CN109956463A - A kind of carbon nanotube and preparation method thereof - Google Patents

A kind of carbon nanotube and preparation method thereof Download PDF

Info

Publication number
CN109956463A
CN109956463A CN201711339359.1A CN201711339359A CN109956463A CN 109956463 A CN109956463 A CN 109956463A CN 201711339359 A CN201711339359 A CN 201711339359A CN 109956463 A CN109956463 A CN 109956463A
Authority
CN
China
Prior art keywords
carbon nanotube
preparation
metal
carbon nanotubes
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711339359.1A
Other languages
Chinese (zh)
Other versions
CN109956463B (en
Inventor
孙公权
许新龙
王素力
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201711339359.1A priority Critical patent/CN109956463B/en
Priority to PCT/CN2017/117054 priority patent/WO2019113993A1/en
Publication of CN109956463A publication Critical patent/CN109956463A/en
Application granted granted Critical
Publication of CN109956463B publication Critical patent/CN109956463B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inert Electrodes (AREA)
  • Catalysts (AREA)

Abstract

本发明涉及一种直径可控碳纳米管及其制备方法，所述方法是将金属有机骨架、金属盐以及氨基化合物在液相中，得到的前驱体在惰性气氛下热处理进行碳化，通过改变前驱体中金属有机骨架的粒径实现碳纳米管直可控。与现有技术相比，本发明具有如下优点：制备过程中通过简单改变溶剂、反应温度等合成条件获得不同粒径的金属有机骨架就可以进而控制碳纳米管的直径；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。The invention relates to a diameter-controllable carbon nanotube and a preparation method thereof. The method comprises the steps of carbonizing a precursor obtained by carbonizing a metal-organic framework, a metal salt and an amino compound in a liquid phase by heat treatment in an inert atmosphere, and changing the precursor The particle size of the metal-organic framework in the bulk can be directly controlled by the carbon nanotubes. Compared with the prior art, the present invention has the following advantages: in the preparation process, the diameter of carbon nanotubes can be further controlled by simply changing synthesis conditions such as solvent and reaction temperature to obtain metal-organic frameworks with different particle sizes; the preparation process is simple and does not require an arc. Electric discharge, chemical vapor deposition and other traditional equipment for preparing carbon nanotubes. At the same time, the prepared carbon nanotubes are doped with a large amount of N in situ, which changes the surface electronic structure of the carbon nanotubes and further improves its electrochemical performance, so that it has great potential application prospects in the fields of energy conversion and storage.

Description

一种碳纳米管及其制备方法A kind of 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 preparation and application of carbon materials, in particular to the preparation and application of a carbon nanotube.

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 nanomaterials composed of carbon atoms. Their unique one-dimensional structure, high degree of graphitization, and excellent electrical and mechanical properties have aroused widespread interest among 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 changing the diameter of carbon nanotubes can significantly affect its electrochemical properties.

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C60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 preparation methods of carbon nanotubes mainly include arc discharge method, laser evaporation method, CVD, solid-phase pyrolysis method, etc. In 1991, Japanese physicist Iijima first discovered carbon nanotubes by the arc discharge method. This method is technically simple, but the obtained carbon nanotubes are mixed with C 60 and other products, and the purity is not high. The CVD method has simple equipment requirements and low cost, and is currently the most feasible and economical method for synthesizing carbon nanotubes. Recently, the method of direct high temperature carbonization of solid phase precursors (such as fullerene carbon black, organometallic compounds, polymers) has been used to prepare carbon nanotubes. N, S and B compounds are added to the precursor to in-situ dope into the carbon nanotubes during the heating process, thereby changing the surface electronic structure of the carbon nanotubes and further improving the electrochemical performance. However, the behavior of precursors during high-temperature pyrolysis is difficult to control, and the resulting carbon nanotubes are usually non-uniform in morphology.

