WO2015081663A1 - Method for preparing aza graphene and nanometer metal graphene by using solid phase cracking method - Google Patents

Method for preparing aza graphene and nanometer metal graphene by using solid phase cracking method Download PDF

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WO2015081663A1
WO2015081663A1 PCT/CN2014/077420 CN2014077420W WO2015081663A1 WO 2015081663 A1 WO2015081663 A1 WO 2015081663A1 CN 2014077420 W CN2014077420 W CN 2014077420W WO 2015081663 A1 WO2015081663 A1 WO 2015081663A1
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graphene
metal
degrees
phthalocyanine
nitrogen
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French (fr)
Chinese (zh)
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薛卫东
赵睿
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四川环碳科技有限公司
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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
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention adopts a solid phase cracking technique to prepare aza-graphene and nano-metal graphene materials, and belongs to the field of high-tech material preparation. Background technique
  • graphene is a zero-bandgap semiconductor in which electrons move at speeds up to 1/300 of the speed of light, and graphene carrier mobility is as high as Sx loScm ⁇ V ⁇ S 4 [3-8].
  • graphene also has good thermal and magnetic properties [9, 10]. The high specific surface area of graphene makes it a huge potential application in the fields of supercapacitors, hydrogen storage, and single molecule chemical sensors [11].
  • the graphite oxide reduction method is the main method for preparing graphene.
  • the method is to carry out strong oxidation treatment of graphite, obtain graphene oxide and then strip it to prepare graphene oxide, and finally obtain graphene by reduction treatment. Due to the severe destruction of the structure of the graphene sheet during the strong oxidation process, although the electron conjugate structure of the graphene sheet is partially restored after the reduction treatment, the performance indexes of the obtained graphene material are still high quality graphene. There is a big gap.
  • the oxidation process of graphite usually requires a large amount of strong acidic oxidants such as concentrated sulfuric acid, concentrated nitric acid and potassium permanganate, and toxic chemicals such as hydrazine hydrate or sodium borohydride are required in the reduction process, which is not only energy-intensive but also inefficient. High cost and serious pollution.
  • the invention patents CN102897756, CN102897757, and the like are required in the reduction process, which is not only energy-intensive but also inefficient. High cost and serious pollution.
  • the epitaxial growth method for preparing graphene needs to be filled with a carbon source gas (formamidine, acetamethylene, acetylene, etc.) at a high temperature, and the gas decomposes and forms graphene on the substrate.
  • a carbon source gas formamidine, acetamethylene, acetylene, etc.
  • the method requires a high temperature of 1000 degrees or more, and requires hydrogen as a reduction.
  • Sexual gas, strict requirements on production conditions, long reaction time, low yield, and the use of a large number of dangerous gases increases production costs. Further application of graphene is limited.
  • Such as invention patents CN102903616, CN102891074 and the like. Nitrogen doping in graphene can adjust the electronic properties of the device and improve the electrical conductivity and electrochemical stability of graphene.
  • the graphene nitrogen doping method mainly includes hydrothermal synthesis method, chemical synthesis method, CVD method, plasma sputtering, etc. (such as invention patents CN102887498, CN102745678, CN101708837, etc.), and the synthesis efficiency and quality of these methods are generally low.
  • the incorporation of metal nanoparticles into graphene is a common practice for electrochemical device modification and electrode modification.
  • the main composite methods include redox method, electrochemical reduction method, etc. (such as CN102174702A, CN102136306A, etc.), the main methods of these methods.
  • the problem is that there is a large amount of chemical waste, and the nanoparticles are easy to aggregate.
  • Phthalocyanine is a class of macrocyclic compounds.
  • the center of the phthalocyanine is an 18- ⁇ system consisting of carbon-nitrogen conjugated double bonds.
  • the ring has a cavity with a diameter of about 2.7 X 10 ⁇ .
  • the two hydrogen atoms in the central cavity can be replaced by more than 70 elements, including almost all metal elements and a part of non-metal elements (as shown in Figure 1), as well as metal oxides.
  • the phthalocyanine polymers generally refer to those polymers containing a phthalocyanine ring structure (Fig. 2).
  • the present invention will use such a compound as a starting material to obtain a graphene-based material by a low-temperature solid phase cracking technique.
  • the present invention provides a method for preparing aza-graphene and metal graphene using a solid phase cracking technique. It involves the use of phthalocyanine compounds, phthalocyanine polymers and their derivatives as starting materials, nitrogen, argon, argon/hydrogen mixtures, argon/ammonia mixtures, nitrogen/hydrogen mixtures, nitrogen/ammonia Under common atmospheres such as gas mixing, the pyrochemical properties of the reference materials are used to prepare nitrogen-containing graphene and metal graphene materials by one-time cracking at 700 degrees or more.
  • the method is characterized as follows: 1.
  • a graphene material with a curling behavior can be obtained by using copper foil or nickel foil as a catalyst, and the material can improve its electrical conductivity and the like.
  • the graphene materials prepared by the invention will be applied to single molecule detection technology, field effect transistor and integrated circuit, transparent conductive electrode, conductive ink, field emission source and vacuum electronic device, absorbing material, super capacitor and biological device. etc.
  • Step 1 The phthalocyanine compound, the phthalocyanine polymer and its derivatives are used as starting materials, and are directly used without other raw materials.
  • Step 2 In the atmosphere furnace, under the protection of a certain gas, with reference to the thermochemical characteristics of the raw materials, the aza-graphene and the metal graphene-based materials are obtained by a one-step cracking under a catalyst-free condition by a temperature-programmed method.
  • Step 1 The technical solution of the present invention is as follows: Step 1: The phthalocyanine compound, the phthalocyanine polymer and its derivatives are used as starting materials, and are directly used without other raw materials.
  • Step 2 In the atmosphere furnace, under the protection of a certain gas, referring to the thermochemical characteristics of the raw materials, using a temperature programmed method, one-time cracking under the condition of a metal catalyst to obtain aza graphenes and metal graphenes having a coiled structure. material.
  • the starting material may be a commercially available or self-made metal phthalocyanine compound and a derivative thereof.
  • metal phthalocyanine compounds and derivatives thereof e.g., nickel phthalocyanine, copper phthalocyanine, iron phthalocyanine, molybdenum phthalocyanine, cobalt phthalocyanine, phthalocyanine gold, silver phthalocyanine, and derivatives thereof).
