 1991, Japanese physicist Iijima discovered carbon nanotubes for the first time through the arc discharge method. This method is technically simple, but the obtained carbon nanotubes are mixed with products such as C 60 , and the purity is not high.
  • the CVD method has simple requirements and low cost, and is the most feasible and economical method for synthesizing carbon nanotubes.
  • direct high-temperature carbonization of solid phase precursors such as fullerene carbon black, organometallic compounds, polymers
  • This method is not only simpler in operation but also
  • the N, S, and B compounds are added to the precursor to be doped into the carbon nanotubes in situ during the heating process, thereby changing the surface electronic structure of the carbon nanotubes, thereby further improving the electrochemical performance.
  • the behavior of the precursor in the high temperature pyrolysis process is difficult to control, and the carbon nanotubes formed are usually in a uniform morphology. It is still challenging to prepare the carbon nanotubes with controlled diameter by pyrolysis.
  • the invention aims to solve the problem that the shape of the carbon nanotubes is uncontrollable by preparing the precursor of the pyrolysis precursor, and proposes a method for preparing the carbon nanotube gas with controllable diameter.
  • the invention adopts the following specific schemes:
  • the element is coated with metal nanoparticles at one end; the carbon nanotubes have an outer diameter of 50-300 nm.
  • the N element is present in the form of one or more of pyridine N, pyrrole N, graphitized N and oxidized N, and the nitrogen element has a mass content of 2% to 8%.
  • the metal nanoparticles are iron and/or cobalt, and the metal nanoparticles have a diameter of 50-300 nm.
  • the metal nanoparticles comprise from 1% to 10% of the total mass of the carbon nanotubes.
  • the outer diameter of the carbon nanotubes is preferably 300 nm; the diameter of the metal nanoparticles is preferably 300 nm.
  • the method for preparing the carbon nanotubes comprises the following steps:
  • Step (3) Preparation of carbon nanotubes: The precursor obtained in the step (2) is subjected to heat treatment under an inert atmosphere to obtain carbon nanotubes end-coated with metal nanoparticles.
  • the zinc salt in the step (1) is one or more of zinc nitrate, zinc chloride and zinc sulfate, and the concentration of the zinc ions in the mixed solution is 0.0125-0.1 mol/L.
  • the ligand in the step (1) is 2-methylimidazole, and the concentration of the organic ligand in the mixed solution is 0.1 to 0.8 mol/L.
  • the solvent in the mixed solution in the step (1) is one of methanol, ethanol, water and DMF.
  • the metal salt in the step (2) is one or more of a chloride, a nitrate or an acetate of cobalt or iron.
  • the amino compound in the step (2) is one or more selected from the group consisting of urea, dicyandiamide, and melamine.
  • the solvent in the step (2) is one or a mixture of two or more of methanol, ethanol and water.
  • the mass ratio of the metal salt to the amino compound in the step (2) is 1:1 to 1:5.
  • the method of removing the solvent in the step (2) is rotary evaporation and/or vacuum drying.
  • the heat treatment process in step (3) is to raise the temperature to 800-1100 ° C for 0.5-3 h, and then to cool to room temperature; the temperature increase rate from room temperature to the heat treatment temperature during the temperature increase is 2-5 ° C / min; The cooling rate during the cooling process is 1-10 ° C / min.
  • the inert atmosphere of the step (3) is a mixture of one or two of nitrogen gas and argon gas.
  • the catalyst is a polymer electrolyte membrane fuel cell and a metal air battery cathode oxygen reduction reaction electrocatalyst.
  • the invention has the following advantages: the diameter of the carbon nanotubes can be directly controlled by controlling the particle size of the metal organic skeleton during the preparation process; the diameter of the carbon nanotubes is uniformly controllable, and the control range is between 50 and 300 nm;
  • the preparation process is simple, no arc discharge, chemical vapor deposition and the like are conventionally prepared for carbon nanotubes.
  • the carbon nanotubes prepared at the same time are doped with a large amount of N, which changes the electronic structure of the carbon nanotube surface and further enhances its electrochemical performance, so that it has potential application prospects in the field of energy conversion and storage.
  • Figure 1 Low-SEM image of a metal-organic framework
  • Figure 4 XRD pattern of carbon nanotubes.
  • the solid powder was placed in a corundum boat, heated to 800 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to remove the product.
  • Carbon nanotubes having an outer diameter of about 200 nm were prepared using 300 nm ZIF-67 as a template.