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：Aiming at the problem of uncontrollable morphology of carbon nanotubes prepared from pyrolysis precursors, the present invention proposes a method for preparing carbon nanotubes with a controllable diameter. The present invention adopts the following specific scheme to achieve:

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％。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。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。A carbon nanotube is characterized in that: the carbon nanotube has a bamboo-like shape, that is, each carbon nanotube is formed by sequentially connecting more than two bamboo-like tube segments, and the carbon nanotube contains N element, and one end is wrapped with metal nanoparticles; the outer diameter of the carbon nanotube is 50-300nm. The N element exists in the form of one or more of pyridine N, pyrrole N, graphitized N and oxide N, and the mass content of nitrogen element is 2%-8%. The carbon nanotube according to claim 1, wherein the metal nanoparticles are iron and/or cobalt, and the diameter of the metal nanoparticles is 50-300 nm. The metal nanoparticles account for 1%-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 preparation method of 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 metal-organic framework: prepare a mixed solution of zinc salt and organic ligand; carry out the reaction at 30-120 °C, and then separate the metal-organic framework;

(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 the precursor: dissolve the metal salt and the amino compound in a solvent, add the metal-organic framework prepared in step (1), and after uniform dispersion, remove the solvent to obtain the 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 step (2) is heat-treated in an inert atmosphere to obtain carbon nanotubes with ends wrapped 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。In step (1), the zinc salt is one or more of zinc nitrate, zinc chloride, and zinc sulfate, and the concentration of 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。In the step (1), the organic ligand is 2-methylimidazole, and the concentration of the organic ligand in the mixed solution is 0.1-0.8 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 described in 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。In step (2), the metal salt is one or more of cobalt or iron chloride, nitrate, and acetate.

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 described in step (2) is one or more 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 described in step (2) is one or more mixed solutions 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 and the amino compound in the step (2) is 1:1-1:5.

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 for removing the solvent in 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。In the step (3), the heat treatment process is to heat up to 800-1100° C. and keep it for 0.5-3 h, and then cool down to room temperature; During the cooling process, the cooling rate 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 in step (3) is one or a mixture of nitrogen and argon.

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 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 nanotube can be directly controlled by controlling the particle size of the metal-organic framework in the preparation process; the diameter of the carbon nanotube is uniform and controllable, and the control range is between 50-300 nm; The preparation process is simple, without arc discharge, chemical vapor deposition and other traditional equipment for preparing carbon nanotubes. At the same time, the prepared carbon nanotubes are doped with a large amount of N in situ, which changes the surface electronic structure of the carbon nanotubes and further improves its electrochemical performance, so that it has great potential application prospects in the fields of energy conversion and storage.

附图说明Description of drawings

图1：金属有机骨架低倍SEM照片Figure 1: Low magnification SEM image of metal organic framework

图2：碳纳米管低倍SEM照片Figure 2: Low magnification SEM image of carbon nanotubes

图3：碳纳米管低倍SEM照片Figure 3: Low magnification SEM image 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, heated and stirred at 80° C. for 5 h, evaporated to dryness, and a solid powder was obtained. The solid powder was taken and placed in a corundum boat, heated to 800°C at a heating rate of 2°C/min under nitrogen protection and kept for 1 h, and then cooled to room temperature at a cooling rate of 5°C/min to take out 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 metal-organic frameworks as templates, carbon nanotubes with uniform diameter distribution cannot be formed

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 dissolved in 100 ml of methanol respectively. The former was slowly added to the latter under stirring, and the stirring was continued for 12 min, and then allowed to stand for 20 h. Centrifuged, washed three times, and vacuum-dried at 150 °C for 8 h to obtain ZIF-67-300. Dissolve 0.2 g of ZIF-67-300 and 1 g of cobalt acetate in 60 ml of ethanol, heat and stir at 80 °C for 5 h, then at room temperature for 48 h, and then evaporate to dryness at 60 °C to obtain a solid powder. The solid powder was taken and placed in a corundum boat, heated to 800°C at a heating rate of 2°C/min under nitrogen protection and kept for 1 h, and then cooled to room temperature at a cooling rate of 5°C/min to take out 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。Carbon nanotubes cannot be grown without amino compounds such as dicyandiamide as carbon and nitrogen sources.