  • the starting material may also be one of non-metal phthalocyanines such as a pure phthalocyanine compound.
  • the starting material may also be one of metal oxide-containing phthalocyanines.
  • the starting material may also be one of a polymer containing a phthalocyanine ring structure or a porphyrin-based polymer containing a phthalocyanine ring-like structure.
  • the gas protection refers to a common protective gas such as a nitrogen gas, an argon gas, an argon/hydrogen gas mixture, an argon gas/ammonia gas mixture gas, a nitrogen/hydrogen gas mixture gas, a nitrogen gas/ammonia gas mixture gas, etc.;
  • the volume ratio is between 0.1:9.9 and 1:9; the flow rate is controlled between 10 and 50 cm ⁇ min" 1 ;
  • the metal catalyst refers to a metal or alloy such as copper foil, copper mesh, nickel foil, or nickel foam.
  • the cracking temperature of the cracking varies depending on the thermochemical characteristics of the raw material, and is generally 700 degrees or more, preferably 800 to 1000 degrees.
  • the time to crack the autocatalytic graphene sheet is 4 to 24 hours. Shortening or prolonging the cracking time has an effect on the size, thickness and quality of the final graphene material.
  • the nitrogen element in the aza graphene-based material is derived from the self-nitrogen atom in the phthalocyanine skeleton. If a higher content of nitrogen atoms is required, a mixture of ammonia gas and inert gas can be introduced during the cracking process.
  • the metal nanoparticles in the graphene-based material containing metal nanoparticles are obtained from the metal species contained in the starting material itself. Taking copper phthalocyanine as an example, a graphene material containing metal copper nanoparticles is finally obtained.
  • any compound containing a phthalocyanine ring and its derivatives can be used as a starting material for obtaining aza graphene and metal graphene; 2. To improve the conductivity or other properties of the material, Ammonia increases the final nitrogen content of the material; 3. Adjusts the experimental parameters such as cracking temperature, gas flow rate, gas flow rate, etc. to effectively control the size, thickness and quality of graphene materials; 4. When using copper foil or nickel foil as catalyst , a graphene material having a curling behavior can also be obtained, which can improve the electrical conductivity and the like; 5. Different raw materials are formulated according to their thermochemical properties. Sequence heating scheme; 6. The present invention also provides a novel technique for once-incorporating nitrogen and stabilizing metal nanoparticles in graphene materials.
  • FIG. 1 Schematic diagram of the molecular structure of copper phthalocyanine
  • FIG. 2 Schematic diagram of a single layer polyphthalocyanine polymer
  • Figure 7 Transmission electron micrograph of graphene material doped with nitrogen atoms with a coiled structure
  • the temperature is raised to 300 degrees per minute at a slow heating rate of 5 degrees, 300 degrees for 1 hour; 5 degrees per minute to 350 degrees, 350 degrees for 1 hour; 5 degrees per minute to 400 degrees, 400 degrees stable 1 Hour: 3 degrees per minute to 500 degrees, 500 degrees stable for 4 hours; 2 degrees per minute to 800 degrees, 800 degrees for 8 hours, and finally naturally to room temperature, to obtain graphene containing metal copper nanoparticles, Its XRD and transmission electron microscopy spectra are shown in Figures 3 and 4.
  • the argon flow rate is controlled at SOcm ⁇ min — 1 .
  • the heating procedure is: heating up to 300 degrees per minute at a slow heating rate of 5 degrees, 300 degrees for 1 hour; heating to 350 degrees per minute at 5 degrees, 350 degrees for 1 hour; heating to 5 degrees per minute to 400 degrees, 400 degrees stable for 1 hour; 3 degrees per minute to 700 degrees, 700 degrees for 4 hours; 2 degrees per minute to 1000 degrees, 1000 degrees for 8 hours, and finally naturally to room temperature, treated with acid
  • a nitrogen-doped graphene material having a coiled structure is obtained, and its topography is shown in FIG.
  • Example 4 Example 4:
  • the cracking gas is an argon/hydrogen mixed gas, and the specific ratio of the mixed gas is 0.8:9.2 by volume, and the flow rate is controlled at 40 cn. ⁇ min- 1 , and at the same time as the cracking temperature of Example 1, a graphene material having a petal-like nitrogen atom impurity was obtained, and its morphology is shown in Fig. 8.
  • the cracking gas is an argon/ammonia gas mixture, and the specific ratio of the mixed gas is 0.5 by volume. : 9.5, the flow rate was controlled at 30 cm '-min 1 , and at the same time as the cracking temperature of Example 1, a high nitrogen-doped copper-containing graphene material was obtained, and elemental analysis showed that the nitrogen content mass ratio was 14.05%.
  • the flow rate of argon gas is controlled at lOcm ⁇ min 4 , and the heating procedure is as follows: Temperature rises to 300 degrees per minute, 300 degrees for 1 hour; 5 degrees per minute to 350 degrees, 350 degrees for 1 hour; 5 degrees per minute Up to 400 degrees, 400 degrees stable for 1 hour; 3 degrees per minute to 500 degrees, 500 degrees stable for 2 hours; 2 degrees per minute to 900 degrees, 900 degrees for 12 hours, and finally naturally to room temperature, to obtain nitrogen
  • the atomic doped graphene containing metallic nickel nanoparticles has a morphology as shown in Fig. 9.
  • Fig. 10 is an XRD pattern of graphene containing metallic nickel nanoparticles.
  • argon gas flow rate is controlled at SOcm ⁇ min- 1 , its heating procedure Yes: Warm up to 300 degrees per minute with a slow heating rate of 5 degrees, 300 degrees for 1 hour; 5 degrees per minute to 350 degrees, 350 degrees for 1 hour; 5 degrees per minute to 400 degrees, 400 degrees stable 1 hour; 3 degrees per minute to 700 degrees, 700 degrees for 4 hours; 2 degrees per minute to 1000 degrees, 1000 degrees for 8 hours, and finally naturally to room temperature, to obtain a nitrogen atom doped with a curly structure Graphene material.
  • the method for synthesizing nitrogen-doped graphene of Chinese invention patent CN201110204957 is: first cleaning and drying the substrate; coating a surface of the substrate with a catalyst containing a catalyst, the catalyst is a water-soluble metal salt; under anaerobic conditions, coating The temperature of the substrate coated with the catalyst is raised to 500 to 1300 ° C, and then the reducing gas is introduced, the catalyst is reduced, and then the gas is introduced. The organic carbon source compound and the gaseous nitrogen source compound are reacted to obtain the nitrogen-doped graphene having a nitrogen doping amount of 3.7%.

