技术领域Technical Field
本发明涉及一种合成单壁/寡壁碳纳米管三元金属催化剂的合成方法。The invention relates to a method for synthesizing a ternary metal catalyst for synthesizing single-walled/few-walled carbon nanotubes.
背景技术Background technique
碳纳米管是一种潜力巨大的超级材料，作为一种由大量碳原子聚集，呈同轴空心管状的纳米级材料，具有优异的物理化学性能。碳纳米管是1991年由日本NEC公司电子技术显微镜专家Iijima在高分辨透射显微镜中发现的一种具有石墨结晶的纳米级管状碳材料。由于碳纳米管具有独特的中空结构、良好的导电性、大的比表面积、适合电解质离子迁移的孔隙，以及交互缠绕可形成纳米尺度的网络结构，因而被认为是超级电容器尤其是高功率的超级电容器理想的电极材料，近年来引起了广泛的关注并成为该领域的研究热点之一。Carbon nanotubes are a super material with great potential. As a nano-scale material composed of a large number of carbon atoms in the shape of coaxial hollow tubes, they have excellent physical and chemical properties. Carbon nanotubes are nano-scale tubular carbon materials with graphite crystals that were discovered by Iijima, an electronic technology microscope expert at NEC Corporation of Japan, in a high-resolution transmission microscope in 1991. Carbon nanotubes have a unique hollow structure, good conductivity, large specific surface area, pores suitable for electrolyte ion migration, and a network structure that can be formed by intertwining at the nanoscale. Therefore, they are considered to be ideal electrode materials for supercapacitors, especially high-power supercapacitors. In recent years, they have attracted widespread attention and become one of the research hotspots in this field.
单壁/寡壁碳纳米管是典型的具有超大长径比的纳米碳材料，在储能、纳米电子器件、复合材料、催化剂载体等诸多领域均有突出表现。但一直以来，高质量单壁/寡壁碳纳米管的合成难以实现。Single-walled/oligo-walled carbon nanotubes are typical nanocarbon materials with a large aspect ratio, and have outstanding performance in many fields such as energy storage, nanoelectronic devices, composite materials, catalyst carriers, etc. However, the synthesis of high-quality single-walled/oligo-walled carbon nanotubes has always been difficult to achieve.
溶胶-凝胶法合成的催化剂在不同工艺条件下焙烧，用化学气相沉积(CVD)生长碳纳米管，相比于传统方法，该方法成本较低，操作简便，只需设定一套程序就能在一台CVD炉上实现催化剂制备和催化剂上生长大量、高质量的单壁/寡壁碳纳米管，但由于合成单壁/寡壁碳纳米管的反应温度较高，因此要求催化剂在高温反应条件下仍需具有稳定性，其中三元金属催化剂具有在高温的严峻服役条件下仍能保持相对稳定，合成单壁/寡壁碳纳米管产量高、质量高等优点，因此本报告在合成催化剂过程中选择三元金属催化剂，该催化剂的制备简单、焙烧工艺简单，简化了制备碳纳米管的工艺流程，得到较为均匀的单壁/寡壁碳纳米管，管径细，产率高，质量高。The catalyst synthesized by the sol-gel method is calcined under different process conditions, and carbon nanotubes are grown by chemical vapor deposition (CVD). Compared with traditional methods, this method has low cost and simple operation. Only a set of programs needs to be set up to prepare the catalyst and grow a large number of high-quality single-walled/oligo-walled carbon nanotubes on the catalyst in a CVD furnace. However, due to the high reaction temperature for the synthesis of single-walled/oligo-walled carbon nanotubes, the catalyst is required to be stable under high-temperature reaction conditions. Among them, ternary metal catalysts have the advantages of being relatively stable under severe high-temperature service conditions, and having high yield and high quality for synthesizing single-walled/oligo-walled carbon nanotubes. Therefore, this report selects ternary metal catalysts in the process of synthesizing catalysts. The catalyst has simple preparation and calcination process, which simplifies the process flow of preparing carbon nanotubes and obtains relatively uniform single-walled/oligo-walled carbon nanotubes with thin tube diameter, high yield and high quality.