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 dissolved in 100 ml of methanol respectively. The former was slowly added to the latter under stirring, and the stirring was continued for 12 min, and then allowed to stand for 20 h. Centrifuged, washed three times, and vacuum-dried at 150 °C for 8 h to obtain ZIF-67-300. Dissolve 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heat and stir at 80°C for 5h, then add 0.2g of ZIF-67-300, stir at room temperature for 48h, and evaporate to dryness at 60°C to obtain solid powder. The solid powder was taken and placed in a corundum boat, heated to 800°C at a heating rate of 2°C/min under nitrogen protection 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。Using 300nm ZIF-67 as template, carbon nanotubes with an outer diameter of about 200nm were prepared.

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 dissolved in 200 ml of methanol respectively. The former was slowly added to the latter under stirring, and the stirring was continued for 12 min, and then allowed to stand for 20 h. Centrifuged, washed three times, and vacuum-dried at 150 °C for 8 h to obtain ZIF-67-150. Dissolve 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heat and stir at 80°C for 5h, then add 0.2g of ZIF-67-150, stir at room temperature for 48h, and evaporate to dryness at 60°C to obtain solid powder. The solid powder was taken and placed in a corundum boat, heated to 800°C at a heating rate of 2°C/min under nitrogen protection 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150nm的ZIF-67为模板，制备出外径约100nm的碳纳米管。Using 150nm ZIF-67 as template, carbon nanotubes with an outer diameter of about 100nm were prepared.

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, 1.470g of zinc nitrate hexahydrate and 3.260g of 2-methylimidazole were dissolved in 50ml of methanol respectively. The former was slowly added to the latter under stirring, and the stirring was continued for 12min, and then allowed to stand for 20h. Centrifuged, washed three times, and vacuum-dried at 150 °C for 8 h to obtain ZIF-8-80. Dissolve 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heat and stir at 80°C for 5h, then add 0.2g of ZIF-8-80, stir at room temperature for 48h, and evaporate to dryness at 60°C to obtain solid powder. The solid powder was taken and placed in a corundum boat, heated to 800°C at a heating rate of 2°C/min under nitrogen protection 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。Using 100nm ZIF-8 as a template, carbon nanotubes with an outer diameter of about 50nm were prepared.

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 dissolved in 100 ml of methanol respectively. The former was slowly added to the latter under stirring, and the stirring was continued for 12 min, and then allowed to stand for 20 h. Centrifuged, washed three times, and vacuum-dried at 150 °C for 8 h to obtain ZIF-67-300. Dissolve 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heat and stir at 80°C for 5h, then add 0.2g of ZIF-67-300, stir at room temperature for 48h, and evaporate to dryness at 60°C to obtain solid powder. The solid powder was taken and placed in a corundum boat, heated to 1000 °C at a heating rate of 2 °C/min under nitrogen protection 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.

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 dissolved in 100 ml of methanol respectively. The former was slowly added to the latter under stirring, and the stirring was continued for 12 min, and then allowed to stand for 20 h. Centrifuged, washed three times, and vacuum-dried at 150 °C for 8 h to obtain ZIF-67-300. Dissolve 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heat and stir at 80°C for 5h, then add 0.2g of ZIF-67-300, stir at room temperature for 48h, and evaporate to dryness at 60°C to obtain solid powder. The solid powder was taken and placed in a corundum boat, heated to 800°C at a heating rate of 2°C/min under nitrogen protection and kept for 2 hours, 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 dissolved in 100 ml of methanol respectively. The former was slowly added to the latter under stirring, and the stirring was continued for 12 min, and then allowed to stand for 20 h. Centrifuged, washed three times, and vacuum-dried at 150 °C for 8 h to obtain ZIF-67-300. Dissolve 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heat and stir at 80°C for 5h, then add 0.1g of ZIF-67-300, stir at room temperature for 48h, and evaporate to dryness at 60°C to obtain solid powder. The solid powder was taken and placed in a corundum boat, heated to 800 °C at a heating rate of 2 °C/min under argon protection 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.