  • Carbon nanotubes having an outer diameter of about 100 nm were prepared using 150 nm ZIF-67 as a template.
  • Carbon nanotubes having an outer diameter of about 50 nm were prepared using 100 nm ZIF-8 as a template.
  • the solid powder was placed in a corundum boat, heated to 1000 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to remove the carbon nanotubes.

Abstract

Provided are a controllable-diameter carbon nanotube and a method for fabrication thereof. The method is: heating, in an inert atmosphere, a precursor obtained by reaction of a metal-organic framework, a metal salt, and an amino compound; performing carbonization; controlling the diameter of the carbon nanotube by means of changing the particle size of the metal-organic framework in the precursor. During the preparation process, the metal-organic framework with different particle sizes is obtained by means of simply changing the synthesis conditions such as solvent and reaction temperature, and thus the diameter of the carbon nanotube is controlled. The prepared carbon nanotubes have a bamboo-like morphology, and are doped in situ with a large amount of N. The method changes the electron structure of the surface of the carbon nanotube, further improving its electrochemical properties, and has great potential prospects for application in the field of energy conversion and storage.

Description

一种碳纳米管及其制备方法Carbon nanotube and preparation method thereof 技术领域Technical field
本发明涉及碳材料制备及其应用领域，具体涉及一种碳纳米管的制备和应用。The invention relates to the field of preparation and application of carbon materials, in particular to the preparation and application of carbon nanotubes.
背景技术Background technique
碳纳米管是由碳原子组成的一种新型的碳纳米材料，其独特的一维结构，高石墨化程度以及优异的电学和力学性能引起科研人员的广泛兴趣，尤其是在电化学能源存储和转换领域被认为具有广阔的应用前景。作为一种一维材料，直径是碳纳米管的一项重要结构参数，并有研究表明，随着改变碳纳米管的直径可以显著影响其电化学性能。Carbon nanotubes are a new type of carbon nanomaterial composed of carbon atoms. Their unique one-dimensional structure, high degree of graphitization and excellent electrical and mechanical properties have attracted wide interest of researchers, especially in electrochemical energy storage and The field of conversion is considered to have broad application prospects. As a one-dimensional material, diameter is an important structural parameter of carbon nanotubes, and studies have shown that the electrochemical properties can be significantly affected by changing the diameter of carbon nanotubes.
目前常用的碳纳米管制备方法主要有：电弧放电法、激光蒸发法、CVD、固相热解法等。1991年日本物理学家Iijima通过电弧放电法生首次发现了碳纳米管，这种方法技术上比较简单，但得到的碳纳米管与C 60等产物混杂，纯度不高。CVD法对设备要求简单，成本较低，是目前合成碳纳米管最可行也是最经济实用的办法。最近，直接高温碳化固相前躯体(如富勒烯碳黑、有机金属化合物、聚合物)的方法被用来制备碳纳米管，这种方法除了在操作上更为简便之外，还可以通过在前驱体中加入N、S、B化合物，使其在加热过程中原位掺杂到碳纳米管中，从而改变碳纳米管表面电子结构，能使其电化学性能得到进一步提升。然而高温热解过程中前驱体的行为难以控制，最终形成的碳纳米管通常形貌不均一，通过热解制备直径可控的碳纳米管仍存在挑战。 At present, the commonly used carbon nanotube preparation methods include arc discharge method, laser evaporation method, CVD, solid phase pyrolysis method and the like. In 1991, Japanese physicist Iijima discovered carbon nanotubes for the first time through the arc discharge method. This method is technically simple, but the obtained carbon nanotubes are mixed with products such as C 60 , and the purity is not high. The CVD method has simple requirements and low cost, and is the most feasible and economical method for synthesizing carbon nanotubes. Recently, direct high-temperature carbonization of solid phase precursors (such as fullerene carbon black, organometallic compounds, polymers) has been used to prepare carbon nanotubes. This method is not only simpler in operation but also The N, S, and B compounds are added to the precursor to be doped into the carbon nanotubes in situ during the heating process, thereby changing the surface electronic structure of the carbon nanotubes, thereby further improving the electrochemical performance. However, the behavior of the precursor in the high temperature pyrolysis process is difficult to control, and the carbon nanotubes formed are usually in a uniform morphology. It is still challenging to prepare the carbon nanotubes with controlled diameter by pyrolysis.
