CN118324123A - Nitrogen-doped carbon micro-tube and preparation method thereof - Google Patents
Nitrogen-doped carbon micro-tube and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 192
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
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- 239000012159 carrier gas Substances 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 2
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- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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Abstract
本发明提供一种氮掺杂碳微米管及其制备方法,属于碳微纳米材料制备技术领域。一种氮掺杂碳微米管材料,所述氮掺杂碳微米管材料为中空管状结构,管的直径为1‑2μm,管的长度为5‑15μm,管壁厚度为10‑50nm。其制备方法包括以下步骤:首先,将含氮化合物热缩聚制备含氮固体碳源,然后,将含氮固体碳源高温热解,热解气体在金属催化剂表面化学气相沉积催化生长碳微米管。本发明的制备方法操作过程简单,可以规模化制备,得到的氮掺杂碳微米管具有独特的微纳米结构和高氮含量,在电化学储能等领域具有广泛的应用前景。
The present invention provides a nitrogen-doped carbon microtube and a preparation method thereof, and belongs to the technical field of carbon micro-nano material preparation. A nitrogen-doped carbon microtube material, the nitrogen-doped carbon microtube material is a hollow tubular structure, the diameter of the tube is 1‑2 μm, the length of the tube is 5‑15 μm, and the thickness of the tube wall is 10‑50 nm. The preparation method thereof comprises the following steps: first, a nitrogen-containing solid carbon source is prepared by thermal polycondensation of a nitrogen-containing compound, and then, the nitrogen-containing solid carbon source is pyrolyzed at high temperature, and the pyrolysis gas is chemically vapor deposited on the surface of a metal catalyst to catalyze the growth of carbon microtubes. The preparation method of the present invention has a simple operation process and can be prepared on a large scale. The obtained nitrogen-doped carbon microtube has a unique micro-nano structure and a high nitrogen content, and has broad application prospects in the fields of electrochemical energy storage and the like.
Description
技术领域Technical Field
本发明涉及一种基于氮掺杂碳微米管及其制备方法,属于碳微米管制备技术领域。The invention relates to a nitrogen-doped carbon microtube and a preparation method thereof, belonging to the technical field of carbon microtube preparation.
背景技术Background technique
目前,碳纳米管凭借优良的电导率和优异的稳定性等优势在各项研究都取得了举世瞩目的成就,而碳微米管作为与碳纳米管结构性能相似的微米尺度碳管,相关的报道与研究却相当少见。碳纳米管因其纳米尺度的原因,导致纳米管之间范德华力、π-π作用较强,易发生团聚,同时,管与管之间相互缠绕,难以在基体中分散。此外,碳纳米管较小的管径限制了较大体积分子进入其空腔,碳纳米管的单分散性和单操作性通常都较差,且碳纳米管的中空部分经常被一些产物部分或全部地堵塞,使得其分子输运和传质等方面遇到了一系列的问题。这些不利因素大大降低了碳纳米管的实际应用价值。而碳微米管则相较于碳纳米管有显著的管径优势,在微电子和微机械器件、微纳反应器、药物输送和微纳流体等领域具有广阔的应用前景。但是,由于催化剂活性随其粒径增加而下降,因此传统上用于合成碳纳米管的方法,对于碳微米管的合成并不适用,目前高效、可控合成碳微米管存在巨大的挑战。At present, carbon nanotubes have achieved remarkable achievements in various researches due to their advantages such as excellent electrical conductivity and excellent stability. However, carbon microtubes, as micrometer-sized carbon tubes with similar structural properties to carbon nanotubes, are rarely reported and studied. Due to their nanometer size, carbon nanotubes have strong van der Waals forces and π-π interactions between nanotubes, which are prone to agglomeration. At the same time, the tubes are entangled with each other and are difficult to disperse in the matrix. In addition, the small diameter of carbon nanotubes limits the entry of larger molecules into their cavities. The monodispersity and monooperability of carbon nanotubes are usually poor, and the hollow part of carbon nanotubes is often partially or completely blocked by some products, which causes a series of problems in molecular transport and mass transfer. These unfavorable factors greatly reduce the practical application value of carbon nanotubes. Compared with carbon nanotubes, carbon microtubes have significant diameter advantages and have broad application prospects in microelectronics and micromechanical devices, micro-nano reactors, drug delivery, and micro-nano fluids. However, since the activity of the catalyst decreases as its particle size increases, the traditional method used to synthesize carbon nanotubes is not applicable to the synthesis of carbon microtubes. Currently, there are huge challenges in the efficient and controllable synthesis of carbon microtubes.
目前合成碳微米管的方法普遍存在条件苛刻和可控性较差的缺点。多孔碳微米管的制备方法和多孔碳微米管(申请公开号CN110028066A)公开了一种以玉米须作为生物质前驱体,通过碳化、活化的方式制备了具有多孔结构的碳微米管的技术,但其无法实现对碳微米管直径的可控调节,且制备的碳微米管属于硬碳材料,无法实现石墨化。一种可持续高产碳微米管的制备方法(授权公告号CN103387220B)公开了一种以尿素、乙二醇为碳源采用高温高压法合成了碳微米管的技术。但该技术存在合成温度和合成压力均高的缺点,合成条件十分苛刻,不利于碳微米管的规模化合成。因此,需要提供一种合成条件温和可控的碳微米管制备方法,即降低碳微米管的合成温度,同时在常压下合成,同时能够对于碳微米管的直径、晶化程度、杂原子掺杂实现精准的调控,最终实现碳微米管的合成可控、规模化、高质量合成。At present, the methods for synthesizing carbon microtubes generally have the disadvantages of harsh conditions and poor controllability. The preparation method of porous carbon microtubes and porous carbon microtubes (application publication number CN110028066A) discloses a technology of preparing carbon microtubes with porous structure by carbonization and activation using corn silk as biomass precursor, but it cannot achieve controllable adjustment of the diameter of carbon microtubes, and the prepared carbon microtubes belong to hard carbon materials and cannot be graphitized. A method for preparing sustainable high-yield carbon microtubes (authorization announcement number CN103387220B) discloses a technology of synthesizing carbon microtubes using urea and ethylene glycol as carbon sources by high temperature and high pressure method. However, this technology has the disadvantages of high synthesis temperature and synthesis pressure, and the synthesis conditions are very harsh, which is not conducive to the large-scale synthesis of carbon microtubes. Therefore, it is necessary to provide a method for preparing carbon microtubes with mild and controllable synthesis conditions, that is, to lower the synthesis temperature of carbon microtubes and synthesize them under normal pressure, while being able to accurately control the diameter, degree of crystallization, and heteroatom doping of the carbon microtubes, ultimately achieving controllable, large-scale, and high-quality synthesis of carbon microtubes.