发明内容Summary of the invention
本发明要解决的技术问题是提供一种工艺较简单、高温稳定性较好的合成单壁/寡壁碳纳米管三元金属催化剂的合成方法，相较于其他制备碳纳米管的方法，该方法制备单壁/寡壁碳纳米管，具有成本较低、操作简单、产率较高等特点，能够得到高质量的具有高温稳定性的用于生长碳纳米管的催化剂，采用载体质量为1g的溶胶-凝胶，固定金属Fe的质量为载体总质量的5％，其中各金属元素的摩尔比均为(1～5):(1～5)。在惰性气氛和空气焙烧的条件下得到三元金属催化剂，在一定温度下生长碳纳米管，得到得到管径较均匀的碳纳米管，可合成1-4nm左右的单壁/寡壁碳纳米管。满足高质量、高产量碳纳米管的要求。The technical problem to be solved by the present invention is to provide a method for synthesizing a ternary metal catalyst for synthesizing single-walled/oligo-walled carbon nanotubes with a relatively simple process and good high-temperature stability. Compared with other methods for preparing carbon nanotubes, the method for preparing single-walled/oligo-walled carbon nanotubes has the characteristics of low cost, simple operation, high yield, etc., and can obtain a high-quality catalyst for growing carbon nanotubes with high-temperature stability. A sol-gel with a carrier mass of 1g is used, and the mass of the fixed metal Fe is 5% of the total mass of the carrier, wherein the molar ratio of each metal element is (1-5): (1-5). The ternary metal catalyst is obtained under the conditions of inert atmosphere and air roasting, and carbon nanotubes are grown at a certain temperature to obtain carbon nanotubes with relatively uniform tube diameters, and single-walled/oligo-walled carbon nanotubes of about 1-4nm can be synthesized. The requirements of high-quality and high-yield carbon nanotubes are met.
为解决上述技术问题，本发明采取的技术方案为：In order to solve the above technical problems, the technical solution adopted by the present invention is:
本发明提供一种合成单壁/寡壁碳纳米管三元金属催化剂的合成方法，所述催化剂由多金属活性组分和载体组成，其中金属活性组分分别是Fe和Mo，与W、Co、Ni中的一种共计三种金属元素组成，其中各金属元素的摩尔比均为(1～5):1，所述载体选自为MgO、Al2O3、SiO2等复合金属氧化物，其中活性金属元素的总质量为载体总质量的3-6％，优选5％。The present invention provides a method for synthesizing a ternary metal catalyst for synthesizing single-walled/oligo-walled carbon nanotubes. The catalyst consists of a multi-metal active component and a carrier, wherein the metal active components are Fe and Mo, and one of W, Co and Ni, a total of three metal elements, wherein the molar ratio of each metal element is (1-5):1, and the carrier is selected from composite metal oxides such as MgO,Al2O3 ,SiO2, etc., wherein the total mass of the active metal elements is 3-6% of the total mass of the carrier, preferably 5%.