发明内容Summary of the invention
本发明针对热解前躯体制备碳纳米管形貌不可控的问题，提出了一种直径可控的碳纳米管气制备方法，本发明采用以下具体方案实现：The invention aims to solve the problem that the shape of the carbon nanotubes is uncontrollable by preparing the precursor of the pyrolysis precursor, and proposes a method for preparing the carbon nanotube gas with controllable diameter. The invention adopts the following specific schemes:
一种碳纳米管，其特征在于：所述碳纳米管呈竹节状形貌，即每根碳纳米管由2段以上的竹节状管段顺序连接而成，所述碳纳米管中含有N元素，一端包裹有金属纳米颗粒；所述碳纳米管的外径为50-300nm。所述N元素存在的形式为吡啶N、吡咯N、石墨化N和氧化N中的一种或两种以上，氮元素质量含量为2％-8％。A carbon nanotube characterized in that the carbon nanotubes have a bamboo-like morphology, that is, each carbon nanotube is sequentially connected by two or more bamboo-shaped tubular segments, and the carbon nanotubes contain N The element is coated with metal nanoparticles at one end; the carbon nanotubes have an outer diameter of 50-300 nm. The N element is present in the form of one or more of pyridine N, pyrrole N, graphitized N and oxidized N, and the nitrogen element has a mass content of 2% to 8%.
所述金属纳米粒子为铁和/或钴，金属纳米粒子的直径为50-300nm。所述金属纳米颗粒占碳纳米管总质量的1％-10％。所述碳纳米管的外径较优为300nm；所述金属纳米粒子的直径较优为300nm。The metal nanoparticles are iron and/or cobalt, and the metal nanoparticles have a diameter of 50-300 nm. The metal nanoparticles comprise from 1% to 10% of the total mass of the carbon nanotubes. The outer diameter of the carbon nanotubes is preferably 300 nm; the diameter of the metal nanoparticles is preferably 300 nm.
所述碳纳米管的制备方法包括以下步骤:The method for preparing the carbon nanotubes comprises the following steps:
(1)金属有机骨架的合成：制备锌盐和有机配体的混合溶液；30-120℃下进行反应，然后分离得到金属有机骨架；(1) Synthesis of a metal organic skeleton: preparing a mixed solution of a zinc salt and an organic ligand; performing a reaction at 30-120 ° C, and then separating to obtain a metal organic skeleton;
(2)前驱体的制备：将金属盐和氨基化合物溶于溶剂，加入步骤(1)中制备的金属有机骨架，分散均匀后，除去溶剂得前驱体；(2) Preparation of precursor: the metal salt and the amino compound are dissolved in a solvent, and the metal organic skeleton prepared in the step (1) is added, and after dispersing uniformly, the solvent is removed to obtain a precursor;
(3)碳纳米管的制备：将步骤(2)所得前驱体在惰性气氛下进行热处理，得末端包裹金属纳米颗粒的碳纳米管。(3) Preparation of carbon nanotubes: The precursor obtained in the step (2) is subjected to heat treatment under an inert atmosphere to obtain carbon nanotubes end-coated with metal nanoparticles.
步骤(1)中所述锌盐为硝酸锌、氯化锌、硫酸锌中的一种或两种以上，锌离子于混合溶液中的浓度为0.0125-0.1mol/L。The zinc salt in the step (1) is one or more of zinc nitrate, zinc chloride and zinc sulfate, and the concentration of the zinc ions in the mixed solution is 0.0125-0.1 mol/L.
步骤(1)中所述机配体为2-甲基咪唑，有机配体于混合溶液中的浓度为0.1-0.8mol/L。The ligand in the step (1) is 2-methylimidazole, and the concentration of the organic ligand in the mixed solution is 0.1 to 0.8 mol/L.
步骤(1)中所述混合溶液中的溶剂为甲醇、乙醇、水和DMF中的一种。The solvent in the mixed solution in the step (1) is one of methanol, ethanol, water and DMF.
步骤(2)中所述金属盐为钴或铁的氯化物、硝酸盐、乙酸盐中的一种或两种以上。The metal salt in the step (2) is one or more of a chloride, a nitrate or an acetate of cobalt or iron.
步骤(2)中所述氨基化合物为尿素、双氰胺、三聚氰胺中的一种或两种以上。The amino compound in the step (2) is one or more selected from the group consisting of urea, dicyandiamide, and melamine.
步骤(2)中所述溶剂为甲醇、乙醇和水中的一种或两种以上的混合溶液。The solvent in the step (2) is one or a mixture of two or more of methanol, ethanol and water.