发明内容Summary of the invention
为了解决现有制备碳微米管技术中存在的不足,本发明提供了一种化学气相沉积催化可控合成氮掺杂碳微米管及其制备方法,能够实现氮掺杂碳微米管的低温、可控和规模化合成。N原子的引入能够改变碳基体的结构产生更多的电化学/催化活性位点,并且会影响材料电荷分布提高碳微米管的导电性。同时,N原子的引入还能够改善碳微米管表面润湿性。总之,氮掺杂可以赋予碳微米管更加优异的物理化学性质,改善其应用性能,大大拓展了碳微米管的应用范围。In order to solve the shortcomings in the existing technology for preparing carbon microtubes, the present invention provides a chemical vapor deposition catalytic controllable synthesis of nitrogen-doped carbon microtubes and a preparation method thereof, which can achieve low-temperature, controllable and large-scale synthesis of nitrogen-doped carbon microtubes. The introduction of N atoms can change the structure of the carbon matrix to produce more electrochemical/catalytic active sites, and can affect the charge distribution of the material to improve the conductivity of the carbon microtubes. At the same time, the introduction of N atoms can also improve the surface wettability of the carbon microtubes. In short, nitrogen doping can give carbon microtubes more excellent physical and chemical properties, improve their application performance, and greatly expand the application range of carbon microtubes.
为了达到上述目的,本发明采用的技术方案如下:In order to achieve the above object, the technical solution adopted by the present invention is as follows:
一种氮掺杂碳微米管,所述的氮掺杂碳微米管为中空管状结构,管的直径为0.7-2μm,管的长度为5-20μm,管壁厚度为10-80nm。A nitrogen-doped carbon microtube is a hollow tubular structure with a tube diameter of 0.7-2 μm, a tube length of 5-20 μm and a tube wall thickness of 10-80 nm.
一种氮掺杂碳微米管的制备方法,所述制备方法,首先,将含氮化合物热缩聚制备含氮固体碳源。其次,将含氮固体碳源、金属镍粉分别置于加热设备的热解区和气相沉积反应区,将含氮固体碳源高温热解,热解气体在金属镍粉表面化学气相沉积催化生长碳微米管。最后,反应后取出样品加入盐酸溶液,进行后处理得到氮掺杂碳微米管材料。具体包括如下步骤:A method for preparing nitrogen-doped carbon microtubes, the preparation method comprising: first, preparing a nitrogen-containing solid carbon source by thermal polycondensation of a nitrogen-containing compound. Secondly, placing the nitrogen-containing solid carbon source and metal nickel powder in a pyrolysis zone and a vapor deposition reaction zone of a heating device respectively, pyrolyzing the nitrogen-containing solid carbon source at high temperature, and catalyzing the growth of carbon microtubes by chemical vapor deposition of the pyrolysis gas on the surface of the metal nickel powder. Finally, after the reaction, the sample is taken out and added with a hydrochloric acid solution, and post-processed to obtain a nitrogen-doped carbon microtube material. Specifically, the steps include:
第一步,制备含氮固体碳源:The first step is to prepare a nitrogen-containing solid carbon source:
将含氮化合物置于带盖刚玉舟内,转移至马弗炉内,从室温升温至400-600℃,反应2-6h,将产物研磨,得到粉末状含氮固体碳源;The nitrogen-containing compound is placed in a corundum boat with a cover, transferred to a muffle furnace, heated from room temperature to 400-600°C, reacted for 2-6 hours, and the product is ground to obtain a powdered nitrogen-containing solid carbon source;
第二步,化学气相沉积法制备氮掺杂碳微米管:The second step is to prepare nitrogen-doped carbon microtubes by chemical vapor deposition:
2.1)将第一步制备得到的含氮固体碳源置于敞口刚玉舟容器A中;将金属镍粉置于敞口刚玉舟容器B中。2.1) The nitrogen-containing solid carbon source prepared in the first step is placed in an open corundum boat container A; and the metal nickel powder is placed in an open corundum boat container B.
2.2)容器A、容器B分别置于一个石英管内,将石英管放入加热设备中,且容器A位于加热设备的热解区,容器B位于加热设备的气相沉积反应区。2.2) Container A and container B are placed in a quartz tube respectively, and the quartz tube is placed in a heating device, with container A located in the pyrolysis zone of the heating device and container B located in the vapor deposition reaction zone of the heating device.
2.3)在石英管中通入载气,载气的流向为从容器A侧到容器B侧;所述热解区与气相沉积反应区升到终温进行恒温反应,其中热解区的终温为650-900℃,气相沉积反应区的终温为700-1000℃,恒温反应时间为30-240min,反应结束后,加热装置自然冷却至室温。步骤2.3)的反应过程中,含氮固体碳源在高温下热解,产生气态含氮碳小分子,在载气的作用下,气态小分子与金属镍粉接触、溶解并逐渐达到饱和。随后在高温和金属镍粉的催化作用下碳原子连接并逐渐扩散沉积,最后生长为氮掺杂碳微米管。2.3) A carrier gas is introduced into the quartz tube, and the flow direction of the carrier gas is from the container A side to the container B side; the pyrolysis zone and the vapor deposition reaction zone are raised to the final temperature for constant temperature reaction, wherein the final temperature of the pyrolysis zone is 650-900°C, and the final temperature of the vapor deposition reaction zone is 700-1000°C, and the constant temperature reaction time is 30-240min. After the reaction is completed, the heating device is naturally cooled to room temperature. In the reaction process of step 2.3), the nitrogen-containing solid carbon source is pyrolyzed at high temperature to produce gaseous nitrogen-containing carbon small molecules. Under the action of the carrier gas, the gaseous small molecules contact and dissolve with the metal nickel powder and gradually reach saturation. Subsequently, under the catalytic action of high temperature and metal nickel powder, carbon atoms are connected and gradually diffused and deposited, and finally grow into nitrogen-doped carbon microtubes.
第三步,将容器B中样品取出,置于烧杯内,加入盐酸溶液,盐酸溶液与容器B中所取出样品的质量比为100:1,反应24-48h。然后抽滤、水洗至溶液呈中性,最后冷冻干燥得到氮掺杂碳微米管材料。In the third step, the sample in container B is taken out, placed in a beaker, and hydrochloric acid solution is added. The mass ratio of hydrochloric acid solution to the sample taken out of container B is 100:1, and the reaction is carried out for 24-48 hours. Then, the solution is filtered and washed with water until it is neutral, and finally freeze-dried to obtain nitrogen-doped carbon microtube material.
进一步的,所述的第一步中,含氮化合物为尿素、硫脲、一氰胺、二氰胺、二氰二胺、三聚氰胺、三聚氰氯中的一种或几种。Furthermore, in the first step, the nitrogen-containing compound is one or more of urea, thiourea, cyanamide, dicyanamide, dicyandiamide, melamine, and cyanuric chloride.