Abstract

A method for preparing aza graphene and nanometer metal graphene by using a solid phase cracking method comprises the following steps: a) using a phthalocyanine compound, a phthalocyanine polymer, and a derivative thereof as starting raw materials, which are directly used with no raw material purification processing; and b) performing cracking in an atmosphere furnace under the protection of a reaction protection gas with reference to thermo chemical features of the raw materials by using a temperature programmed method under the action of a metal catalyst or with no catalyst, to obtain a final aza graphene and nanometer metal graphene material.

Description

说 明 书  Description
一种固相裂解法制备氮杂石墨烯和纳米金属石墨烯的方法 技术领域 本发明采用一种固相裂解技术制备氮杂石墨烯和纳米金属石墨烯材料，属于高新材料 制备领域。 背景技术  TECHNICAL FIELD The present invention adopts a solid phase cracking technique to prepare aza-graphene and nano-metal graphene materials, and belongs to the field of high-tech material preparation. Background technique
2004 年 Geim 等利用胶带在天然石墨上反复剥离制得石墨烯以来 [1]，石墨烯因其独 特的单层片状六角蜂巢晶格结构在科学界引起前所未有的轰动，其独一无二的优异性能和 巨大的潜在应用价值更是引起了全世界广泛关注。从化学键合方式上，构成石墨烯二维结 构的碳原子以 sp2方式杂化， 这种杂化方式使得碳原子与相邻的三个碳原子通过 σ键形成 稳定的 C-C键， 赋予了石墨烯极高的力学性能 [2]。 同时在垂直于石墨烯平面上大量碳原 子提供的 π电子离域形成大 π键， 电子可以在其中自由移动， 因此石墨烯通常都具有优 异的导电性。 比如石墨烯是一种零带隙半导体， 电子在其中运动速度可达光速的 1/300， 石墨烯载流子迁移速率高达 Sx loScm^V^S4等 [3-8]。 此外， 石墨烯还具有较好的热学性 能和磁学性能 [9， 10]。 石墨烯较高的比表面积使其在超级电容器， 储氢， 单分子化学传 感器等领域具有巨大的潜在应用 [11]。 In 2004, Geim et al. used tape to repeatedly strip off natural graphite to produce graphene [1]. Graphene has caused unprecedented sensation in the scientific community due to its unique single-layered hexagonal honeycomb lattice structure, and its unique superior performance and The huge potential application value has caused widespread concern around the world. From the chemical bonding mode, the carbon atoms constituting the two-dimensional structure of graphene are hybridized by sp 2 method, which makes the carbon atoms and the adjacent three carbon atoms form a stable CC bond through the sigma bond, and imparts graphite. Extremely high mechanical properties [2]. At the same time, the π-electron delocalization provided by a large number of carbon atoms perpendicular to the plane of the graphene forms a large π bond, and electrons can move freely therein, and thus graphene generally has excellent conductivity. For example, graphene is a zero-bandgap semiconductor in which electrons move at speeds up to 1/300 of the speed of light, and graphene carrier mobility is as high as Sx loScm^V^S 4 [3-8]. In addition, graphene also has good thermal and magnetic properties [9, 10]. The high specific surface area of graphene makes it a huge potential application in the fields of supercapacitors, hydrogen storage, and single molecule chemical sensors [11].
目前， 氧化石墨还原法为制备石墨烯的主要方法， 该方法是将石墨进行强氧化处理， 得到氧化石墨烯后再对其进行剥离制备氧化石墨烯，最后经过还原处理得到石墨烯。由于 在强氧化过程中会严重破坏石墨烯片层的结构，虽然经过还原处理，石墨烯片层的电子共 轭结构得到部分恢复，所得石墨烯材料的各项性能指标仍与高质量的石墨烯存在较大的差 距。此外，石墨的氧化过程通常需要大量的强酸性氧化剂如浓硫酸、浓硝酸和高猛酸钾等， 而且还原过程中还需要水合肼或者硼氢化钠等有毒化学物质， 不仅能耗大、效率低下、成 本高而且污染严重。 如发明专利 CN102897756、 CN102897757 等。  At present, the graphite oxide reduction method is the main method for preparing graphene. The method is to carry out strong oxidation treatment of graphite, obtain graphene oxide and then strip it to prepare graphene oxide, and finally obtain graphene by reduction treatment. Due to the severe destruction of the structure of the graphene sheet during the strong oxidation process, although the electron conjugate structure of the graphene sheet is partially restored after the reduction treatment, the performance indexes of the obtained graphene material are still high quality graphene. There is a big gap. In addition, the oxidation process of graphite usually requires a large amount of strong acidic oxidants such as concentrated sulfuric acid, concentrated nitric acid and potassium permanganate, and toxic chemicals such as hydrazine hydrate or sodium borohydride are required in the reduction process, which is not only energy-intensive but also inefficient. High cost and serious pollution. For example, the invention patents CN102897756, CN102897757, and the like.
外延生长法制备石墨烯需要在高温下， 充入碳源气体 （甲垸、 乙垸、 乙炔等）， 气体 分解并在基底形成石墨烯，该方法需要 1000度以上的高温，且需要氢气作为还原性气体， 对生产条件要求严格， 反应时间长， 产率低下， 且大量危险气体的使用增加了生产成本也 限制了石墨烯的进一步应用。 如发明专利 CN102903616、 CN102891074 等。 在石墨烯中掺氮可调整器件的电子特性， 提高石墨烯的导电性能及其电化学稳定性。 目前石墨烯掺氮方法主要有水热合成法、 化学合成法、 CVD法、 等离子体溅射等 （如发明 专利 CN102887498、 CN102745678、 CN101708837等）， 这些方法合成效率和质量普遍较 低。而在石墨烯中掺入金属纳米粒子是电化学器件改性和电极修饰等的通常做法， 目前主 要复合方法有氧化还原法、 电化学还原法等 （如 CN102174702A、 CN102136306A等）， 这些方法的主要问题是有大量的化学废液， 纳米粒子易聚集。 The epitaxial growth method for preparing graphene needs to be filled with a carbon source gas (formamidine, acetamethylene, acetylene, etc.) at a high temperature, and the gas decomposes and forms graphene on the substrate. The method requires a high temperature of 1000 degrees or more, and requires hydrogen as a reduction. Sexual gas, strict requirements on production conditions, long reaction time, low yield, and the use of a large number of dangerous gases increases production costs. Further application of graphene is limited. Such as invention patents CN102903616, CN102891074 and the like. Nitrogen doping in graphene can adjust the electronic properties of the device and improve the electrical conductivity and electrochemical stability of graphene. At present, the graphene nitrogen doping method mainly includes hydrothermal synthesis method, chemical synthesis method, CVD method, plasma sputtering, etc. (such as invention patents CN102887498, CN102745678, CN101708837, etc.), and the synthesis efficiency and quality of these methods are generally low. The incorporation of metal nanoparticles into graphene is a common practice for electrochemical device modification and electrode modification. At present, the main composite methods include redox method, electrochemical reduction method, etc. (such as CN102174702A, CN102136306A, etc.), the main methods of these methods. The problem is that there is a large amount of chemical waste, and the nanoparticles are easy to aggregate.
因此， 迫切需要开发一种采用新型原料的、 方法简单易行、 对设备无特殊要求、 成本 低、效率高、零污染、零排放、易推广使用、能解决现有石墨烯制备技术中存在的成本高、 效率低、质量差等问题，并可无需生成中间产品石墨烯从原材料一次生产出的氮杂石墨烯 和纳米金属石墨烯的方法。  Therefore, there is an urgent need to develop a new raw material, which is simple and easy to implement, has no special requirements on equipment, low cost, high efficiency, zero pollution, zero emission, easy to promote and use, and can solve the existing existing graphene preparation technology. High cost, low efficiency, poor quality, etc., and the method of producing aza-graphene and nano-metal graphene produced by the intermediate product graphene from the raw material at one time.
酞菁是一类大环化合物， 酞菁分子中心是一个由碳氮共轭双键组成的 18-π体系， 环 内有一个空腔， 直径约 2.7 X 10_ η。 中心腔内的两个氢原子可以被 70多种元素取代， 包 括几乎所有的金属元素和一部分非金属元素 （如图 1所示）， 以及金属氧化物等。 而酞菁 聚合物泛指那些含有酞菁环结构的高分子 （如图 2)。 本发明将以此类化合物作为起始原 料， 采用低温固相裂解技术得到石墨烯类材料。 参考文献：  Phthalocyanine is a class of macrocyclic compounds. The center of the phthalocyanine is an 18-π system consisting of carbon-nitrogen conjugated double bonds. The ring has a cavity with a diameter of about 2.7 X 10 η. The two hydrogen atoms in the central cavity can be replaced by more than 70 elements, including almost all metal elements and a part of non-metal elements (as shown in Figure 1), as well as metal oxides. The phthalocyanine polymers generally refer to those polymers containing a phthalocyanine ring structure (Fig. 2). The present invention will use such a compound as a starting material to obtain a graphene-based material by a low-temperature solid phase cracking technique. references:
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3498-3502.  3498-3502.
发明内容 Summary of the invention
本发明提供一种采用固相裂解技术制备氮杂石墨烯和金属石墨烯的方法。它涉及以酞 菁化合物、 酞菁聚合物及其衍生物为起始原料， 在氮气、 氩气、 氩气 /氢气混合气、 氩气 / 氨气混合气、 氮气 /氢气混合气、 氮气 /氨气混合等常用气氛下， 参考原料的热化学特性， 于 700度以上一次性裂解制备得到含氮石墨烯和金属石墨烯类材料。其方法特征如下： 1. 用酞菁化合物、酞菁聚合物及其衍生物作为唯一起始原料一步固相裂解得到氮杂石墨烯和 纳米金属石墨烯类材料； 2. 裂解温度低， 节约能耗； 3. 采用惰性气体保护， 可在非氢气 氛环境中裂解得到石墨烯类材料， 安全性高； 4. 调节裂解温度以及气体流量等实验参数 能有效控制石墨烯类材料的大小， 厚度以及品质； 5. 在以铜箔或者镍箔作为催化剂还能 得到具有卷曲行为的石墨烯材料，可材料的提高其导电性能等。本发明制得的石墨烯类材 料将应用于单分子探测技术、场效应管及其集成电路、透明导电电极、 导电油墨、场发射 源及其真空电子器件、 吸波材料、 超级电容和生物器件等方面。  The present invention provides a method for preparing aza-graphene and metal graphene using a solid phase cracking technique. It involves the use of phthalocyanine compounds, phthalocyanine polymers and their derivatives as starting materials, nitrogen, argon, argon/hydrogen mixtures, argon/ammonia mixtures, nitrogen/hydrogen mixtures, nitrogen/ammonia Under common atmospheres such as gas mixing, the pyrochemical properties of the reference materials are used to prepare nitrogen-containing graphene and metal graphene materials by one-time cracking at 700 degrees or more. The method is characterized as follows: 1. One-step solid phase cleavage using a phthalocyanine compound, a phthalocyanine polymer and a derivative thereof as a sole starting material to obtain aza graphene and a nano metal graphene material; 2. Low cracking temperature and energy saving Consumption; 3. Inert gas protection, can be cracked in a non-hydrogen atmosphere to obtain graphene materials, high safety; 4. Adjust the cracking temperature and gas flow and other experimental parameters can effectively control the size and thickness of graphene materials Quality; 5. A graphene material with a curling behavior can be obtained by using copper foil or nickel foil as a catalyst, and the material can improve its electrical conductivity and the like. The graphene materials prepared by the invention will be applied to single molecule detection technology, field effect transistor and integrated circuit, transparent conductive electrode, conductive ink, field emission source and vacuum electronic device, absorbing material, super capacitor and biological device. etc.
本发明技术方案一如下：  The technical solution of the present invention is as follows:
步骤一： 以酞菁化合物、酞菁聚合物及其衍生物为起始原料， 不做其他原料处理直接 使用。  Step 1: The phthalocyanine compound, the phthalocyanine polymer and its derivatives are used as starting materials, and are directly used without other raw materials.