步骤(2)中所述金属盐和氨基化合物的质量比1:1-1:5。The mass ratio of the metal salt to the amino compound in the step (2) is 1:1 to 1:5.
步骤(2)中所述除去溶剂的方法为旋转蒸发和/或真空干燥。The method of removing the solvent in the step (2) is rotary evaporation and/or vacuum drying.
步骤(3)所述热处理过程为升温至800-1100℃并保持0.5-3h，然后降温至室温；所述升温过程中从室温升温至热处理温度的升温速率为2-5℃/min；所述降温过程中降温速率为1-10℃/min。The heat treatment process in step (3) is to raise the temperature to 800-1100 ° C for 0.5-3 h, and then to cool to room temperature; the temperature increase rate from room temperature to the heat treatment temperature during the temperature increase is 2-5 ° C / min; The cooling rate during the cooling process is 1-10 ° C / min.
步骤(3)所述惰性气氛为氮气、氩气中的一种或两种的混合气。The inert atmosphere of the step (3) is a mixture of one or two of nitrogen gas and argon gas.
所述催化剂为聚合物电解质膜燃料电池和金属空气电池阴极氧还原反应电催化剂。The catalyst is a polymer electrolyte membrane fuel cell and a metal air battery cathode oxygen reduction reaction electrocatalyst.
与现有技术相比，本发明具有如下优点：制备过程中通过控制金属有机骨架的粒径可以直接控制碳纳米管的直径；碳纳米管直径均一可控，控制范围在50-300nm之间；制备工艺简单、无需电弧放电，化学气相沉积等传统制备碳纳米管的设备。同时制备的碳纳米管原位掺杂了大量N，改变碳纳米管表面电子结构，进一步提升其电化学性能，使其在能量的转换与存储领域均有较大的潜在应用前景。Compared with the prior art, the invention has the following advantages: the diameter of the carbon nanotubes can be directly controlled by controlling the particle size of the metal organic skeleton during the preparation process; the diameter of the carbon nanotubes is uniformly controllable, and the control range is between 50 and 300 nm; The preparation process is simple, no arc discharge, chemical vapor deposition and the like are conventionally prepared for carbon nanotubes. The carbon nanotubes prepared at the same time are doped with a large amount of N, which changes the electronic structure of the carbon nanotube surface and further enhances its electrochemical performance, so that it has potential application prospects in the field of energy conversion and storage.
附图说明DRAWINGS
图1：金属有机骨架低倍SEM照片；Figure 1: Low-SEM image of a metal-organic framework;
图2：碳纳米管低倍SEM照片；Figure 2: Low-power SEM photograph of carbon nanotubes;
图3：碳纳米管低倍SEM照片；Figure 3: Low-power SEM photograph of carbon nanotubes;
图4：碳纳米管XRD图。Figure 4: XRD pattern of carbon nanotubes.
具体实施方式Detailed ways
比较例1Comparative example 1
将2g双氰胺和1g乙酸钴溶于60ml乙醇，在80℃下加热搅拌5h后蒸干，获得固体粉末。取固体粉末置于刚玉舟，在氮气保护下以2℃/min升温速率加热至800℃并保温1h，再以5℃/min降温速率冷却至室温取出产物。2 g of dicyandiamide and 1 g of cobalt acetate were dissolved in 60 ml of ethanol, and the mixture was heated and stirred at 80 ° C for 5 hours, and then evaporated to dryness to give a solid powder. The solid powder was placed in a corundum boat, heated to 800 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to remove the product.
没有金属有机骨架作为模板，无法形成直径分布均匀的碳纳米管。Without the metal-organic framework as a template, it is impossible to form carbon nanotubes having a uniform diameter distribution.
比较例2Comparative example 2
20℃下，将1.436g的六水合硝酸钴和3.244g的2-甲基咪唑分别溶于100ml甲醇，前者在搅拌下缓慢加入后者中，继续搅拌12min，然后静置20h。离心分离，洗涤三次，在150℃下真空干燥8h，获得ZIF-67-300。将0.2g的ZIF-67-300和1g乙酸钴溶于60ml乙醇，在80℃下加热搅拌5h，再在室温下搅拌48h，然后60℃蒸干获得固体粉末。取固体粉末置于刚玉舟，在氮气保护下以2℃/min升温速率加热至800℃并保温1h，再以5℃/min降温速率冷却至室温取出产物。At 20 ° C, 1.436 g of cobalt nitrate hexahydrate and 3.244 g of 2-methylimidazole were separately dissolved in 100 ml of methanol, and the former was slowly added to the latter under stirring, stirring was continued for 12 min, and then allowed to stand for 20 h. The mixture was centrifuged, washed three times, and vacuum dried at 150 ° C for 8 h to obtain ZIF-67-300. 0.2 g of ZIF-67-300 and 1 g of cobalt acetate were dissolved in 60 ml of ethanol, stirred under heating at 80 ° C for 5 h, then at room temperature for 48 h, and then evaporated to dryness at 60 ° C to obtain a solid powder. The solid powder was placed in a corundum boat, heated to 800 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to remove the product.