Claims (17)

1. a kind of carbon nanotube, it is characterised in that: the carbon nanotube be in Bamboo-shaped pattern, i.e. every carbon nanotube by 2 sections with On Bamboo-shaped pipeline section be linked in sequence, N element is contained in the carbon nanotube, one end is enclosed with metal nanoparticle；Institute The outer diameter for stating carbon nanotube is 50-300nm.
2. carbon nanotube as described in claim 1, it is characterised in that: form existing for the N element is pyridine N, pyrroles N, stone One or more of inkization N and oxidation N, nitrogen mass content are 2%-8%.
3. carbon nanotube as described in claim 1, it is characterised in that: the metal nanoparticle is iron and/or cobalt, metal nano The diameter of particle is 50-300nm.
4. carbon nanotube as described in claim 1, it is characterised in that: the metal nanoparticle accounts for carbon nanotube gross mass 1%-10%.
5. the carbon nanotube as described in claim 1-4 is any, it is characterised in that: the more excellent outer diameter of the carbon nanotube is 300nm； The more excellent diameter of the metal nanoparticle is 300nm.
6. a kind of preparation method of any carbon nanotube of claim 1-5, it is characterised in that: include the following steps,
(1) synthesis of metal organic framework: the mixed solution of zinc salt and organic ligand is prepared；It is reacted at 30-120 DEG C, so Isolated metal organic framework afterwards；
(2) preparation of presoma: metal salt and amino-compound are dissolved in solvent, it is organic that the metal prepared in step (1) is added Skeleton after being uniformly dispersed, removes solvent and obtains presoma；
(3) preparation of carbon nanotube: presoma obtained by step (2) is heat-treated under an inert atmosphere, obtains end package gold The carbon nanotube of metal nano-particle.
7. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: zinc salt described in step (1) be zinc nitrate, One or more of zinc chloride, zinc sulfate, concentration of the zinc ion in mixed solution are 0.0125-0.1mol/L.
8. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: machine ligand described in step (1) is 2- first Base imidazoles, concentration of the organic ligand in mixed solution are 0.1-0.8mol/L.
9. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: in mixed solution described in step (1) Solvent is one of methanol, ethyl alcohol, water and DMF.
10. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: metal salt described in step (2) be cobalt or One or more of the chloride of iron, nitrate, acetate.
11. the preparation method of carbon nanotube as claimed in claim 5, it is characterised in that: amino-compound described in step (2) is One or more of urea, dicyandiamide, melamine.
12. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: solvent described in step (2) be methanol, The mixed solution of one or more of second alcohol and water.
13. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: metal salt and amino described in step (2) The mass ratio 1:1-1:5 of compound.
14. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: remove the side of solvent described in step (2) Method is rotary evaporation and/or vacuum drying.
15. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: step (3) heat treatment process is to rise Temperature is to 800-1100 DEG C and keeps 0.5-3h, is then cooled to room temperature；From room temperature to heat treatment temperature in the temperature-rise period The heating rate of degree is 2-5 DEG C/min；Rate of temperature fall is 1-10 DEG C/min in the temperature-fall period.
16. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: step (3) inert atmosphere is nitrogen The gaseous mixture of one or both of gas, argon gas.
17. the application of carbon nanotube as described in claim 1-5 is any, it is characterised in that: the catalyst is polymer electrolytic Membrane fuel cell and metal air battery cathodes oxygen reduction reaction elctro-catalyst.
CN201711339359.1A 2017-12-14 2017-12-14 A kind of carbon nanotube and preparation method thereof Active CN109956463B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201711339359.1A CN109956463B (en) 2017-12-14 2017-12-14 A kind of carbon nanotube and preparation method thereof
PCT/CN2017/117054 WO2019113993A1 (en) 2017-12-14 2017-12-19 Carbon nanotube and method for fabrication thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711339359.1A CN109956463B (en) 2017-12-14 2017-12-14 A kind of carbon nanotube and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109956463A true CN109956463A (en) 2019-07-02
CN109956463B CN109956463B (en) 2022-07-05