发明另提供一种合成单壁/寡壁碳纳米管三元金属催化剂的合成方法，该催化剂由活性组分和载体两部分组成，其制备方法如下：The invention also provides a method for synthesizing a ternary metal catalyst for synthesizing single-walled/oligo-walled carbon nanotubes. The catalyst consists of two parts: an active component and a carrier. The preparation method thereof is as follows:
(1)将多金属活性组分溶于水中得到溶剂；(1) dissolving the multi-metal active component in water to obtain a solvent;
(2)加入金属载体盐，选取合适的氧化物载体，固定载体金属盐质量；(2) adding metal carrier salt, selecting a suitable oxide carrier, and fixing the mass of the carrier metal salt;
(3)加入金属络合剂，水浴加热搅拌，得到均一的溶液，形成溶胶，加热蒸发得到凝胶；(3) adding a metal complexing agent, heating and stirring in a water bath to obtain a uniform solution to form a sol, and heating and evaporating to obtain a gel;
(4)将(3)中得到的凝胶放入60～140℃烘箱内，发泡成型，得到多孔材料；(4) placing the gel obtained in (3) in an oven at 60 to 140° C. for foaming to obtain a porous material;
(5)将(4)中得到的多孔材料研磨至粉末后，放入600-1000℃惰性气体中高温焙烧1～5h；(5) grinding the porous material obtained in (4) into powder, and calcining it at 600-1000° C. in an inert gas for 1-5 h;
(6)将(5)中得到的材料降至室温后，放入空气中400～700℃高温焙烧1～10h，随后降至室温，得到合成单壁/寡壁碳纳米管三元金属催化剂。(6) After the material obtained in (5) is cooled to room temperature, it is placed in air and calcined at 400-700°C for 1-10 hours, and then cooled to room temperature to obtain a ternary metal catalyst for synthesizing single-walled/oligo-walled carbon nanotubes.
进一步地，在上述技术方案中，(3)中所述的金属络合剂，保证络合剂质量大于多金属活性组分及载体的质量和。Furthermore, in the above technical solution, the metal complexing agent described in (3) ensures that the mass of the complexing agent is greater than the sum of the masses of the multi-metal active component and the carrier.
进一步地，在上述技术方案中，中所述的金属络合剂，络合剂重量用量为多金属活性组分及载体的质量的2-4倍。Furthermore, in the above technical solution, the weight amount of the metal complexing agent is 2-4 times the weight of the multi-metal active component and the carrier.
进一步地，在上述技术方案中，(3)中金属络合剂为有机酸中的柠檬酸、酒石酸、草酸中的一种或多种，金属络合剂可起到分散金属离子的作用。Furthermore, in the above technical solution, the metal complexing agent in (3) is one or more of citric acid, tartaric acid and oxalic acid in the organic acid, and the metal complexing agent can play a role in dispersing metal ions.
进一步地，在上述技术方案中，(5)中所述焙烧温度为600-1000℃，惰性气氛为亚青、氮气、氦气等一种或多种。Furthermore, in the above technical solution, the calcination temperature in (5) is 600-1000° C., and the inert atmosphere is one or more of cyan, nitrogen, helium, etc.
进一步地，在上述技术方案中，(6)中所述温度为400～700℃，不同的温度焙烧可影响催化剂中金属的颗粒大小及载体的比表面积。Furthermore, in the above technical solution, the temperature in (6) is 400-700° C. Calcination at different temperatures can affect the particle size of the metal in the catalyst and the specific surface area of the carrier.
本技术提供一种合成单壁/寡壁碳纳米管三元金属催化剂的合成方法，将金属盐溶液混合，通过溶胶-凝胶法制备三元金属催化剂，具有优异的高温稳定性。所述三元金属催化剂在高温的严峻服役条件下仍能保持相对稳定，该催化剂的制备简单、焙烧工艺简单，简化了制备碳纳米管的工艺流程，得到较为均匀的碳纳米管，可合成1-4nm左右的单壁碳纳米管及寡壁碳纳米管，管径细，产率高，质量高。The present technology provides a method for synthesizing a ternary metal catalyst for synthesizing single-walled/oligo-walled carbon nanotubes, wherein a metal salt solution is mixed, and a ternary metal catalyst is prepared by a sol-gel method, which has excellent high-temperature stability. The ternary metal catalyst can still remain relatively stable under severe service conditions at high temperatures, and the catalyst is simple to prepare and the calcination process is simple, which simplifies the process flow for preparing carbon nanotubes, and obtains relatively uniform carbon nanotubes, and can synthesize single-walled carbon nanotubes and oligo-walled carbon nanotubes of about 1-4 nm, with thin tube diameters, high yields, and high quality.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明提供的碳纳米管的TEM图；FIG1 is a TEM image of a carbon nanotube provided by the present invention;
图2为本发明提供的碳纳米管的SEM图及管径分布图；FIG2 is a SEM image and a diameter distribution diagram of the carbon nanotubes provided by the present invention;
图3为本发明对比例的碳纳米管的SEM图。FIG. 3 is a SEM image of carbon nanotubes of a comparative example of the present invention.