没有氨基化合物(例如双氰胺)作为碳氮源，无法生长出碳纳米管。Without an amino compound (for example, dicyandiamide) as a carbon and nitrogen source, carbon nanotubes cannot be grown.
实施例1Example 1
20℃下，将1.436g的六水合硝酸钴和3.244g的2-甲基咪唑分别溶于100ml甲醇，前者在搅拌下缓慢加入后者中，继续搅拌12min，然后静置20h。离心分离，洗涤三次，在150℃下真空干燥8h，获得ZIF-67-300。将2g双氰胺和1g乙酸钴溶于60ml乙醇，在80℃下加热搅拌5h，再加入0.2g的ZIF-67-300，室温下搅拌48h后，60℃ 蒸干获得固体粉末。取固体粉末置于刚玉舟，在氮气保护下以2℃/min升温速率加热至800℃并保温1h，再以5℃/min降温速率冷却至室温取出碳纳米管。At 20 ° C, 1.436 g of cobalt nitrate hexahydrate and 3.244 g of 2-methylimidazole were separately dissolved in 100 ml of methanol, and the former was slowly added to the latter under stirring, stirring was continued for 12 min, and then allowed to stand for 20 h. The mixture was centrifuged, washed three times, and vacuum dried at 150 ° C for 8 h to obtain ZIF-67-300. 2 g of dicyandiamide and 1 g of cobalt acetate were dissolved in 60 ml of ethanol, and the mixture was stirred under heating at 80 ° C for 5 hours, and then 0.2 g of ZIF-67-300 was added thereto. After stirring at room temperature for 48 hours, it was evaporated to dryness at 60 ° C to obtain a solid powder. The solid powder was placed in a corundum boat, heated to 800 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to take out the carbon nanotubes.
以300nm的ZIF-67为模板，制备出外径约200nm的碳纳米管。Carbon nanotubes having an outer diameter of about 200 nm were prepared using 300 nm ZIF-67 as a template.
实施例2Example 2
20℃下，将1.436g的六水合硝酸钴和3.244g的2-甲基咪唑分别溶于200ml甲醇，前者在搅拌下缓慢加入后者中，继续搅拌12min，然后静置20h。离心分离，洗涤三次，在150℃下真空干燥8h，获得ZIF-67-150。将2g双氰胺和1g乙酸钴溶于60ml乙醇，在80℃下加热搅拌5h，再加入0.2g的ZIF-67-150，室温下搅拌48h后，60℃蒸干获得固体粉末。取固体粉末置于刚玉舟，在氮气保护下以2℃/min升温速率加热至800℃并保温1h，再以5℃/min降温速率冷却至室温取出碳纳米管。At 20 ° C, 1.436 g of cobalt nitrate hexahydrate and 3.244 g of 2-methylimidazole were separately dissolved in 200 ml of methanol, and the former was slowly added to the latter under stirring, stirring was continued for 12 min, and then allowed to stand for 20 h. The mixture was centrifuged, washed three times, and vacuum dried at 150 ° C for 8 h to obtain ZIF-67-150. 2 g of dicyandiamide and 1 g of cobalt acetate were dissolved in 60 ml of ethanol, and the mixture was stirred under heating at 80 ° C for 5 hours, and then 0.2 g of ZIF-67-150 was added thereto. After stirring at room temperature for 48 hours, it was evaporated to dryness at 60 ° C to obtain a solid powder. The solid powder was placed in a corundum boat, heated to 800 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to remove the carbon nanotubes.
以150nm的ZIF-67为模板，制备出外径约100nm的碳纳米管。Carbon nanotubes having an outer diameter of about 100 nm were prepared using 150 nm ZIF-67 as a template.