步骤二： 于气氛炉中， 以一定气体保护下， 参考原料的热化学特性， 采用程序升温方 法， 在无催化剂条件下一次性裂解得到氮杂石墨烯类和金属石墨烯类材料。  Step 2: In the atmosphere furnace, under the protection of a certain gas, with reference to the thermochemical characteristics of the raw materials, the aza-graphene and the metal graphene-based materials are obtained by a one-step cracking under a catalyst-free condition by a temperature-programmed method.
本发明技术方案二如下： 步骤一： 以酞菁化合物、酞菁聚合物及其衍生物为起始原料， 不做其他原料处理直接 使用。 The technical solution of the present invention is as follows: Step 1: The phthalocyanine compound, the phthalocyanine polymer and its derivatives are used as starting materials, and are directly used without other raw materials.
步骤二： 于气氛炉中， 以一定气体保护下， 参考原料的热化学特性， 采用程序升温方 法，在有金属催化剂条件下一次性裂解得到具有卷曲结构的氮杂石墨烯类和金属石墨烯类 材料。  Step 2: In the atmosphere furnace, under the protection of a certain gas, referring to the thermochemical characteristics of the raw materials, using a temperature programmed method, one-time cracking under the condition of a metal catalyst to obtain aza graphenes and metal graphenes having a coiled structure. material.
所述起始原料可以是市售或自制金属酞菁类化合物及其衍生物。优选过渡族金属酞菁 类化合物及其衍生物（如酞菁镍、 酞菁铜、 酞菁铁、 酞菁钼、 酞菁钴、 酞菁金、 酞菁银及 其衍生物等） 之一。  The starting material may be a commercially available or self-made metal phthalocyanine compound and a derivative thereof. Preferred are transition metal phthalocyanine compounds and derivatives thereof (e.g., nickel phthalocyanine, copper phthalocyanine, iron phthalocyanine, molybdenum phthalocyanine, cobalt phthalocyanine, phthalocyanine gold, silver phthalocyanine, and derivatives thereof).
所述起始原料还可以是纯酞菁化合物等非金属酞菁类物质之一。  The starting material may also be one of non-metal phthalocyanines such as a pure phthalocyanine compound.
所述起始原料还可以是含金属氧化物酞菁类物质之一。  The starting material may also be one of metal oxide-containing phthalocyanines.
所述起始原料还可以是含有酞菁环结构的高分子或含类酞菁环结构的卟啉类聚合物 之一。  The starting material may also be one of a polymer containing a phthalocyanine ring structure or a porphyrin-based polymer containing a phthalocyanine ring-like structure.
所述气体保护是指在氮气、 氩气、 氩气 /氢气混合气、 氩气 /氨气混合气、 氮气 /氢气混 合气、 氮气 /氨气混合气等常用的保护气体； 混合气具体比例为体积比 0.1 :9.9~1 :9之间； 流速控制在 10~50 cm^min"1之间； The gas protection refers to a common protective gas such as a nitrogen gas, an argon gas, an argon/hydrogen gas mixture, an argon gas/ammonia gas mixture gas, a nitrogen/hydrogen gas mixture gas, a nitrogen gas/ammonia gas mixture gas, etc.; The volume ratio is between 0.1:9.9 and 1:9; the flow rate is controlled between 10 and 50 cm^min"1;
所述金属催化剂是指铜箔、 铜网、 镍箔、 泡沫镍等金属或合金。  The metal catalyst refers to a metal or alloy such as copper foil, copper mesh, nickel foil, or nickel foam.
所述裂解的裂解温度根据原料的热化学特性有所不同， 一般为 700 度以上， 优选为 800~1000度。  The cracking temperature of the cracking varies depending on the thermochemical characteristics of the raw material, and is generally 700 degrees or more, preferably 800 to 1000 degrees.
在优选裂解温度下， 裂解自催化生成石墨烯片层的时间为 4~24小时， 缩短或者延长 裂解时间对最终石墨烯材料大小， 厚度和品质有影响。  At the preferred cracking temperature, the time to crack the autocatalytic graphene sheet is 4 to 24 hours. Shortening or prolonging the cracking time has an effect on the size, thickness and quality of the final graphene material.
氮杂石墨烯类材料中氮元素的获得来自酞菁骨架中自身氮原子，如需要得到更高含量 的氮原子， 可在裂解过程中通入氨气和惰性气体的混合气。  The nitrogen element in the aza graphene-based material is derived from the self-nitrogen atom in the phthalocyanine skeleton. If a higher content of nitrogen atoms is required, a mixture of ammonia gas and inert gas can be introduced during the cracking process.
含金属纳米粒子的石墨烯类材料中金属纳米颗粒的获得来自起始原料自身所含金属 类别， 以酞菁铜为例， 最终将得到含有金属铜纳米粒子的石墨烯材料。  The metal nanoparticles in the graphene-based material containing metal nanoparticles are obtained from the metal species contained in the starting material itself. Taking copper phthalocyanine as an example, a graphene material containing metal copper nanoparticles is finally obtained.
本发明技术特点： 1. 任何含有酞菁环的化合物及其衍生物都可作为得到氮杂石墨烯 和金属石墨烯的起始原料； 2. 为提高材料导电性或者其他性质， 可通过通入氨气增加材 料最终含氮量； 3. 调节裂解温度、 气体流量、 气体流速等实验参数能有效控制石墨烯类 材料的大小， 厚度以及品质； 4. 在以铜箔或者镍箔等作为催化剂时， 还可得到具有卷曲 行为的石墨烯材料， 可提高其导电性能等； 5.不同的原料根据其热化学特性制定不同的程 序升温方案； 6. 本发明还提供了一种在石墨烯材料中一次性掺入氮和稳定金属纳米颗粒 的新技术。 Technical Features of the Invention: 1. Any compound containing a phthalocyanine ring and its derivatives can be used as a starting material for obtaining aza graphene and metal graphene; 2. To improve the conductivity or other properties of the material, Ammonia increases the final nitrogen content of the material; 3. Adjusts the experimental parameters such as cracking temperature, gas flow rate, gas flow rate, etc. to effectively control the size, thickness and quality of graphene materials; 4. When using copper foil or nickel foil as catalyst , a graphene material having a curling behavior can also be obtained, which can improve the electrical conductivity and the like; 5. Different raw materials are formulated according to their thermochemical properties. Sequence heating scheme; 6. The present invention also provides a novel technique for once-incorporating nitrogen and stabilizing metal nanoparticles in graphene materials.