具体实施方式Detailed ways
下面对本发明通过结合实施例进一步详细说明。但具体实施范围不限于所举例子。The present invention is further described in detail below by combining embodiments, but the specific implementation scope is not limited to the examples given.
实施例1：Embodiment 1:
提供一种合成单壁/寡壁碳纳米管三元金属催化剂的合成方法，该催化剂由金属活性组分和载体两部分组成，其制备步骤如下：A method for synthesizing a ternary metal catalyst for synthesizing single-walled/oligo-walled carbon nanotubes is provided. The catalyst consists of two parts: a metal active component and a carrier. The preparation steps are as follows:
(1)金属盐的溶解，将0.3607g的Fe(NO3)3·9H2O、0.1564g(NH4)6Mo7O24、0.2276g(NH4)10H2(W2O7)6等三种金属盐溶解在50ml水中；(1) Dissolution of metal salts: 0.3607 g of Fe(NO3 )3 ·9H2 O, 0.1564 g of (NH4 )6 Mo7 O24 , and 0.2276 g of (NH4 )10 H2 (W2 O7 )6 were dissolved in 50 ml of water;
(2)加入6.41g载体金属盐硝酸镁；(2) adding 6.41 g of carrier metal salt magnesium nitrate;
(3)加入金属离子络合剂，80℃水浴加热搅拌，制成均一的溶液，再形成溶胶，最后形成凝胶；称取络合剂柠檬酸的质量大于活性金属盐和载体总质量；(3) adding a metal ion complexing agent, heating and stirring in a water bath at 80° C. to form a uniform solution, then forming a sol, and finally forming a gel; weighing the mass of the complexing agent citric acid to be greater than the total mass of the active metal salt and the carrier;
(4)将(3)中得到的凝胶放入110℃烘箱内发泡成型，制成多孔材料；(4) placing the gel obtained in (3) in an oven at 110° C. for foaming to form a porous material;
(5)将(4)中得到的多孔材料用玛瑙研钵研磨得到黄色粉末，得到用于生长碳纳米管的高熵合金纳米催化剂，放入800℃的惰性气氛中焙烧2h，得到的催化剂活性金属的金属离子摩尔比为1:1:1。(5) The porous material obtained in (4) was ground into a yellow powder using an agate mortar to obtain a high entropy alloy nanocatalyst for growing carbon nanotubes, which was then calcined in an inert atmosphere at 800° C. for 2 h. The molar ratio of the metal ions of the active metal in the obtained catalyst was 1:1:1.
(6)将(5)降至室温后，放入空气中，升温至500℃焙烧4h，随后降至室温，得到的黑色粉末样品即为与催化剂混杂在一起的碳纳米管产物，得到管径较为均匀的碳纳米管，管径细，产量高；(6) After (5) is cooled to room temperature, it is placed in air, heated to 500°C and calcined for 4 hours, and then cooled to room temperature. The obtained black powder sample is the carbon nanotube product mixed with the catalyst, and the obtained carbon nanotubes have relatively uniform diameters, thin diameters, and high yields.
(7)催化剂用于生长碳纳米管产量测试：(7) Catalyst used to grow carbon nanotubes yield test:
催化剂用于生长碳纳米管是在内径为48mm反应管中进行，称取0.2g催化剂置于石英舟均匀平铺，在Ar中吹扫以80mL min-1的流速吹扫0.5h，排尽反应管内空气，再以5℃min-1升温至500℃，以流量为80mL min-1纯氢将催化剂还原2h；再升温至800℃，反应气为CH4和H2的混合气(VCH4:VH2＝40:80)，总流量为120mL min-1，反应2h，用来生长碳纳米管。随后在Ar气氛中自然降至室温，计算反应中碳纳米管的产量，产量用g·gcat-1·h-1来计算。计算公式为：mbefore为生长碳纳米管前的催化剂质量，mafter为生长碳纳米管后的催化剂质量，t为碳纳米管生长的反应时间，碳纳米管生长在本技术方案上催化剂的产量见表1。The catalyst is used to grow carbon nanotubes in a reaction tube with an inner diameter of 48 mm. 0.2 g of catalyst is weighed and placed in a quartz boat and evenly spread. The reaction tube is purged at a flow rate of 80 mL min-1 for 0.5 h in Ar to exhaust the air in the reaction tube. The temperature is then raised to 500 ° C at a rate of 5 ° C min-1 . The catalyst is reduced for 2 h with a flow rate of 80 mL min-1 of pure hydrogen. The temperature is then raised to 800 ° C. The reaction gas is a mixture of CH4 and H2 (VCH4 :VH2 = 40:80) with a total flow rate of 120 mL min-1 . The reaction is carried out for 2 h to grow carbon nanotubes. The temperature is then naturally reduced to room temperature in an Ar atmosphere. The yield of carbon nanotubes in the reaction is calculated. The yield is calculated in g·gcat-1 ·h-1 . The calculation formula is: mbefore is the mass of the catalyst before the growth of carbon nanotubes, mafter is the mass of the catalyst after the growth of carbon nanotubes, t is the reaction time of the growth of carbon nanotubes, and the yield of the catalyst for the growth of carbon nanotubes in this technical solution is shown in Table 1.
实施例2：Embodiment 2:
(1)金属盐的溶解，在0.3607g的Fe(NO3)3·9H2O、0.1564g(NH4)6Mo7O24、0.3414g(NH4)10H2(W2O7)6等三种金属盐溶解在50ml水中；(1) Dissolution of metal salts: 0.3607 g of Fe(NO3 )3 ·9H2 O, 0.1564 g of (NH4 )6 Mo7 O24 , and 0.3414 g of (NH4 )10 H2 (W2 O7 )6 were dissolved in 50 ml of water;
(2)与实施例1相同；(2) Same as Example 1;
(3)加入金属离子络合剂，80℃水浴搅拌，制成均一的溶液，再形成溶胶，最后形成凝胶；称取络合剂柠檬酸的质量大于活性金属盐和载体总质量；(3) adding a metal ion complexing agent, stirring in a water bath at 80° C. to form a uniform solution, then forming a sol, and finally forming a gel; weighing the mass of the complexing agent citric acid to be greater than the total mass of the active metal salt and the carrier;
(4)将(3)中得到的凝胶放入110℃烘箱内，发泡成型，制成多孔材料；(4) placing the gel obtained in (3) in an oven at 110° C. for foaming to form a porous material;
(5)将(4)中得到的多孔材料研磨成粉末，放得到用于生长碳纳米管的高熵合金纳米粒子催化剂。入800℃的惰性气氛中焙烧2h，得到的催化剂活性金属的金属离子摩尔比为1:1:1.5；(5) Grinding the porous material obtained in (4) into powder to obtain a high entropy alloy nanoparticle catalyst for growing carbon nanotubes. The powder is placed in an inert atmosphere at 800° C. and calcined for 2 h. The molar ratio of the metal ions of the active metals in the obtained catalyst is 1:1:1.5;
(6)将(5)降至室温后，放入空气中，升温至500℃焙烧4h，随后降至室温，得到的黑色粉末样品即为与催化剂混杂在一起的碳纳米管产物，得到管径较为均匀的碳纳米管，管径细，产量高；(6) After (5) is cooled to room temperature, it is placed in air, heated to 500°C and calcined for 4 hours, and then cooled to room temperature. The obtained black powder sample is the carbon nanotube product mixed with the catalyst, and the obtained carbon nanotubes have relatively uniform diameters, thin diameters, and high yields.