实施例3Example 3
20℃下，将1.470g的六水合硝酸锌和3.260的2-甲基咪唑分别溶于50ml甲醇，前者在搅拌下缓慢加入后者中，继续搅拌12min，然后静置20h。离心分离，洗涤三次，在150℃温度下真空干燥8h，获得ZIF-8-80。将2g双氰胺和1g乙酸钴溶于60ml乙醇，在80℃下加热搅拌5h，再加入0.2g的ZIF-8-80，室温下搅拌48h后，60℃蒸干获得固体粉末。取固体粉末置于刚玉舟，在氮气保护下以2℃/min升温速率加热至800℃并保温1h，再以5℃/min降温速率冷却至室温取出碳纳米管。At 20 ° C, 1.470 g of zinc nitrate hexahydrate and 3.60 of 2-methylimidazole were separately dissolved in 50 ml of methanol, the former was slowly added to the latter under stirring, stirring was continued for 12 min, and then allowed to stand for 20 h. The mixture was centrifuged, washed three times, and vacuum-dried at 150 ° C for 8 h to obtain ZIF-8-80. 2 g of dicyandiamide and 1 g of cobalt acetate were dissolved in 60 ml of ethanol, and the mixture was stirred under heating at 80 ° C for 5 hours, and then 0.2 g of ZIF-8-80 was added thereto. After stirring at room temperature for 48 hours, it was evaporated to dryness at 60 ° C to obtain a solid powder. The solid powder was placed in a corundum boat, heated to 800 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to take out the carbon nanotubes.
以100nm的ZIF-8为模板，制备出外径约50nm的碳纳米管。Carbon nanotubes having an outer diameter of about 50 nm were prepared using 100 nm ZIF-8 as a template.
实施例4Example 4
20℃下，将1.436g的六水合硝酸钴和3.244g的2-甲基咪唑分别溶于100ml甲醇，前者在搅拌下缓慢加入后者中，继续搅拌12min，然后静置20h。离心分离，洗涤三次，在150℃下真空干燥8h，获得ZIF-67-300。将2g双氰胺和1g乙酸钴溶于60ml乙醇，在80℃下加热搅拌5h，再加入0.2g的ZIF-67-300，室温下搅拌48h后，60℃蒸干获得固体粉末。取固体粉末置于刚玉舟，在氮气保护下以2℃/min升温速率加热至1000℃并保温1h，再以5℃/min降温速率冷却至室温取出碳纳米管。At 20 ° C, 1.436 g of cobalt nitrate hexahydrate and 3.244 g of 2-methylimidazole were separately dissolved in 100 ml of methanol, and the former was slowly added to the latter under stirring, stirring was continued for 12 min, and then allowed to stand for 20 h. The mixture was centrifuged, washed three times, and vacuum dried at 150 ° C for 8 h to obtain ZIF-67-300. 2 g of dicyandiamide and 1 g of cobalt acetate were dissolved in 60 ml of ethanol, and the mixture was stirred under heating at 80 ° C for 5 hours, and then 0.2 g of ZIF-67-300 was added thereto. After stirring at room temperature for 48 hours, it was evaporated to dryness at 60 ° C to obtain a solid powder. The solid powder was placed in a corundum boat, heated to 1000 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to remove the carbon nanotubes.
实施例5Example 5
20℃下，将1.436g的六水合硝酸钴和3.244g的2-甲基咪唑分别溶于100ml甲醇，前者在搅拌下缓慢加入后者中，继续搅拌12min，然后静置20h。离心分离，洗涤三次，在150℃下真空干燥8h，获得ZIF-67-300。将2g双氰胺和1g乙酸钴溶于60ml乙醇，在80℃下加热搅拌5h，再加入0.2g的ZIF-67-300，室温下搅拌48h后，60℃蒸干获得固体粉末。取固体粉末置于刚玉舟，在氮气保护下以2℃/min升温速率加热至800℃并保温2h，再以5℃/min降温速率冷却至室温取出碳纳米管。At 20 ° C, 1.436 g of cobalt nitrate hexahydrate and 3.244 g of 2-methylimidazole were separately dissolved in 100 ml of methanol, and the former was slowly added to the latter under stirring, stirring was continued for 12 min, and then allowed to stand for 20 h. The mixture was centrifuged, washed three times, and vacuum dried at 150 ° C for 8 h to obtain ZIF-67-300. 2 g of dicyandiamide and 1 g of cobalt acetate were dissolved in 60 ml of ethanol, and the mixture was stirred under heating at 80 ° C for 5 hours, and then 0.2 g of ZIF-67-300 was added thereto. After stirring at room temperature for 48 hours, it was evaporated to dryness at 60 ° C to obtain a solid powder. The solid powder was placed in a corundum boat, heated to 800 ° C at a heating rate of 2 ° C / min under nitrogen atmosphere and kept for 2 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to take out the carbon nanotubes.
