WO2015081663A1 - Procédé de préparation d'un graphène aza et d'un métal-graphène nanométrique par utilisation d'un procédé de craquage en phase solide - Google Patents

Procédé de préparation d'un graphène aza et d'un métal-graphène nanométrique par utilisation d'un procédé de craquage en phase solide 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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PCT/CN2014/077420
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English (en)
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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Publication of WO2015081663A1 publication Critical patent/WO2015081663A1/fr

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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

L'invention concerne un procédé de préparation de graphène AZA et d'un métal-graphène nanométrique par utilisation d'un procédé de craquage en phase solide, comprenant les étapes suivantes : a) utilisation d'un composé phtalocyanine, d'un polymère de phtalocyanine et d'un dérivé de ce dernier en tant que matières premières de départ, qui sont directement utilisés sans traitement par purification des matières premières ; et b) mise en œuvre d'un craquage dans un four atmosphérique sous la protection d'un gaz de protection de la réaction par référence aux caractéristiques thermochimiques des matières premières par utilisation d'un procédé à température programmée sous l'action d'un catalyseur métallique ou sans catalyseur, pour obtenir un matériau final graphène AZA et métal-graphène nanométrique.
PCT/CN2014/077420 2013-12-04 2014-05-14 Procédé de préparation d'un graphène aza et d'un métal-graphène nanométrique par utilisation d'un procédé de craquage en phase solide WO2015081663A1 (fr)

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CN201310652296.0 2013-12-04
CN201310652296.0A CN103663441B (zh) 2013-12-04 2013-12-04 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

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CN103663441B (zh) * 2013-12-04 2016-03-23 四川环碳科技有限公司 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
US10392256B2 (en) * 2014-11-07 2019-08-27 Xuyang SUN Method for preparing graphene by using molten inorganic salt reaction bed
CN104445160B (zh) * 2014-11-07 2017-04-12 孙旭阳 一种熔融态无机盐反应床制备石墨烯的方法
CN104477889A (zh) * 2014-12-03 2015-04-01 连丽君 一种于硅基片上直接生长石墨烯膜的方法
CN104449239A (zh) * 2014-12-18 2015-03-25 四川环碳科技有限公司 一种氮杂石墨烯复合的电磁屏蔽导电底漆及其制备方法
CN104860298B (zh) * 2015-03-25 2018-02-16 孙旭阳 利用熔融态反应床制备石墨烯的方法
CN104777207B (zh) * 2015-04-10 2017-11-28 武汉大学 一种三维氮掺杂石墨烯复合材料及其制备方法和应用
CN104952631B (zh) * 2015-06-15 2017-10-17 四川环碳科技有限公司 采用固相裂解技术制备石墨烯/碳纳米管复合材料的方法
CN105810945A (zh) * 2016-05-26 2016-07-27 江苏深苏电子科技有限公司 锂离子电池负极材料氮掺杂三维多孔石墨烯的制备方法
CN108636438B (zh) * 2018-05-16 2021-10-26 成都理工大学 一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用
CN109755519A (zh) * 2018-12-29 2019-05-14 湖南中科星城石墨有限公司 一种以延展性碳材料包覆的锂电池阳极材料及其制备方法
CN109786698A (zh) * 2018-12-29 2019-05-21 湖南中科星城石墨有限公司 一种以无机可延展碳材料为壳包覆的核壳结构锂离子电池阴极材料及其制备方法
CN111874888B (zh) * 2020-08-06 2021-09-14 电子科技大学 一种微米尺度方块状碳材料的超宽频吸波剂的制备方法
CN114733546A (zh) * 2022-03-28 2022-07-12 云南锡业集团（控股）有限责任公司研发中心 一种氮掺杂的碳负载铟纳米粒子的制备方法

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