(7)催化剂用于生长碳纳米管产量测试与实施例1相同，催化剂生长碳纳米管的产量见表1，产量较高。(7) The test of the yield of carbon nanotubes grown by the catalyst is the same as that in Example 1. The yield of carbon nanotubes grown by the catalyst is shown in Table 1, and the yield is relatively high.
实施例3：Embodiment 3:
(1)金属盐的溶解，将0.3607g的Fe(NO3)3·9H2O、0.1564g(NH4)6Mo7O24、0.2599g Co(NO3)2·6H2O等三种金属盐溶解在50ml水中；(1) Dissolution of metal salts: 0.3607 g of Fe(NO3 )3 ·9H2 O, 0.1564 g of (NH4 )6 Mo7 O24 , and 0.2599 g of Co(NO3 )2 ·6H2 O were dissolved in 50 ml of water;
(2)与实施例1相同；(2) Same as Example 1;
(3)加入金属离子络合剂，80℃水浴搅拌，制成均一的溶液，再形成溶胶，最后形成凝胶；称取络合剂柠檬酸的质量大于活性金属盐和载体总质量；(3) adding a metal ion complexing agent, stirring in a water bath at 80° C. to form a uniform solution, then forming a sol, and finally forming a gel; weighing the mass of the complexing agent citric acid to be greater than the total mass of the active metal salt and the carrier;
(4)将(3)中得到的凝胶放入110℃烘箱内，发泡成型，制成多孔材料；(4) placing the gel obtained in (3) in an oven at 110° C. for foaming to form a porous material;
(5)将(4)中得到的多孔材料研磨成粉末，放得到用于生长碳纳米管的高熵合金纳米粒子催化剂。入800℃的惰性气氛中焙烧2h，得到的催化剂活性金属的金属离子摩尔比为1:1:1；(5) Grinding the porous material obtained in (4) into powder, placing it into an inert atmosphere at 800° C. for 2 h to obtain a high entropy alloy nanoparticle catalyst for growing carbon nanotubes, and calcining the powder for 2 h in an inert atmosphere. The molar ratio of the metal ions of the catalyst active metal is 1:1:1;
(6)将(5)降至室温后，放入空气中，升温至500℃焙烧4h，随后降至室温，得到的黑色粉末样品即为与催化剂混杂在一起的碳纳米管产物，得到管径较为均匀的碳纳米管，管径细，产量高；(6) After (5) is cooled to room temperature, it is placed in air, heated to 500°C and calcined for 4 hours, and then cooled to room temperature. The obtained black powder sample is the carbon nanotube product mixed with the catalyst, and the obtained carbon nanotubes have relatively uniform diameters, thin diameters, and high yields.
(7)催化剂用于生长碳纳米管产量测试与实施例1相同，催化剂生长碳纳米管的产量见表1，产量较高。(7) The test of the yield of carbon nanotubes grown by the catalyst is the same as that in Example 1. The yield of carbon nanotubes grown by the catalyst is shown in Table 1, and the yield is relatively high.