实施例6Example 6
20℃下，将1.436g的六水合硝酸钴和3.244g的2-甲基咪唑分别溶于100ml甲醇，前者在搅拌下缓慢加入后者中，继续搅拌12min，然后静置20h。离心分离，洗涤三次，在150℃下真空干燥8h，获得ZIF-67-300。将2g双氰胺和1g乙酸钴溶于60ml乙醇，在80℃下加热搅拌5h，再加入0.1g的ZIF-67-300，室温下搅拌48h后，60℃蒸干获得固体粉末。取固体粉末置于刚玉舟，在氩气保护下以2℃/min升温速率加热至800℃并保温1h，再以5℃/min降温速率冷却至室温取出碳纳米管。At 20 ° C, 1.436 g of cobalt nitrate hexahydrate and 3.244 g of 2-methylimidazole were separately dissolved in 100 ml of methanol, and the former was slowly added to the latter under stirring, stirring was continued for 12 min, and then allowed to stand for 20 h. The mixture was centrifuged, washed three times, and vacuum dried at 150 ° C for 8 h to obtain ZIF-67-300. 2 g of dicyandiamide and 1 g of cobalt acetate were dissolved in 60 ml of ethanol, and the mixture was stirred under heating at 80 ° C for 5 hours, and then 0.1 g of ZIF-67-300 was added thereto. After stirring at room temperature for 48 hours, it was evaporated to dryness at 60 ° C to obtain a solid powder. The solid powder was placed in a corundum boat, heated to 800 ° C at a heating rate of 2 ° C / min under argon atmosphere for 1 h, and then cooled to room temperature at a cooling rate of 5 ° C / min to remove the carbon nanotubes.

Claims (17)

  1. 一种碳纳米管，其特征在于：所述碳纳米管呈竹节状形貌，即每根碳纳米管由2段以上的竹节状管段顺序连接而成，所述碳纳米管中含有N元素，一端包裹有金属纳米颗粒；所述碳纳米管的外径为50-300nm。A carbon nanotube characterized in that the carbon nanotubes have a bamboo-like morphology, that is, each carbon nanotube is sequentially connected by two or more bamboo-shaped tubular segments, and the carbon nanotubes contain N The element is coated with metal nanoparticles at one end; the carbon nanotubes have an outer diameter of 50-300 nm.
  2. 如权利要求1所述碳纳米管，其特征在于：所述N元素存在的形式为吡啶N、吡咯N、石墨化N和氧化N中的一种或两种以上，氮元素质量含量为2％-8％。The carbon nanotube according to claim 1, wherein the N element is present in the form of one or more of pyridine N, pyrrole N, graphitized N and oxidized N, and the nitrogen element has a mass content of 2%. -8%.
  3. 如权利要求1所述碳纳米管，其特征在于：所述金属纳米粒子为铁和/或钴，金属纳米粒子的直径为50-300nm。The carbon nanotube according to claim 1, wherein the metal nanoparticle is iron and/or cobalt, and the metal nanoparticle has a diameter of 50 to 300 nm.
  4. 如权利要求1所述碳纳米管，其特征在于：所述金属纳米颗粒占碳纳米管总质量的1％-10％。The carbon nanotube according to claim 1, wherein said metal nanoparticles comprise from 1% to 10% by mass based on the total mass of the carbon nanotubes.
  5. 如权利要求1-4任一所述碳纳米管，其特征在于：所述碳纳米管的外径较优为300nm；所述金属纳米粒子的直径较优为300nm。The carbon nanotube according to any one of claims 1 to 4, wherein the outer diameter of the carbon nanotube is preferably 300 nm; and the diameter of the metal nanoparticle is preferably 300 nm.
  6. 一种权利要求1-5任一所述碳纳米管的制备方法，其特征在于：包括以下步骤，A method for preparing a carbon nanotube according to any one of claims 1 to 5, characterized in that it comprises the following steps:
    (1)金属有机骨架的合成：制备锌盐和有机配体的混合溶液；30-120℃下进行反应，然后分离得到金属有机骨架；(1) Synthesis of a metal organic skeleton: preparing a mixed solution of a zinc salt and an organic ligand; performing a reaction at 30-120 ° C, and then separating to obtain a metal organic skeleton;
    (2)前驱体的制备：将金属盐和氨基化合物溶于溶剂，加入步骤(1)中制备的金属有机骨架，分散均匀后，除去溶剂得前驱体；(2) Preparation of precursor: the metal salt and the amino compound are dissolved in a solvent, and the metal organic skeleton prepared in the step (1) is added, and after dispersing uniformly, the solvent is removed to obtain a precursor;
    (3)碳纳米管的制备：将步骤(2)所得前驱体在惰性气氛下进行热处理，得末端包裹金属纳米颗粒的碳纳米管。(3) Preparation of carbon nanotubes: The precursor obtained in the step (2) is subjected to heat treatment under an inert atmosphere to obtain carbon nanotubes end-coated with metal nanoparticles.
  7. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(1)中所述锌盐为硝酸锌、氯化锌、硫酸锌中的一种或两种以上，锌离子于混合溶液中的浓度为0.0125-0.1mol/L。The method for preparing a carbon nanotube according to claim 6, wherein the zinc salt in the step (1) is one or more of zinc nitrate, zinc chloride and zinc sulfate, and the zinc ion is mixed in the solution. The concentration in the range is 0.0125-0.1 mol/L.
  8. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(1)中所述机配体为2-甲基咪唑，有机配体于混合溶液中的浓度为0.1-0.8mol/L。The method for preparing a carbon nanotube according to claim 6, wherein the ligand in the step (1) is 2-methylimidazole, and the concentration of the organic ligand in the mixed solution is 0.1-0.8 mol/L. .
  9. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(1)中所述混合溶液中的溶剂为甲醇、乙醇、水和DMF中的一种。The method for preparing a carbon nanotube according to claim 6, wherein the solvent in the mixed solution in the step (1) is one of methanol, ethanol, water and DMF.
  10. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(2)中所述金属盐为钴或铁的氯化物、硝酸盐、乙酸盐中的一种或两种以上。The method for producing a carbon nanotube according to claim 6, wherein the metal salt in the step (2) is one or more of a chloride, a nitrate or an acetate of cobalt or iron.
  11. 如权利要求5所述碳纳米管的制备方法，其特征在于：步骤(2)中所述氨基化合物为尿素、双氰胺、三聚氰胺中的一种或两种以上。The method for producing a carbon nanotube according to claim 5, wherein the amino compound in the step (2) is one or more selected from the group consisting of urea, dicyandiamide and melamine.
  12. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(2)中所述溶剂为甲醇、乙醇和水中的一种或两种以上的混合溶液。The method for producing a carbon nanotube according to claim 6, wherein the solvent in the step (2) is one or a mixture of two or more of methanol, ethanol and water.
  13. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(2)中所述金属盐和氨基化合物的质量比1:1-1:5。The method for preparing a carbon nanotube according to claim 6, wherein the mass ratio of the metal salt to the amino compound in the step (2) is 1:1 to 1:5.
  14. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(2)中所述除去溶剂的方法为旋转蒸发和/或真空干燥。The method for preparing a carbon nanotube according to claim 6, wherein the method for removing the solvent in the step (2) is rotary evaporation and/or vacuum drying.
  15. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(3)所述热处理过程为升温至800-1100℃并保持0.5-3h，然后降温至室温；所述升温过程中从室温升温至热处理温度的升温速率为2-5℃/min；所述降温过程中降温速率为1-10℃ /min。The method for preparing a carbon nanotube according to claim 6, wherein the heat treatment in the step (3) is to raise the temperature to 800-1100 ° C for 0.5-3 h, and then to cool to room temperature; The heating rate to the heat treatment temperature is 2-5 ° C / min; the cooling rate during the cooling is 1-10 ° C / min.
  16. 如权利要求6所述碳纳米管的制备方法，其特征在于：步骤(3)所述惰性气氛为氮气、氩气中的一种或两种的混合气。The method for preparing a carbon nanotube according to claim 6, wherein the inert atmosphere in the step (3) is a mixture of one or two of nitrogen and argon.
  17. 如权利要求1-5任一所述碳纳米管的应用，其特征在于：所述催化剂为聚合物电解质膜燃料电池和金属空气电池阴极氧还原反应电催化剂。The use of the carbon nanotube according to any one of claims 1 to 5, wherein the catalyst is a polymer electrolyte membrane fuel cell and a metal air battery cathode oxygen reduction reaction electrocatalyst.
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