Family

ID=66819878

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711339359.1A Active CN109956463B (en) 2017-12-14 2017-12-14 A kind of carbon nanotube and preparation method thereof

Country Status (2)

Country Link
CN (1) CN109956463B (en)
WO (1) WO2019113993A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110683530A (en) * 2019-08-26 2020-01-14 广西大学 A method for in-situ synthesis of cobalt-nitrogen co-doped carbon nanotubes
CN110813362A (en) * 2019-12-03 2020-02-21 湘潭大学 A kind of high nitrogen content carbon nanotube catalyst and its preparation method and application
CN111138367A (en) * 2019-12-07 2020-05-12 北京科技大学 A kind of cobalt metal organic framework material and preparation method and application thereof
CN111193039A (en) * 2020-01-08 2020-05-22 华中科技大学 A kind of method and product for preparing oxygen reduction catalyst from biomass
CN112103518A (en) * 2020-09-15 2020-12-18 上海理工大学 Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material
CN112331869A (en) * 2020-11-06 2021-02-05 五邑大学 Cobalt-nitrogen double-doped hybrid carbon material and preparation method thereof
CN113036112A (en) * 2021-03-04 2021-06-25 宁波晟默贸易有限公司 Preparation method of lithium-sulfur battery electrode material with nitrogen-rich porous carbon framework
CN113800509A (en) * 2021-10-11 2021-12-17 安徽工业大学 Method for preparing high-nitrogen-doped graphitized porous carbon material by metal nitrate catalytic carbonization method
CN115939394A (en) * 2022-12-06 2023-04-07 山东省科学院能源研究所 Nitrogen-doped carbon nanotube packaging nickel nanoparticle framework and preparation and application thereof
WO2023137840A1 (en) * 2022-01-19 2023-07-27 苏州大学 Preparation method for co, n, and s co-doped carbon nano-bead composite material and use thereof