进一步的,所述的步骤2.1)中,所述的含氮固体碳源与金属镍粉的质量比为1:0.1-2。所述的金属镍粉的粒径为100-300nm。Furthermore, in the step 2.1), the mass ratio of the nitrogen-containing solid carbon source to the metal nickel powder is 1:0.1-2. The particle size of the metal nickel powder is 100-300 nm.
进一步的,所述的步骤2.3)中,载气为氮气、氩气、氦气、甲烷、乙烯中的一种。Furthermore, in the step 2.3), the carrier gas is one of nitrogen, argon, helium, methane and ethylene.
进一步的,所述的第一步中的升温速率为2-10℃/min。所述的步骤2.3)中,热解区与气相沉积反应区均以1-10℃/min升温速率升到终温。Furthermore, the heating rate in the first step is 2-10°C/min. In the step 2.3), the pyrolysis zone and the vapor deposition reaction zone are both heated to the final temperature at a heating rate of 1-10°C/min.
进一步的,所述的第三步中盐酸溶液的浓度为2-8mol/L。所述第三步中的冷冻干燥温度为-52℃,时间为24-72h。Furthermore, the concentration of the hydrochloric acid solution in the third step is 2-8 mol/L. The freeze-drying temperature in the third step is -52°C and the time is 24-72 hours.
与现有技术相比,本发明的有益效果是:Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明通过固体碳源热解化学气相沉积的策略实现高纯度氮掺杂碳微米管制备。(1) The present invention realizes the preparation of high-purity nitrogen-doped carbon microtubes through the strategy of solid carbon source pyrolysis and chemical vapor deposition.
(2)氮掺杂碳微米管的结构可调,通过调节含氮固体碳源的比例、金属镍粉的粒径、反应温度、恒温时间等因素能够实现对中空微米管状结构的形貌、尺寸以及氮含量的调控。(2) The structure of nitrogen-doped carbon microtubes is adjustable. By adjusting factors such as the proportion of nitrogen-containing solid carbon source, the particle size of metal nickel powder, reaction temperature, and constant temperature time, the morphology, size, and nitrogen content of the hollow microtube structure can be controlled.
(3)本发明方法操作简单、易于放大,反应条件温和可控,原料广泛,制备的氮掺杂碳微米管在电化学储能领域具有广阔应用前景。(3) The method of the present invention is simple to operate and easy to scale up. The reaction conditions are mild and controllable, and the raw materials are extensive. The prepared nitrogen-doped carbon microtubes have broad application prospects in the field of electrochemical energy storage.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明实施例1中得到的氮掺杂碳微米管的扫描电镜照片;FIG1 is a scanning electron microscope photograph of nitrogen-doped carbon microtubes obtained in Example 1 of the present invention;
图2为本发明实施例1中得到的氮掺杂碳微米管的XRD图谱;FIG2 is an XRD pattern of nitrogen-doped carbon microtubes obtained in Example 1 of the present invention;
图3为本发明实施例1中得到的氮掺杂碳微米管的Raman图谱;FIG3 is a Raman spectrum of nitrogen-doped carbon microtubes obtained in Example 1 of the present invention;
图4为本发明实施例1中得到的氮掺杂碳微米管的XPS谱图的N1s图;FIG4 is an N1s graph of the XPS spectrum of the nitrogen-doped carbon microtubes obtained in Example 1 of the present invention;
图5为本发明实施例2中得到的氮掺杂碳微米管的扫描电镜图;FIG5 is a scanning electron microscope image of nitrogen-doped carbon microtubes obtained in Example 2 of the present invention;
图6为本发明实施例3中得到的氮掺杂碳微米管的扫描电镜图;FIG6 is a scanning electron microscope image of nitrogen-doped carbon microtubes obtained in Example 3 of the present invention;
图7为本发明实施例4中得到的氮掺杂碳微米管的扫描电镜图;FIG7 is a scanning electron microscope image of nitrogen-doped carbon microtubes obtained in Example 4 of the present invention;
图8为本发明实施例5中得到的氮掺杂碳微米管的扫描电镜图。FIG8 is a scanning electron microscope image of the nitrogen-doped carbon microtubes obtained in Example 5 of the present invention.
具体实施方式Detailed ways
下面结合具体实施方式对本发明做进一步阐述,但是本发明不局限于以下实施例。The present invention is further described below in conjunction with specific implementation modes, but the present invention is not limited to the following embodiments.
实施例1:Embodiment 1:
一种氮掺杂碳微米管的制备方法,包括以下步骤:A method for preparing nitrogen-doped carbon microtubes comprises the following steps:
(1)含氮固体碳源制备步骤:称取三聚氰胺置于带盖刚玉舟内,转移至马弗炉内,以10℃/min的速率升温至550℃,反应4h,将产物研磨,得到粉末状含氮固体碳源。(1) Preparation steps of nitrogen-containing solid carbon source: weigh melamine and place it in a corundum boat with a cover, transfer it to a muffle furnace, heat it to 550° C. at a rate of 10° C./min, react for 4 h, grind the product to obtain a powdered nitrogen-containing solid carbon source.
(2)将2.0g含氮固体碳源粉末平铺刚玉舟容器A底部,0.2g规格为粒径为200nm金属镍粉平铺在刚玉舟容器B的底部,将容器A和容器B放入石英管内部。(2) Spread 2.0 g of nitrogen-containing solid carbon source powder on the bottom of a corundum boat container A, and spread 0.2 g of metal nickel powder with a particle size of 200 nm on the bottom of a corundum boat container B. Place container A and container B inside a quartz tube.
(3)将(2)中的石英管放入两段加热炉中,使得石英管内容器A和容器B分别位于热解区和气相沉积反应区;向石英管内通入氩气,盛有含氮固体碳源粉末的容器A位于载气上游,盛有金属镍粉的容器B位于载气下游。(3) The quartz tube in (2) is placed in a two-stage heating furnace so that container A and container B in the quartz tube are located in the pyrolysis zone and the vapor deposition reaction zone, respectively; argon gas is introduced into the quartz tube, container A containing nitrogen-containing solid carbon source powder is located upstream of the carrier gas, and container B containing metal nickel powder is located downstream of the carrier gas.
(4)容器A所在热解区从室温以10℃/min的速率升温至800℃,容器B所在的气相沉积反应区以10℃/min的速率升温至800℃,恒温反应60min;反应结束后,加热装置自然冷却至室温。(4) The pyrolysis zone where container A is located is heated from room temperature to 800°C at a rate of 10°C/min, and the vapor deposition reaction zone where container B is located is heated from room temperature to 800°C at a rate of 10°C/min, and the reaction is carried out at a constant temperature for 60 minutes. After the reaction is completed, the heating device is naturally cooled to room temperature.
(5)将容器B中样品取出,置于烧杯内,加入50mL浓度为2mol/L的盐酸溶液,反应48h,去除金属镍粉。将除去金属镍粉的样品抽滤、水洗至溶液呈中性,最后在-52℃下冷冻干燥72h,得到氮掺杂碳微米管材料。(5) Take out the sample in container B, place it in a beaker, add 50 mL of 2 mol/L hydrochloric acid solution, react for 48 hours, and remove the metal nickel powder. Filter the sample after removing the metal nickel powder, wash with water until the solution is neutral, and finally freeze-dry at -52°C for 72 hours to obtain a nitrogen-doped carbon microtube material.
本实施案例制备的氮掺杂碳微米管的扫描电镜如图1所示,扫描电镜显示制得的氮掺杂碳微米管具有规整的微纳米结构,微米管的直径为1μm,长度约为10μm,壁厚为60nm。对氮掺杂碳微米管进行XRD分析,如图2所示,具有明显的碳表征特征衍射峰存在,表明前驱体在金属镍粉的催化作用下成功转化为碳材料。对氮掺杂碳微米管进行Raman分析,如图3所示,Raman谱图存在碳的两个特征峰,ID/IG值较低,表明氮掺杂微米管具有较高的石墨化程度。The scanning electron microscope of the nitrogen-doped carbon microtubes prepared in this embodiment is shown in Figure 1. The scanning electron microscope shows that the prepared nitrogen-doped carbon microtubes have a regular micro-nano structure, and the diameter of the microtubes is 1μm, the length is about 10μm, and the wall thickness is 60nm. XRD analysis of the nitrogen-doped carbon microtubes, as shown in Figure 2, has obvious carbon-characteristic diffraction peaks, indicating that the precursor is successfully converted into carbon material under the catalytic action of metal nickel powder. Raman analysis of the nitrogen-doped carbon microtubes, as shown in Figure 3, has two characteristic peaks of carbon in the Raman spectrum, and the ID / IG value is low, indicating that the nitrogen-doped microtubes have a high degree of graphitization.
图4为本实施例制备的氮掺杂碳微米管的XPS谱图的N1s图,其被拟合为三个特征峰,对应着吡啶氮(~398.7eV)、吡咯氮(~399.7eV)和石墨氮(~401.2eV),该图说明碳微米管中氮原子的存在,成功实现氮掺杂。Figure 4 is the N1s graph of the XPS spectrum of the nitrogen-doped carbon microtubes prepared in this embodiment, which is fitted into three characteristic peaks, corresponding to pyridinic nitrogen (~398.7 eV), pyrrolic nitrogen (~399.7 eV) and graphitic nitrogen (~401.2 eV). This figure illustrates the presence of nitrogen atoms in the carbon microtubes and the successful realization of nitrogen doping.
实施例2:Embodiment 2:
一种氮掺杂碳微米管的制备方法,包括以下步骤:A method for preparing nitrogen-doped carbon microtubes comprises the following steps:
(1)含氮固体碳源制备步骤,称取三聚氰胺置于带盖刚玉舟内,转移至马弗炉内,以10℃/min的速率升温至550℃,反应4h,将产物研磨,得到粉末状含氮固体碳源。(1) Preparation step of nitrogen-containing solid carbon source: weigh melamine and place it in a corundum boat with a cover, transfer it to a muffle furnace, heat it to 550° C. at a rate of 10° C./min, react for 4 h, grind the product to obtain a powdered nitrogen-containing solid carbon source.
(2)将2.0g含氮固体碳源粉末平铺刚玉舟容器A底部,1.0g粒径为200nm金属镍粉平铺在刚玉舟容器B的底部,将容器A和容器B放入石英管内部。(2) Spread 2.0 g of nitrogen-containing solid carbon source powder on the bottom of a corundum boat container A, and spread 1.0 g of metal nickel powder with a particle size of 200 nm on the bottom of a corundum boat container B. Place container A and container B inside a quartz tube.
(3)将(2)中的石英管放入两段加热炉中,使得石英管内容器A和容器B分别位于热解区和气相沉积反应区;向石英管内通入氩气,盛有含氮固体碳源粉末的容器A位于载气上游,盛有金属镍粉的容器B位于载气下游。(3) The quartz tube in (2) is placed in a two-stage heating furnace so that container A and container B in the quartz tube are located in the pyrolysis zone and the vapor deposition reaction zone, respectively; argon gas is introduced into the quartz tube, container A containing nitrogen-containing solid carbon source powder is located upstream of the carrier gas, and container B containing metal nickel powder is located downstream of the carrier gas.
(4)容器A所在热解区从室温以10℃/min的速率升温至800℃,容器B所在的气相沉积反应区以10℃/min的速率升温至800℃,恒温反应60min;反应结束后,加热装置自然冷却至室温。(4) The pyrolysis zone where container A is located is heated from room temperature to 800°C at a rate of 10°C/min, and the vapor deposition reaction zone where container B is located is heated from room temperature to 800°C at a rate of 10°C/min, and the reaction is carried out at a constant temperature for 60 minutes. After the reaction is completed, the heating device is naturally cooled to room temperature.
(5)将容器B中样品取出,置于烧杯内,加入45mL浓度为2mol/L的盐酸溶液,反应48h,去除金属镍粉。将除去金属镍粉的样品抽滤、水洗至溶液呈中性,最后在-52℃下冷冻干燥72h,得到氮掺杂碳微米管材料。(5) Take out the sample in container B, place it in a beaker, add 45 mL of 2 mol/L hydrochloric acid solution, react for 48 hours, and remove the metal nickel powder. Filter the sample after removing the metal nickel powder, wash with water until the solution is neutral, and finally freeze-dry at -52°C for 72 hours to obtain a nitrogen-doped carbon microtube material.
本实施案例制备的氮掺杂碳微米管的扫描电镜如图5所示,扫描电镜显示制得的氮掺杂碳微米管具有规整的微纳米结构,微米管的直径为1.5μm,长度约为9μm,壁厚为60nm。The scanning electron micrograph of the nitrogen-doped carbon microtubes prepared in this embodiment is shown in FIG5 . The scanning electron micrograph shows that the prepared nitrogen-doped carbon microtubes have a regular micro-nanostructure, and the diameter of the microtubes is 1.5 μm, the length is about 9 μm, and the wall thickness is 60 nm.
对氮掺杂碳微米管进行XRD分析,具有明显的碳表征特征衍射峰存在,表明前驱体在金属镍粉的催化作用下成功转化为碳材料。对氮掺杂碳微米管进行Raman分析,Raman谱图存在碳的两个特征峰,ID/IG值较低,表明氮掺杂微米管具有较高的石墨化程度。对氮掺杂碳微米管进行XPS分析,其中N1s衍射峰的存在表明成功实现氮掺杂。XRD analysis of nitrogen-doped carbon microtubes showed obvious carbon-characteristic diffraction peaks, indicating that the precursor was successfully converted into carbon material under the catalytic action of metal nickel powder. Raman analysis of nitrogen-doped carbon microtubes showed two characteristic peaks of carbon in the Raman spectrum, and the ID / IG value was low, indicating that the nitrogen-doped microtubes had a high degree of graphitization. XPS analysis of nitrogen-doped carbon microtubes showed that the presence of N1s diffraction peaks indicated that nitrogen doping was successfully achieved.
实施例3:Embodiment 3:
一种氮掺杂碳微米管的制备方法,包括以下步骤:A method for preparing nitrogen-doped carbon microtubes comprises the following steps:
(1)含氮固体碳源制备步骤,称取三聚氰胺置于带盖刚玉舟内,转移至马弗炉内,以10℃/min的速率升温至550℃,反应4h,将产物研磨,得到粉末状含氮固体碳源。(1) Preparation step of nitrogen-containing solid carbon source: weigh melamine and place it in a corundum boat with a cover, transfer it to a muffle furnace, heat it to 550° C. at a rate of 10° C./min, react for 4 h, grind the product to obtain a powdered nitrogen-containing solid carbon source.
(2)将2.0g含氮固体碳源粉末平铺刚玉舟容器A底部,2.0g粒径为200nm金属镍粉平铺在刚玉舟容器B的底部,将容器A和容器B放入石英管内部。(2) Spread 2.0 g of nitrogen-containing solid carbon source powder on the bottom of a corundum boat container A, and spread 2.0 g of metal nickel powder with a particle size of 200 nm on the bottom of a corundum boat container B. Place container A and container B inside a quartz tube.
(3)将(2)中的石英管放入两段加热炉中,使得石英管内容器A和容器B分别位于热解区和气相沉积反应区;向石英管内通入氩气,盛有含氮固体碳源粉末的容器A位于载气上游,盛有金属镍粉的容器B位于载气下游。(3) The quartz tube in (2) is placed in a two-stage heating furnace so that container A and container B in the quartz tube are located in the pyrolysis zone and the vapor deposition reaction zone, respectively; argon gas is introduced into the quartz tube, container A containing nitrogen-containing solid carbon source powder is located upstream of the carrier gas, and container B containing metal nickel powder is located downstream of the carrier gas.
(4)容器A所在热解区从室温以10℃/min的速率升温至800℃,容器B所在的气相沉积反应区以10℃/min的速率升温至800℃,恒温反应60min;反应结束后,加热装置自然冷却至室温。(4) The pyrolysis zone where container A is located is heated from room temperature to 800°C at a rate of 10°C/min, and the vapor deposition reaction zone where container B is located is heated from room temperature to 800°C at a rate of 10°C/min, and the reaction is carried out at a constant temperature for 60 minutes. After the reaction is completed, the heating device is naturally cooled to room temperature.
(5)将容器B中样品取出,置于烧杯内,加入40mL浓度为2mol/L的盐酸溶液,反应48h,去除金属镍粉。将除去金属镍粉的样品抽滤、水洗至溶液呈中性,最后在-52℃下冷冻干燥72h,得到氮掺杂碳微米管材料。(5) Take out the sample in container B, place it in a beaker, add 40 mL of 2 mol/L hydrochloric acid solution, react for 48 hours, and remove the metal nickel powder. Filter the sample after removing the metal nickel powder, wash with water until the solution is neutral, and finally freeze-dry at -52°C for 72 hours to obtain a nitrogen-doped carbon microtube material.
本实施案例制备的氮掺杂碳微米管的扫描电镜如图6所示,扫描电镜显示制得的氮掺杂碳微米管具有规整的微纳米结构,微米管的直径为1.2μm,长度约为6μm,壁厚约为60nm。The scanning electron micrograph of the nitrogen-doped carbon microtubes prepared in this embodiment is shown in FIG6 . The scanning electron micrograph shows that the prepared nitrogen-doped carbon microtubes have a regular micro-nanostructure, and the diameter of the microtubes is 1.2 μm, the length is about 6 μm, and the wall thickness is about 60 nm.
对氮掺杂碳微米管进行XRD分析,具有明显的碳表征特征衍射峰存在,表明前驱体在金属镍粉的催化作用下成功转化为碳材料。对氮掺杂碳微米管进行Raman分析,Raman谱图存在碳的两个特征峰,ID/IG值较低,表明氮掺杂微米管具有较高的石墨化程度。对氮掺杂碳微米管进行XPS分析,其中N1s衍射峰的存在表明成功实现氮掺杂。XRD analysis of nitrogen-doped carbon microtubes showed obvious carbon-characteristic diffraction peaks, indicating that the precursor was successfully converted into carbon material under the catalytic action of metal nickel powder. Raman analysis of nitrogen-doped carbon microtubes showed two characteristic peaks of carbon in the Raman spectrum, and the ID / IG value was low, indicating that the nitrogen-doped microtubes had a high degree of graphitization. XPS analysis of nitrogen-doped carbon microtubes showed that the presence of N1s diffraction peaks indicated that nitrogen doping was successfully achieved.
实施例4:Embodiment 4:
一种氮掺杂碳微米管的制备方法,包括以下步骤:A method for preparing nitrogen-doped carbon microtubes comprises the following steps:
(1)含氮固体碳源制备步骤,称取三聚氰胺置于带盖刚玉舟内,转移至马弗炉内,以10℃/min的速率升温至550℃,反应4h,将产物研磨,得到粉末状含氮固体碳源。(1) Preparation step of nitrogen-containing solid carbon source: weigh melamine and place it in a corundum boat with a cover, transfer it to a muffle furnace, heat it to 550° C. at a rate of 10° C./min, react for 4 h, grind the product to obtain a powdered nitrogen-containing solid carbon source.
(2)将2.0g含氮固体碳源粉末平铺刚玉舟容器A底部,0.2g粒径为200nm金属镍粉平铺在刚玉舟容器B的底部,将容器A和容器B放入石英管内部。(2) Spread 2.0 g of nitrogen-containing solid carbon source powder on the bottom of a corundum boat container A, and spread 0.2 g of metal nickel powder with a particle size of 200 nm on the bottom of a corundum boat container B. Place container A and container B into a quartz tube.
(3)将(2)中的石英管放入两段加热炉中,使得石英管内容器A和容器B分别位于热解区和气相沉积反应区;向石英管内通入氩气,盛有含氮固体碳源粉末的容器A位于载气上游,盛有金属镍粉的容器B位于载气下游。(3) The quartz tube in (2) is placed in a two-stage heating furnace so that container A and container B in the quartz tube are located in the pyrolysis zone and the vapor deposition reaction zone, respectively; argon gas is introduced into the quartz tube, container A containing nitrogen-containing solid carbon source powder is located upstream of the carrier gas, and container B containing metal nickel powder is located downstream of the carrier gas.
(4)容器A所在热解区从室温以10℃/min的速率升温至700℃,容器B所在的气相沉积反应区以10℃/min的速率升温至700℃,恒温反应60min;反应结束后,加热装置自然冷却至室温。(4) The temperature of the pyrolysis zone where container A is located is increased from room temperature to 700°C at a rate of 10°C/min, and the temperature of the vapor deposition reaction zone where container B is located is increased to 700°C at a rate of 10°C/min, and the reaction is carried out at a constant temperature for 60 minutes. After the reaction is completed, the heating device is naturally cooled to room temperature.
(5)将容器B中样品取出,置于烧杯内,加入50mL浓度为2mol/L的盐酸溶液,反应48h,去除金属镍粉。将除去金属镍粉的样品抽滤、水洗至溶液呈中性,最后在-52℃下冷冻干燥72h,得到氮掺杂碳微米管材料。(5) Take out the sample in container B, place it in a beaker, add 50 mL of 2 mol/L hydrochloric acid solution, react for 48 hours, and remove the metal nickel powder. Filter the sample after removing the metal nickel powder, wash with water until the solution is neutral, and finally freeze-dry at -52°C for 72 hours to obtain a nitrogen-doped carbon microtube material.
本实施案例制备的氮掺杂碳微米管的扫描电镜如图7所示,扫描电镜显示制得的氮掺杂碳微米管具有规整的微纳米结构,微米管的直径为0.7μm,长度约为20μm,壁厚约为50nm。The scanning electron micrograph of the nitrogen-doped carbon microtubes prepared in this embodiment is shown in FIG7 . The scanning electron micrograph shows that the prepared nitrogen-doped carbon microtubes have a regular micro-nanostructure, and the diameter of the microtubes is 0.7 μm, the length is about 20 μm, and the wall thickness is about 50 nm.
对氮掺杂碳微米管进行XRD分析,具有明显的碳表征特征衍射峰存在,对氮掺杂碳微米管进行Raman分析,Raman谱图存在碳的两个特征峰,结果均表明前驱体在镍金属粉末的作用下成功转化为碳材料。对氮掺杂碳微米管进行XPS分析,其中N1s衍射峰的存在表明成功实现氮掺杂。XRD analysis of nitrogen-doped carbon microtubes showed obvious carbon-characteristic diffraction peaks, and Raman analysis of nitrogen-doped carbon microtubes showed two characteristic peaks of carbon in the Raman spectrum, both of which indicated that the precursor was successfully converted into carbon material under the action of nickel metal powder. XPS analysis of nitrogen-doped carbon microtubes showed that the presence of N1s diffraction peaks indicated that nitrogen doping was successfully achieved.
实施例5:Embodiment 5:
一种氮掺杂碳微米管的制备方法,包括以下步骤:A method for preparing nitrogen-doped carbon microtubes comprises the following steps:
(1)含氮固体碳源制备步骤,称取三聚氰胺置于带盖刚玉舟内,转移至马弗炉内,以10℃/min的速率升温至550℃,反应4h,将产物研磨,得到粉末状含氮固体碳源。(1) Preparation step of nitrogen-containing solid carbon source: weigh melamine and place it in a corundum boat with a cover, transfer it to a muffle furnace, heat it to 550° C. at a rate of 10° C./min, react for 4 h, grind the product to obtain a powdered nitrogen-containing solid carbon source.
(2)将2.0g含氮固体碳源粉末平铺刚玉舟容器A底部,0.2g粒径为200nm金属镍粉平铺在刚玉舟容器B的底部,将容器A和容器B放入石英管内部。(2) Spread 2.0 g of nitrogen-containing solid carbon source powder on the bottom of a corundum boat container A, and spread 0.2 g of metal nickel powder with a particle size of 200 nm on the bottom of a corundum boat container B. Place container A and container B into a quartz tube.
(3)将(2)中的石英管放入两段加热炉中,使得石英管内容器A和容器B分别位于热解区和气相沉积反应区;向石英管内通入氩气,盛有含氮固体碳源粉末的容器A位于载气上游,盛有金属镍粉的容器B位于载气下游。(3) The quartz tube in (2) is placed in a two-stage heating furnace so that container A and container B in the quartz tube are located in the pyrolysis zone and the vapor deposition reaction zone, respectively; argon gas is introduced into the quartz tube, container A containing nitrogen-containing solid carbon source powder is located upstream of the carrier gas, and container B containing metal nickel powder is located downstream of the carrier gas.
(4)容器A所在热解区从室温以10℃/min的速率升温至900℃,容器B所在的气相沉积反应区以10℃/min的速率升温至900℃,恒温反应60min;反应结束后,加热装置自然冷却至室温。(4) The pyrolysis zone where container A is located is heated from room temperature to 900°C at a rate of 10°C/min, and the vapor deposition reaction zone where container B is located is heated from room temperature to 900°C at a rate of 10°C/min, and the reaction is carried out at a constant temperature for 60 minutes. After the reaction is completed, the heating device is naturally cooled to room temperature.
(5)将容器B中样品取出,置于烧杯内,加入50mL浓度为2mol/L的盐酸溶液,反应48h,去除金属镍粉。将除去金属镍粉的样品抽滤、水洗至溶液呈中性,最后在-52℃下冷冻干燥72h,得到氮掺杂碳微米管材料。(5) Take out the sample in container B, place it in a beaker, add 50 mL of 2 mol/L hydrochloric acid solution, react for 48 hours, and remove the metal nickel powder. Filter the sample after removing the metal nickel powder, wash with water until the solution is neutral, and finally freeze-dry at -52°C for 72 hours to obtain a nitrogen-doped carbon microtube material.
本实施案例制备的氮掺杂碳微米管的扫描电镜如图8所示,扫描电镜显示制得的氮掺杂碳微米管具有规整的微纳米结构,微米管的直径为1μm,长度约为12μm,壁厚约为70nm。The scanning electron micrograph of the nitrogen-doped carbon microtubes prepared in this embodiment is shown in FIG8 . The scanning electron micrograph shows that the prepared nitrogen-doped carbon microtubes have a regular micro-nanostructure, and the diameter of the microtubes is 1 μm, the length is about 12 μm, and the wall thickness is about 70 nm.
对氮掺杂碳微米管进行XRD分析,具有明显的碳表征特征衍射峰存在,表明前驱体在镍金属催化剂的作用下成功转化为碳材料。对氮掺杂碳微米管进行Raman分析,Raman谱图存在碳的两个特征峰,ID/IG值较低,表明氮掺杂微米管具有较高的石墨化程度,这得益于高温下金属镍粉优异的催化作用。对氮掺杂碳微米管进行XPS分析,其中N1s衍射峰的存在表明成功实现氮掺杂。XRD analysis of nitrogen-doped carbon microtubes showed obvious carbon-characteristic diffraction peaks, indicating that the precursor was successfully converted into carbon material under the action of nickel metal catalyst. Raman analysis of nitrogen-doped carbon microtubes showed two characteristic peaks of carbon in the Raman spectrum, and the ID / IG value was low, indicating that the nitrogen-doped microtubes had a high degree of graphitization, which was due to the excellent catalytic effect of metal nickel powder at high temperature. XPS analysis of nitrogen-doped carbon microtubes showed that the presence of N1s diffraction peak indicated that nitrogen doping was successfully achieved.
实施例6:Embodiment 6:
一种氮掺杂碳微米管的制备方法,包括以下步骤:A method for preparing nitrogen-doped carbon microtubes comprises the following steps:
(1)含氮固体碳源制备步骤,称取硫脲置于带盖刚玉舟内,转移至马弗炉内,以10℃/min的速率升温至550℃,反应4h,将产物研磨,得到粉末状含氮固体碳源。(1) Preparation step of nitrogen-containing solid carbon source: weigh thiourea and place it in a corundum boat with a cover, transfer it to a muffle furnace, heat it to 550° C. at a rate of 10° C./min, react for 4 h, grind the product to obtain a powdered nitrogen-containing solid carbon source.
(2)将2.0g含氮固体碳源粉末平铺刚玉舟容器A底部,2.0g粒径为200nm金属镍粉平铺在刚玉舟容器B的底部,将容器A和容器B放入石英管内部。(2) Spread 2.0 g of nitrogen-containing solid carbon source powder on the bottom of a corundum boat container A, and spread 2.0 g of metal nickel powder with a particle size of 200 nm on the bottom of a corundum boat container B. Place container A and container B inside a quartz tube.
(3)将(2)中的石英管放入两段加热炉中,使得石英管内容器A和容器B分别位于热解区和气相沉积反应区;向石英管内通入氩气,盛有含氮固体碳源粉末的容器A位于载气上游,盛有金属镍粉的容器B位于载气下游。(3) The quartz tube in (2) is placed in a two-stage heating furnace so that container A and container B in the quartz tube are located in the pyrolysis zone and the vapor deposition reaction zone, respectively; argon gas is introduced into the quartz tube, container A containing nitrogen-containing solid carbon source powder is located upstream of the carrier gas, and container B containing metal nickel powder is located downstream of the carrier gas.
(4)容器A所在热解区从室温以10℃/min的速率升温至900℃,容器B所在的气相沉积反应区以10℃/min的速率升温至1000℃,恒温反应100min;反应结束后,加热装置自然冷却至室温。(4) The pyrolysis zone where container A is located is heated from room temperature to 900°C at a rate of 10°C/min, and the vapor deposition reaction zone where container B is located is heated from room temperature to 1000°C at a rate of 10°C/min, and the reaction is carried out at a constant temperature for 100 minutes. After the reaction is completed, the heating device is naturally cooled to room temperature.
(5)将容器B中样品取出,置于烧杯内,加入50mL浓度为2mol/L的盐酸溶液,反应48h,去除金属镍粉。将除去金属镍粉的样品抽滤、水洗至溶液呈中性,最后在-52℃下冷冻干燥72h,得到氮掺杂碳微米管材料。(5) Take out the sample in container B, place it in a beaker, add 50 mL of 2 mol/L hydrochloric acid solution, react for 48 hours, and remove the metal nickel powder. Filter the sample after removing the metal nickel powder, wash with water until the solution is neutral, and finally freeze-dry at -52°C for 72 hours to obtain a nitrogen-doped carbon microtube material.
本实施案例制备的氮掺杂碳微米管的直径为1μm,长度约为10μm,壁厚约为80nm。对氮掺杂碳微米管进行XRD分析,具有明显的碳表征特征衍射峰存在,表明前驱体在镍金属催化剂的作用下成功转化为碳材料。对氮掺杂碳微米管进行Raman分析,Raman谱图存在碳的两个特征峰,ID/IG值较低,表明在高气相沉积温度下氮掺杂微米管具有较高的石墨化程度。对氮掺杂碳微米管进行XPS分析,其中N1s衍射峰的存在表明成功实现氮掺杂。The diameter of the nitrogen-doped carbon microtubes prepared in this embodiment is 1 μm, the length is about 10 μm, and the wall thickness is about 80 nm. XRD analysis of the nitrogen-doped carbon microtubes showed the presence of obvious carbon-characteristic diffraction peaks, indicating that the precursor was successfully converted into carbon material under the action of nickel metal catalyst. Raman analysis of the nitrogen-doped carbon microtubes showed two characteristic peaks of carbon in the Raman spectrum, and the ID / IG value was low, indicating that the nitrogen-doped microtubes had a high degree of graphitization at high vapor deposition temperature. XPS analysis of the nitrogen-doped carbon microtubes showed that the presence of the N1s diffraction peak indicated that nitrogen doping was successfully achieved.
实施例7:Embodiment 7:
一种氮掺杂碳微米管的制备方法,包括以下步骤:A method for preparing nitrogen-doped carbon microtubes comprises the following steps:
(1)含氮固体碳源制备步骤,称取尿素置于带盖刚玉舟内,转移至马弗炉内,以10℃/min的速率升温至400℃,反应6h,将产物研磨,得到粉末状含氮固体碳源。(1) Preparation step of nitrogen-containing solid carbon source: weigh urea and place it in a corundum boat with a cover, transfer it to a muffle furnace, heat it to 400° C. at a rate of 10° C./min, react for 6 h, grind the product to obtain a powdered nitrogen-containing solid carbon source.
(2)将2.0g含氮固体碳源粉末平铺刚玉舟容器A底部,4.0g粒径为200nm金属镍粉平铺在刚玉舟容器B的底部,将容器A和容器B放入石英管内部。(2) Spread 2.0 g of nitrogen-containing solid carbon source powder on the bottom of a corundum boat container A, and spread 4.0 g of metal nickel powder with a particle size of 200 nm on the bottom of a corundum boat container B. Place container A and container B into a quartz tube.
(3)将(2)中的石英管放入两段加热炉中,使得石英管内容器A和容器B分别位于热解区和气相沉积反应区;向石英管内通入氩气,盛有含氮固体碳源粉末的容器A位于载气上游,盛有金属镍粉的容器B位于载气下游。(3) The quartz tube in (2) is placed in a two-stage heating furnace so that container A and container B in the quartz tube are located in the pyrolysis zone and the vapor deposition reaction zone, respectively; argon gas is introduced into the quartz tube, container A containing nitrogen-containing solid carbon source powder is located upstream of the carrier gas, and container B containing metal nickel powder is located downstream of the carrier gas.
(4)容器A所在热解区从室温以10℃/min的速率升温至650℃,容器B所在的气相沉积反应区以10℃/min的速率升温至800℃,恒温反应30min;反应结束后,加热装置自然冷却至室温。(4) The temperature of the pyrolysis zone where container A is located is increased from room temperature to 650°C at a rate of 10°C/min, and the temperature of the vapor deposition reaction zone where container B is located is increased to 800°C at a rate of 10°C/min, and the reaction is carried out at a constant temperature for 30 minutes. After the reaction is completed, the heating device is naturally cooled to room temperature.
(5)将容器B中样品取出,置于烧杯内,加入50mL浓度为2mol/L的盐酸溶液,反应48h,去除金属镍粉。将除去金属镍粉的样品抽滤、水洗至溶液呈中性,最后在-52℃下冷冻干燥72h,得到氮掺杂碳微米管材料。(5) Take out the sample in container B, place it in a beaker, add 50 mL of 2 mol/L hydrochloric acid solution, react for 48 hours, and remove the metal nickel powder. Filter the sample after removing the metal nickel powder, wash with water until the solution is neutral, and finally freeze-dry at -52°C for 72 hours to obtain a nitrogen-doped carbon microtube material.
本实施案例制备的氮掺杂碳微米管的直径为1μm,长度约为5μm,壁厚约为40nm。对氮掺杂碳微米管进行XRD分析,具有明显的碳表征特征衍射峰存在,对氮掺杂碳微米管进行Raman分析,Raman谱图存在碳的两个特征峰,结果均表明前驱体在镍金属粉末的作用下成功转化为碳材料。对氮掺杂碳微米管进行XPS分析,其中N1s衍射峰的存在表明成功实现氮掺杂。The diameter of the nitrogen-doped carbon microtubes prepared in this embodiment is 1 μm, the length is about 5 μm, and the wall thickness is about 40 nm. XRD analysis of the nitrogen-doped carbon microtubes showed the presence of obvious carbon-characteristic diffraction peaks. Raman analysis of the nitrogen-doped carbon microtubes showed two characteristic peaks of carbon in the Raman spectrum. The results all showed that the precursor was successfully converted into carbon material under the action of nickel metal powder. XPS analysis of the nitrogen-doped carbon microtubes showed that the presence of the N1s diffraction peak indicated that nitrogen doping was successfully achieved.
实施例8:Embodiment 8:
一种氮掺杂碳微米管的制备方法,包括以下步骤:A method for preparing nitrogen-doped carbon microtubes comprises the following steps:
(1)含氮固体碳源制备步骤,称取二氰二胺置于带盖刚玉舟内,转移至马弗炉内,以10℃/min的速率升温至600℃,反应2h,将产物研磨,得到粉末状含氮固体碳源。(1) Preparation step of nitrogen-containing solid carbon source: weigh dicyandiamide and place it in a corundum boat with a cover, transfer it to a muffle furnace, heat it to 600° C. at a rate of 10° C./min, react for 2 h, grind the product to obtain a powdered nitrogen-containing solid carbon source.
(2)将2.0g含氮固体碳源粉末平铺刚玉舟容器A底部,0.5g粒径为200nm金属镍粉平铺在刚玉舟容器B的底部,将容器A和容器B放入石英管内部。(2) Spread 2.0 g of nitrogen-containing solid carbon source powder on the bottom of a corundum boat container A, and spread 0.5 g of metal nickel powder with a particle size of 200 nm on the bottom of a corundum boat container B. Place container A and container B into a quartz tube.
(3)将(2)中的石英管放入两段加热炉中,使得石英管内容器A和容器B分别位于热解区和气相沉积反应区;向石英管内通入氩气,盛有含氮固体碳源粉末的容器A位于载气上游,盛有金属镍粉的容器B位于载气下游。(3) The quartz tube in (2) is placed in a two-stage heating furnace so that container A and container B in the quartz tube are located in the pyrolysis zone and the vapor deposition reaction zone, respectively; argon gas is introduced into the quartz tube, container A containing nitrogen-containing solid carbon source powder is located upstream of the carrier gas, and container B containing metal nickel powder is located downstream of the carrier gas.
(4)容器A所在热解区从室温以10℃/min的速率升温至650℃,容器B所在的气相沉积反应区以10℃/min的速率升温至800℃,恒温反应240min;反应结束后,加热装置自然冷却至室温。(4) The pyrolysis zone where container A is located is heated from room temperature to 650°C at a rate of 10°C/min, and the vapor deposition reaction zone where container B is located is heated from room temperature to 800°C at a rate of 10°C/min, and the reaction is carried out at a constant temperature for 240 minutes. After the reaction is completed, the heating device is naturally cooled to room temperature.
(5)将容器B中样品取出,置于烧杯内,加入50mL浓度为2mol/L的盐酸溶液,反应48h,去除金属镍粉。将除去金属镍粉的样品抽滤、水洗至溶液呈中性,最后在-52℃下冷冻干燥72h,得到氮掺杂碳微米管材料。(5) Take out the sample in container B, place it in a beaker, add 50 mL of 2 mol/L hydrochloric acid solution, react for 48 hours, and remove the metal nickel powder. Filter the sample after removing the metal nickel powder, wash with water until the solution is neutral, and finally freeze-dry at -52°C for 72 hours to obtain a nitrogen-doped carbon microtube material.
本实施案例制备的氮掺杂碳微米管的直径为1.2μm,长度约为20μm,壁厚约为40nm。对氮掺杂碳微米管进行XRD分析,具有明显的碳表征特征衍射峰存在,对氮掺杂碳微米管进行Raman分析,Raman谱图存在碳的两个特征峰,结果均表明前驱体在镍金属粉末的作用下成功转化为碳材料。对氮掺杂碳微米管进行XPS分析,其中N1s衍射峰的存在表明成功实现氮掺杂。The diameter of the nitrogen-doped carbon microtubes prepared in this embodiment is 1.2 μm, the length is about 20 μm, and the wall thickness is about 40 nm. XRD analysis of the nitrogen-doped carbon microtubes showed the presence of obvious carbon-characteristic diffraction peaks. Raman analysis of the nitrogen-doped carbon microtubes showed two characteristic peaks of carbon in the Raman spectrum. The results all showed that the precursor was successfully converted into carbon material under the action of nickel metal powder. XPS analysis of the nitrogen-doped carbon microtubes showed that the presence of the N1s diffraction peak indicated that nitrogen doping was successfully achieved.
以上所述实施例仅表达本发明的实施方式,但并不能因此而理解为对本发明专利的范围的限制,应当指出,对于本领域的技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些均属于本发明的保护范围。The above-described embodiments merely express the implementation methods of the present invention, but they cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.
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