实施例4：Embodiment 4:
(1)金属盐的溶解，将0.3607g的Fe(NO3)3·9H2O、0.1564g(NH4)6Mo7O24、0.2597g Ni(NO3)2·6H2O等三种金属盐溶解在50ml水中；(1) Dissolution of metal salts: 0.3607 g of Fe(NO3 )3 ·9H2 O, 0.1564 g of (NH4 )6 Mo7 O24 , and 0.2597 g of Ni(NO3 )2 ·6H2 O were dissolved in 50 ml of water;
(2)与实施例1相同；(2) Same as Example 1;
(3)加入金属离子络合剂，80℃水浴搅拌，制成均一的溶液，再形成溶胶，最后形成凝胶；称取络合剂柠檬酸的质量大于活性金属盐和载体总质量；(3) adding a metal ion complexing agent, stirring in a water bath at 80° C. to form a uniform solution, then forming a sol, and finally forming a gel; weighing the mass of the complexing agent citric acid to be greater than the total mass of the active metal salt and the carrier;
(4)将(3)中得到的凝胶放入110℃烘箱内，发泡成型，制成多孔材料；(4) placing the gel obtained in (3) in an oven at 110° C. for foaming to form a porous material;
(5)将(4)中得到的多孔材料研磨成粉末，放得到用于生长碳纳米管的高熵合金纳米粒子催化剂。入800℃的惰性气氛中焙烧2h，得到的催化剂活性金属的金属离子摩尔比为1:1:1；(5) Grinding the porous material obtained in (4) into powder, placing it into an inert atmosphere at 800° C. for 2 h to obtain a high entropy alloy nanoparticle catalyst for growing carbon nanotubes, and calcining the powder for 2 h in an inert atmosphere. The molar ratio of the metal ions of the catalyst active metal is 1:1:1;
(6)将(5)降至室温后，放入空气中，升温至500℃焙烧4h，随后降至室温，得到的黑色粉末样品即为与催化剂混杂在一起的碳纳米管产物，得到管径较为均匀的碳纳米管，管径细，产量高；(6) After (5) is cooled to room temperature, it is placed in air, heated to 500°C and calcined for 4 hours, and then cooled to room temperature. The obtained black powder sample is the carbon nanotube product mixed with the catalyst, and the obtained carbon nanotubes have relatively uniform diameters, thin diameters, and high yields.
(7)催化剂用于生长碳纳米管产量测试与实施例1相同，催化剂生长碳纳米管的产量见表1，产量较高。(7) The test of the yield of carbon nanotubes grown by the catalyst is the same as that in Example 1. The yield of carbon nanotubes grown by the catalyst is shown in Table 1, and the yield is relatively high.
对比例1：Comparative Example 1:
(1)金属盐的溶解，将0.3607g的Fe(NO3)3·9H2O、0.2276g(NH4)10H2(W2O7)6、等两种金属盐溶解在50ml水中；(1) Dissolution of metal salts: 0.3607 g of Fe(NO3 )3 ·9H2 O and 0.2276 g of (NH4 )10 H2 (W2 O7 )6 were dissolved in 50 ml of water;
(2)与实施例1相同；(2) Same as Example 1;
(3)加入金属离子络合剂，80℃水浴搅拌，制成均一的溶液，再形成溶胶，最后形成凝胶；称取络合剂柠檬酸的质量大于活性金属盐和载体总质量；(3) adding a metal ion complexing agent, stirring in a water bath at 80° C. to form a uniform solution, then forming a sol, and finally forming a gel; weighing the mass of the complexing agent citric acid to be greater than the total mass of the active metal salt and the carrier;
(4)将(3)中得到的凝胶放入110℃烘箱内，发泡成型，制成多孔材料；(4) placing the gel obtained in (3) in an oven at 110° C. for foaming to form a porous material;
(5)将(4)中得到的多孔材料研磨成粉末，放得到用于生长碳纳米管的高熵合金纳米粒子催化剂。入800℃的惰性气氛中焙烧2h，得到的催化剂活性金属的金属离子摩尔比为1:1；(5) Grinding the porous material obtained in (4) into powder, placing it into an inert atmosphere at 800° C. for 2 h to obtain a high entropy alloy nanoparticle catalyst for growing carbon nanotubes, and calcining the powder for 2 h in an inert atmosphere. The molar ratio of the metal ions of the active metals in the obtained catalyst is 1:1;
(6)将(5)降至室温后，放入空气中，升温至500℃焙烧4h，随后降至室温，得到的黑色粉末样品即为与催化剂混杂在一起的碳纳米管产物；(6) After (5) is cooled to room temperature, it is placed in air, heated to 500°C and calcined for 4 hours, and then cooled to room temperature. The obtained black powder sample is the carbon nanotube product mixed with the catalyst;
(7)催化剂用于生长碳纳米管产量测试与实施例1相同，催化剂生长碳纳米管的产量见表1。(7) The test of the yield of carbon nanotubes grown by the catalyst is the same as that in Example 1. The yield of carbon nanotubes grown by the catalyst is shown in Table 1.
对比例2：Comparative Example 2:
(1)金属盐的溶解，将0.3607g的Fe(NO3)3·9H2O、0.2599g Co(NO3)2·6H2O等两种金属盐溶解在50ml水中；(1) Dissolution of metal salts: 0.3607 g of Fe(NO3 )3 ·9H2 O and 0.2599 g of Co(NO3 )2 ·6H2 O were dissolved in 50 ml of water;
(2)与实施例1相同；(2) Same as Example 1;
(3)加入金属离子络合剂，80℃水浴搅拌，制成均一的溶液，再形成溶胶，最后形成凝胶；称取络合剂柠檬酸的质量大于活性金属盐和载体总质量；(3) adding a metal ion complexing agent, stirring in a water bath at 80° C. to form a uniform solution, then forming a sol, and finally forming a gel; weighing the mass of the complexing agent citric acid to be greater than the total mass of the active metal salt and the carrier;
(4)将(3)中得到的凝胶放入110℃烘箱内，发泡成型，制成多孔材料；(4) placing the gel obtained in (3) in an oven at 110° C. for foaming to form a porous material;
(5)将(4)中得到的多孔材料研磨成粉末，放得到用于生长碳纳米管的高熵合金纳米粒子催化剂。入800℃的惰性气氛中焙烧2h，得到的催化剂活性金属的金属离子摩尔比为1:1；(5) Grinding the porous material obtained in (4) into powder, placing it into an inert atmosphere at 800° C. for 2 h to obtain a high entropy alloy nanoparticle catalyst for growing carbon nanotubes, and calcining the powder for 2 h in an inert atmosphere. The molar ratio of the metal ions of the active metals in the obtained catalyst is 1:1;
(6)将(5)降至室温后，放入空气中，升温至500℃焙烧4h，随后降至室温，得到的黑色粉末样品即为与催化剂混杂在一起的碳纳米管产物；(6) After (5) is cooled to room temperature, it is placed in air, heated to 500°C and calcined for 4 hours, and then cooled to room temperature. The obtained black powder sample is the carbon nanotube product mixed with the catalyst;
(7)催化剂用于生长碳纳米管产量测试与实施例1相同，催化剂生长碳纳米管的产量见表1。(7) The test of the yield of carbon nanotubes grown by the catalyst is the same as that in Example 1. The yield of carbon nanotubes grown by the catalyst is shown in Table 1.
表1：实施例1-5在1000℃生长碳纳米管的产量表Table 1: Yield of carbon nanotubes grown at 1000°C in Examples 1-5
从表1可见，三元金属催化剂合成的碳纳米管的产量较高，具有较好的高温稳定性，有利于生长碳纳米管，实施例1-4中的催化剂都表现出了较好的高温稳定性，其中实施例1中的催化剂生长出的碳纳米管的产量最高，产量5.4g·gcat-1·h-1。As can be seen from Table 1, the yield of carbon nanotubes synthesized by the ternary metal catalyst is high, and has good high temperature stability, which is conducive to the growth of carbon nanotubes. The catalysts in Examples 1-4 all show good high temperature stability, among which the catalyst in Example 1 has the highest yield of carbon nanotubes grown, with a yield of 5.4 g·gcat-1 ·h-1 .
从图1和图2可见，采用实施例1合成的碳纳米管管径较为均匀，既可合成1-4nm的单壁碳纳米管及寡壁碳纳米管，管径细，产量高。As can be seen from FIG. 1 and FIG. 2 , the diameter of the carbon nanotubes synthesized by Example 1 is relatively uniform, and both single-walled carbon nanotubes and oligo-walled carbon nanotubes with a diameter of 1-4 nm can be synthesized, with a thin diameter and high yield.
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