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111489898A (en) * 2020-04-16 2020-08-04 嘉兴学院 Preparation method of low-cost ZnNCN material
CN112090441B (en) * 2020-09-28 2023-04-25 浙江师范大学 Preparation method, product and application of a cobalt-based carbon nanomaterial
CN112853378B (en) * 2021-01-18 2023-10-10 南昌航空大学 Preparation method of Bi-NC catalyst for carbon dioxide electroreduction
CN113788470A (en) * 2021-09-29 2021-12-14 中北大学 Preparation method of nitrogen-doped carbon nanotube with cup stack structure
CN114751399B (en) * 2022-04-29 2024-04-09 北京航空航天大学 Carbon nanotube domain-limited metal nanowire material, and preparation method and application thereof
CN115215325B (en) * 2022-07-08 2023-08-29 安徽大学 Composite electromagnetic wave absorbing material and preparation method and application thereof
CN115475646A (en) * 2022-09-20 2022-12-16 哈尔滨工业大学（深圳） Carbon nanotube-based catalyst and preparation method and application thereof
CN116364907B (en) * 2023-05-22 2023-08-29 天津巴莫科技有限责任公司 Lithium-rich manganese-based layered cathode material, preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1627933A1 (en) * 2004-08-09 2006-02-22 C.R.F. Società Consortile per Azioni Method and device for adsorbing and/or desorbing hydrogen with the aid of shape memory materials
KR20100031345A (en) * 2008-09-12 2010-03-22 재단법인서울대학교산학협력재단 Hybrid composite of carbonnanotube and metal-organic frameworks having high surface area, high hydrogen storage capacity and enhanced moisture-stability, and process for preparing same
WO2014046107A1 (en) * 2012-09-20 2014-03-27 国立大学法人京都大学 Metal nanoparticle complex and method for producing same
CN104745149A (en) * 2015-03-05 2015-07-01 北京科技大学 Preparation method for carbon-containing material metal organic framework-based composite phase change material
CN104944410A (en) * 2015-06-01 2015-09-30 北京理工大学 Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material
CN105413730A (en) * 2015-11-25 2016-03-23 青岛大学 Preparation method of cobalt electro-catalysis oxygen reduction material wrapping nitrogen-doped carbon nanotube
CN105618789A (en) * 2014-10-29 2016-06-01 中国科学院大连化学物理研究所 Preparation method of nitrogen-doped carbon nano tube packaging cobalt nanoparticles
CN106904596A (en) * 2017-03-06 2017-06-30 武汉理工大学 The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101450799A (en) * 2007-11-29 2009-06-10 索尼株式会社 Nitrogen doped carbon nanotube and preparation method thereof, and carbon nanotube element
CN104016328B (en) * 2013-02-28 2015-12-23 中国科学院大连化学物理研究所 A kind of preparation method of nitrogenous carbon nanotube
CN105084339B (en) * 2015-06-25 2017-06-16 中国科学技术大学 N doping multi-walled carbon nano-tubes and preparation method thereof
CN105776181B (en) * 2016-04-29 2018-12-21 大连理工大学 Preparation method of sheet-like nanoporous carbon and carbon nanotube composite material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1627933A1 (en) * 2004-08-09 2006-02-22 C.R.F. Società Consortile per Azioni Method and device for adsorbing and/or desorbing hydrogen with the aid of shape memory materials
KR20100031345A (en) * 2008-09-12 2010-03-22 재단법인서울대학교산학협력재단 Hybrid composite of carbonnanotube and metal-organic frameworks having high surface area, high hydrogen storage capacity and enhanced moisture-stability, and process for preparing same
WO2014046107A1 (en) * 2012-09-20 2014-03-27 国立大学法人京都大学 Metal nanoparticle complex and method for producing same
CN105618789A (en) * 2014-10-29 2016-06-01 中国科学院大连化学物理研究所 Preparation method of nitrogen-doped carbon nano tube packaging cobalt nanoparticles
CN104745149A (en) * 2015-03-05 2015-07-01 北京科技大学 Preparation method for carbon-containing material metal organic framework-based composite phase change material
CN104944410A (en) * 2015-06-01 2015-09-30 北京理工大学 Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material
CN105413730A (en) * 2015-11-25 2016-03-23 青岛大学 Preparation method of cobalt electro-catalysis oxygen reduction material wrapping nitrogen-doped carbon nanotube
CN106904596A (en) * 2017-03-06 2017-06-30 武汉理工大学 The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110683530A (en) * 2019-08-26 2020-01-14 广西大学 A method for in-situ synthesis of cobalt-nitrogen co-doped carbon nanotubes
CN110813362A (en) * 2019-12-03 2020-02-21 湘潭大学 A kind of high nitrogen content carbon nanotube catalyst and its preparation method and application
CN111138367B (en) * 2019-12-07 2021-07-27 北京科技大学 Cobalt metal organic framework material and preparation method and application thereof
CN111138367A (en) * 2019-12-07 2020-05-12 北京科技大学 A kind of cobalt metal organic framework material and preparation method and application thereof
CN111193039A (en) * 2020-01-08 2020-05-22 华中科技大学 A kind of method and product for preparing oxygen reduction catalyst from biomass
CN112103518B (en) * 2020-09-15 2022-07-29 上海理工大学 Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material
CN112103518A (en) * 2020-09-15 2020-12-18 上海理工大学 Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material
CN112331869A (en) * 2020-11-06 2021-02-05 五邑大学 Cobalt-nitrogen double-doped hybrid carbon material and preparation method thereof
CN113036112A (en) * 2021-03-04 2021-06-25 宁波晟默贸易有限公司 Preparation method of lithium-sulfur battery electrode material with nitrogen-rich porous carbon framework
CN113800509A (en) * 2021-10-11 2021-12-17 安徽工业大学 Method for preparing high-nitrogen-doped graphitized porous carbon material by metal nitrate catalytic carbonization method
CN113800509B (en) * 2021-10-11 2024-02-06 安徽工业大学 Method for preparing high-nitrogen-doped graphitized porous carbon material by metal nitrate catalytic carbonization method
WO2023137840A1 (en) * 2022-01-19 2023-07-27 苏州大学 Preparation method for co, n, and s co-doped carbon nano-bead composite material and use thereof
CN115939394A (en) * 2022-12-06 2023-04-07 山东省科学院能源研究所 Nitrogen-doped carbon nanotube packaging nickel nanoparticle framework and preparation and application thereof