附图说明 DRAWINGS
图 1 酞菁铜分子结构示意图 Figure 1 Schematic diagram of the molecular structure of copper phthalocyanine
图 2 单层聚酞菁高分子示意图 Figure 2 Schematic diagram of a single layer polyphthalocyanine polymer
图 3 氮原子掺杂的含有金属铜纳米粒子的石墨烯材料的 XRD图谱 Fig. 3 XRD pattern of nitrogen-doped graphene material containing metallic copper nanoparticles
图 4 氮原子掺杂的含有金属铜纳米粒子的石墨烯材料透射电镜照片 Figure 4 Transmission electron micrograph of graphene material containing nitrogen-doped metal copper nanoparticles
图 5 氮原子掺杂的石墨烯材料 XRD图谱 Figure 5 X-ray pattern of nitrogen-doped graphene material
图 6 氮原子掺杂的石墨烯材料透射电镜照片 Figure 6. Transmission electron micrograph of graphene material doped with nitrogen atoms
图 7 具有卷曲结构的氮原子掺杂的石墨烯材料透射电镜照片 Figure 7: Transmission electron micrograph of graphene material doped with nitrogen atoms with a coiled structure
图 8 具有花瓣状的氮原子掺杂的石墨烯材料扫描电镜照片 Figure 8 Scanning electron micrograph of graphene material with petal nitrogen atoms doped
图 9 氮原子掺杂的含有金属镍纳米粒子的石墨烯材料透射电镜照片 Figure 9 Transmission electron micrograph of graphene material containing nitrogen-doped metal nickel nanoparticles
图 10 氮原子掺杂的含有金属镍纳米粒子的石墨烯材料的 XRD图谱 具体实施方式 Figure 10 XRD pattern of nitrogen-doped graphene material containing metal nickel nanoparticles
下面结合具体实施方式对本发明做进一步的详细描述。 在不脱离本发明上述思想情 况下，根据本领域普通技术知识和惯用手段做出的各种替换或变更，均包含在本发明的范 围内。  The present invention will be further described in detail below in conjunction with the specific embodiments. Various alterations and modifications may be made without departing from the spirit and scope of the invention.
实施例 1： Example 1:
以 30.0克市售酞菁铜为起始原料， 不做任何纯化处理。 于石英管式炉中， 以高纯氩 气保护下， 氩气流速控制在 SOcm^min—1 , 在如下升温方案下裂解得到 20.7克最终金属石 墨烯类材料。 即以缓慢升温速度 5度每分钟升温至 300度， 300度稳定 1小时； 以 5度每 分钟升温至 350度， 350度稳定 1小时； 以 5度每分钟升温至 400度， 400度稳定 1小时； 以 3度每分钟升温至 500度， 500度稳定 4小时； 以 2度每分钟升温至 800度， 800度稳 定 8小时， 最后自然降至室温， 得到含有金属铜纳米粒子的石墨烯， 其 XRD和透射电镜 图谱见图 3和图 4。 30.0 g of commercially available copper phthalocyanine was used as a starting material, and no purification treatment was carried out. In a quartz tube furnace, under the protection of high purity argon gas, the argon gas flow rate is controlled at SOcm^min- 1 , and 20.7 g of the final metal graphene-based material is obtained by cracking under the following temperature rising scheme. That is, the temperature is raised to 300 degrees per minute at a slow heating rate of 5 degrees, 300 degrees for 1 hour; 5 degrees per minute to 350 degrees, 350 degrees for 1 hour; 5 degrees per minute to 400 degrees, 400 degrees stable 1 Hour: 3 degrees per minute to 500 degrees, 500 degrees stable for 4 hours; 2 degrees per minute to 800 degrees, 800 degrees for 8 hours, and finally naturally to room temperature, to obtain graphene containing metal copper nanoparticles, Its XRD and transmission electron microscopy spectra are shown in Figures 3 and 4.
实施例 2 ： Example 2:
以自制的酞菁铜为起始原料， 首先如实施例 1 制备得到含有金属铜纳米粒子的石墨 烯， 然后用纯 HC1、纯 H2S04等强酸溶解， 室温搅拌几小时后得到不含金属粒子的石墨烯 材料， 其 XRD、 透射电镜分别见图 5和图 6。 Taking homemade copper phthalocyanine as a starting material, first, graphene containing metal copper nanoparticles was prepared as in Example 1, and then dissolved with a strong acid such as pure HC1 or pure H 2 SO 4 , and stirred at room temperature for several hours to obtain a metal-free metal. Graphene Materials, XRD, transmission electron microscopy are shown in Figure 5 and Figure 6, respectively.
实施例 3： Example 3:
以市售酞菁铜为起始原料， 不做任何纯化处理， 于石英管式炉中， 以铜箔或者镍箔为 基底材料， 在高纯氩气保护下， 氩气流速控制在 SOcm^min—1 , 其升温程序是： 以缓慢升 温速度 5度每分钟升温至 300度， 300度稳定 1小时； 以 5度每分钟升温至 350度， 350 度稳定 1小时； 以 5度每分钟升温至 400度， 400度稳定 1小时；以 3度每分钟升温至 700 度， 700度稳定 4小时； 以 2度每分钟升温至 1000度， 1000度稳定 8小时， 最后自然降 至室温， 用酸处理得到具有卷曲结构的氮原子掺杂的石墨烯材料， 其形貌图见图 7。 实施例 4： Taking commercially available copper phthalocyanine as the starting material, without any purification treatment, in the quartz tube furnace, with copper foil or nickel foil as the base material, under the protection of high purity argon, the argon flow rate is controlled at SOcm^min — 1 , The heating procedure is: heating up to 300 degrees per minute at a slow heating rate of 5 degrees, 300 degrees for 1 hour; heating to 350 degrees per minute at 5 degrees, 350 degrees for 1 hour; heating to 5 degrees per minute to 400 degrees, 400 degrees stable for 1 hour; 3 degrees per minute to 700 degrees, 700 degrees for 4 hours; 2 degrees per minute to 1000 degrees, 1000 degrees for 8 hours, and finally naturally to room temperature, treated with acid A nitrogen-doped graphene material having a coiled structure is obtained, and its topography is shown in FIG. Example 4:
以市售酞菁铜为起始原料， 不做任何纯化处理， 于石英管式炉中， 裂解气为氩气 /氢 气混合气体， 混合气具体比例为体积比 0.8:9.2， 流速控制在 40 cn^min—1 , 同时如实施例 1裂解温度， 得到具有花瓣状的氮原子参杂的石墨烯材料， 其形貌图见图 8。 The commercially available copper phthalocyanine is used as the starting material without any purification treatment. In the quartz tube furnace, the cracking gas is an argon/hydrogen mixed gas, and the specific ratio of the mixed gas is 0.8:9.2 by volume, and the flow rate is controlled at 40 cn. ^min- 1 , and at the same time as the cracking temperature of Example 1, a graphene material having a petal-like nitrogen atom impurity was obtained, and its morphology is shown in Fig. 8.
实施例 5： Example 5
以市售酞菁铜为起始原料， 不做任何纯化处理， 于石英管式炉中， 如实施例一所示， 裂解气为氩气 /氨气混合气体，混合气具体比例为体积比 0.5:9.5，流速控制在 30 cm'-min 1 , 同时如实施例 1裂解温度，得到高氮掺杂含铜的石墨烯材料，元素分析显示氮含量质量比 为 14.05% ο Taking commercially available copper phthalocyanine as a starting material, without any purification treatment, in a quartz tube furnace, as shown in the first embodiment, the cracking gas is an argon/ammonia gas mixture, and the specific ratio of the mixed gas is 0.5 by volume. : 9.5, the flow rate was controlled at 30 cm '-min 1 , and at the same time as the cracking temperature of Example 1, a high nitrogen-doped copper-containing graphene material was obtained, and elemental analysis showed that the nitrogen content mass ratio was 14.05%.
Figure imgf000008_0001
Figure imgf000008_0001
实施例 6： Example 6:
以酞菁镍为起始原料， 不做任何纯化处理， 于石英管式炉中， 以高纯氩气保护下， 氩 气流速控制在 lOcm^min4 , 其升温程序如下： 以缓慢升温速度 5度每分钟升温至 300度， 300度稳定 1小时； 以 5度每分钟升温至 350度， 350度稳定 1小时； 以 5度每分钟升温 至 400度， 400度稳定 1小时； 以 3度每分钟升温至 500度， 500度稳定 2小时； 以 2度 每分钟升温至 900度， 900度稳定 12小时， 最后自然降至室温， 得到氮原子掺杂的含有 金属镍纳米粒子的石墨烯， 其形貌见图 9， 图 10为含有金属镍纳米粒子的石墨烯的 XRD 图。 Taking nickel phthalocyanine as the starting material, without any purification treatment, in the quartz tube furnace, under the protection of high purity argon gas, the flow rate of argon gas is controlled at lOcm^min 4 , and the heating procedure is as follows: Temperature rises to 300 degrees per minute, 300 degrees for 1 hour; 5 degrees per minute to 350 degrees, 350 degrees for 1 hour; 5 degrees per minute Up to 400 degrees, 400 degrees stable for 1 hour; 3 degrees per minute to 500 degrees, 500 degrees stable for 2 hours; 2 degrees per minute to 900 degrees, 900 degrees for 12 hours, and finally naturally to room temperature, to obtain nitrogen The atomic doped graphene containing metallic nickel nanoparticles has a morphology as shown in Fig. 9. Fig. 10 is an XRD pattern of graphene containing metallic nickel nanoparticles.
实施例 7： Example 7
以 10.0克市售酞菁铜为起始原料， 不做任何纯化处理。 于箱式气氛炉中， 以高纯氩 气保护下， 氩气流速控制在 SOcm^min4 , 以缓慢升温速度 5度每分钟升温至 300度， 300 度稳定 1小时； 以 5度每分钟升温至 350度， 350度稳定 1小时；以 5度每分钟升温至 400 度， 400度稳定 1小时； 以 3度每分钟升温至 500度， 500度稳定 4小时； 以 2度每分钟 升温至 700度， 在 700度稳定 12小时， 最后自然降至室温， 在上述升温方案下裂解得到 7.1克金属石墨烯类材料。 10.0 g of commercially available copper phthalocyanine was used as a starting material, and no purification treatment was carried out. In a box-type atmosphere furnace, under the protection of high-purity argon gas, the argon gas flow rate is controlled at SOcm^min 4 , and the temperature is raised to 300 degrees per minute at a slow heating rate of 5 degrees, and stabilized at 300 degrees for 1 hour; Up to 350 degrees, 350 degrees stable for 1 hour; 5 degrees per minute to 400 degrees, 400 degrees for 1 hour; 3 degrees per minute to 500 degrees, 500 degrees for 4 hours; 2 degrees per minute to 700 The degree was stabilized at 700 °C for 12 hours, and finally naturally dropped to room temperature, and 7.1 g of a metal graphene-based material was obtained by cleavage under the above-mentioned heating scheme.
实施例 8： Example 8
以聚酞菁为起始原料， 不做任何纯化处理， 于石英管式炉中， 以铜箔为催化剂， 以高 纯氩气保护下， 氩气流速控制在 SOcm^min—1 , 其升温程序是： 以缓慢升温速度 5度每分 钟升温至 300度， 300度稳定 1小时； 以 5度每分钟升温至 350度， 350度稳定 1小时； 以 5度每分钟升温至 400度， 400度稳定 1小时； 以 3度每分钟升温至 700度， 700度稳 定 4小时； 以 2度每分钟升温至 1000度， 1000度稳定 8小时， 最后自然降至室温， 得到 具有卷曲结构的氮原子掺杂的石墨烯材料。 Using polyphthalocyanine as starting material, without any purification treatment, in quartz tube furnace, with copper foil as catalyst, under high purity argon gas protection, argon gas flow rate is controlled at SOcm^min- 1 , its heating procedure Yes: Warm up to 300 degrees per minute with a slow heating rate of 5 degrees, 300 degrees for 1 hour; 5 degrees per minute to 350 degrees, 350 degrees for 1 hour; 5 degrees per minute to 400 degrees, 400 degrees stable 1 hour; 3 degrees per minute to 700 degrees, 700 degrees for 4 hours; 2 degrees per minute to 1000 degrees, 1000 degrees for 8 hours, and finally naturally to room temperature, to obtain a nitrogen atom doped with a curly structure Graphene material.
实施例 9： Example 9
以 20.0克市售酞菁铜为起始原料， 不做任何纯化处理。 于箱式气氛炉中， 以高纯氩 气保护下， 氩气流速控制在 SOcm^min4 , 以缓慢升温速度 5度每分钟升温至 300度， 300 度稳定 1小时； 以 5度每分钟升温至 350度， 350度稳定 1小时；以 5度每分钟升温至 400 度， 400度稳定 1小时； 以 3度每分钟升温至 500度， 500度稳定 4小时； 以 2度每分钟 升温至 1000度， 1000度稳定 4小时， 最后自然降至室温， 得到 14.6克含有金属铜纳米粒 子的石墨烯类材料。 20.0 g of commercially available copper phthalocyanine was used as a starting material, and no purification treatment was carried out. In a box-type atmosphere furnace, under the protection of high-purity argon gas, the argon gas flow rate is controlled at SOcm^min 4 , and the temperature is raised to 300 degrees per minute at a slow heating rate of 5 degrees, and stabilized at 300 degrees for 1 hour; Up to 350 degrees, 350 degrees stable for 1 hour; 5 degrees per minute to 400 degrees, 400 degrees for 1 hour; 3 degrees per minute to 500 degrees, 500 degrees for 4 hours; 2 degrees per minute to 1000 The degree was stabilized at 1000 ° for 4 hours, and finally naturally dropped to room temperature, and 14.6 g of a graphene-based material containing metallic copper nanoparticles was obtained.
对照例： Control example:
中国发明专利 CN201110204957的掺氮石墨烯的合成方法的步骤是： 先清洗、干燥衬 底； 在衬底表面涂覆含有催化剂的溶液， 该催化剂为水溶性金属盐； 在无氧条件下， 将涂 覆有催化剂的衬底的温度升至 500〜1300°C， 再通入还原气体， 还原催化剂， 接着通入气 态的有机碳源化合物和气态的氮源化合物进行反应， 得到所述掺氮石墨烯， 其掺氮量为 3.7%。 The method for synthesizing nitrogen-doped graphene of Chinese invention patent CN201110204957 is: first cleaning and drying the substrate; coating a surface of the substrate with a catalyst containing a catalyst, the catalyst is a water-soluble metal salt; under anaerobic conditions, coating The temperature of the substrate coated with the catalyst is raised to 500 to 1300 ° C, and then the reducing gas is introduced, the catalyst is reduced, and then the gas is introduced. The organic carbon source compound and the gaseous nitrogen source compound are reacted to obtain the nitrogen-doped graphene having a nitrogen doping amount of 3.7%.

Claims

^ m ^ ^ m ^
1. 一种固相裂解法制备氮杂石墨烯和纳米金属石墨烯的方法，该方法包括以下步骤顺序： a): 以酞菁类化合物、 酞菁聚合物及其衍生物为起始原料， 不做其他原料纯化处理直 接使用；  A method for preparing aza-graphene and nano-metal graphene by a solid phase cracking method, the method comprising the following sequence of steps: a): starting from a phthalocyanine compound, a phthalocyanine polymer and a derivative thereof, Do not use other raw materials for purification and use directly;
b): 于气氛炉中， 在反应保护气体保护下， 参考原料的热化学特性， 采用程序升温方 法，在无催化剂或有金属催化剂作用下裂解得到最终的氮杂石墨烯类和纳米金属石墨烯类 材料。  b): in the atmosphere furnace, under the protection of protective gas, refer to the thermochemical characteristics of the raw materials, using a temperature-programmed method, cracking without catalyst or metal catalyst to obtain the final aza graphene and nano-metal graphene Class materials.
2. 如权利要求书 1所述方法，其特征在于所述起始原料为金属酞菁类化合物及其衍生物。 2. Process according to claim 1, characterized in that the starting material is a metal phthalocyanine compound and a derivative thereof.
3. 如权利要求书 2所述方法， 优选过渡族金属酞菁类化合物及其衍生物之一。 3. The method according to claim 2, which is preferably one of a transition metal phthalocyanine compound and a derivative thereof.
4. 如权利要求书 1所述方法，其特征在于所述起始原料为包括纯酞菁化合物在内的非金 属酞菁类物质之一。 The method according to claim 1, wherein said starting material is one of non-metal phthalocyanines including a pure phthalocyanine compound.
5. 如权利要求书 1所述方法，其特征在于所述起始原料为含金属氧化物酞菁类物质之一。 5. The method of claim 1 wherein said starting material is one of a metal oxide containing phthalocyanine.
6. 如权利要求书 1所述方法，其特征在于所述起始原料为含有酞菁环结构的高分子或含 类酞菁环结构的卟啉类聚合物之一。 The method according to claim 1, wherein the starting material is one of a polymer containing a phthalocyanine ring structure or a porphyrin-based polymer containing a phthalocyanine ring-like structure.
7. 如权利要求书 1所述方法， 其特征在于所述金属催化剂是指包括铜箔、 铜网、 镍箔、 泡沫镍在内的金属或合金。 7. The method of claim 1 wherein said metal catalyst is a metal or alloy comprising copper foil, copper mesh, nickel foil, nickel foam.
8. 如权利要求书 1所述方法， 其特征在于所述反应保护气体为氮气、 氩气、 氩气 /氢气混 合气、 氩气 /氨气混合气、 氮气 /氢气混合气、 氮气 /氨气混合气之一； 混合气具体比例为体 积比 0.1 :9.9-1 :9之间； 流速控制在 10-50 cm^min 之间。  8. The method according to claim 1, wherein the reactive shielding gas is nitrogen, argon, argon/hydrogen mixed gas, argon/ammonia mixed gas, nitrogen/hydrogen mixed gas, nitrogen/ammonia gas. One of the mixed gases; the specific ratio of the mixed gas is between 0.1:9.9-1:9; the flow rate is controlled between 10-50 cm^min.
9. 如权利要求书 1所述方法， 其特征在于所述裂解的自催化温度在 700度以上。 9. The method of claim 1 wherein said pyrolysis has an autocatalytic temperature of greater than 700 degrees.
10. 如权利要求书 9所述方法， 其特征在于所述自催化温度为 800 1000度。  10. The method of claim 9 wherein said autocatalytic temperature is 800 1000 degrees.
11.如权利要求书 10所述方法， 其特征在于裂解自催化生成石墨烯片层的时间为 4~24小 时。  11. Process according to claim 10, characterized in that the time to cleave the self-catalyzed graphene sheets is from 4 to 24 hours.
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