Also Published As

Publication number Publication date
WO2019113993A1 (en) 2019-06-20
CN109956463B (en) 2022-07-05

Similar Documents

Publication Publication Date Title
CN109956463B (en) A kind of carbon nanotube and preparation method thereof
Luo et al. A review on the synthesis of transition metal nitride nanostructures and their energy related applications
CN109518222B (en) Bismuth-based catalyst for electrocatalytic CO2 reduction to formic acid, preparation method and application thereof
CN104944410B (en) A kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite
CN109309214B (en) Preparation method of carbon-coated nickel nano composite material
CN105895886B (en) A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof
Wang et al. Highly dispersed β-NiS nanoparticles in porous carbon matrices by a template metal–organic framework method for lithium-ion cathode
CN106564875B (en) A kind of preparation method of the nitrogen co-doped hollow carbon nano-particle of monodisperse cobalt
CN104108710B (en) A kind of N doping porous graphene and preparation method thereof
CN104016328B (en) A kind of preparation method of nitrogenous carbon nanotube
CN109962246A (en) A supported low platinum core-shell catalyst and its preparation and application
CN106549163A (en) A preparation method and application of cobalt and nitrogen co-doped ultra-thin nano-carbon sheets
CN110860289A (en) A kind of preparation method and application of metal single-atom material
CN110272035A (en) A kind of nano cages and the application of the method and its preparation preparing nano cages with metal ion catalysis organic ligand
Xu et al. A highly efficient and free-standing copper single atoms anchored nitrogen-doped carbon nanofiber cathode toward reliable Li–CO2 batteries
CN102623696A (en) Preparation method and application of a core-shell carbon-coated iron nitride nanocomposite particle
CN108689398A (en) A kind of preparation method of controllable nitrogen-doped carbon nanometer pipe
CN106602023B (en) A kind of method of fabricated in situ graphite phase carbon nitride-oxidation carbon/carbon-copper composite material
CN111777058A (en) Preparation of a kind of carbon nanotube and its application in lithium ion battery
Zhou et al. Polymerization inspired synthesis of MnO@ carbon nanowires with long cycling stability for lithium ion battery anodes: Growth mechanism and electrochemical performance
Chen et al. A polarization boosted strategy for the modification of transition metal dichalcogenides as electrocatalysts for water‐splitting
Tang et al. Carbon-coated Li4Ti5O12 tablets derived from metal-organic frameworks as anode material for lithium-ion batteries
Zakharova et al. MoO2/C composites prepared by tartaric acid and glucose-assisted sol-gel processes as anode materials for lithium-ion batteries
CN110265225A (en) The method for preparing N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle composite material
CN107413365A (en) A kind of preparation method of N doping super large tube chamber carbon nano tube compound material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant