CN111908443A - Preparation method of self-doped porous carbon - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 241000512259 Ascophyllum nodosum Species 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000001994 activation Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000004913 activation Effects 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims 1
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- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 13
- 125000005842 heteroatom Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012190 activator Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241001474374 Blennius Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
技术领域technical field
本发明属于吸附材料的制备方法技术领域,涉及一种自掺杂多孔碳的制备方法。The invention belongs to the technical field of preparation methods of adsorbent materials, and relates to a preparation method of self-doped porous carbon.
背景技术Background technique
多孔碳由于热力学稳定性好、化学稳定性高,在酸碱中均可以保持化学惰性、孔道结构发达、比表面积高、表面活性强以及能够方便地进行功能性修饰而在催化、分离、能源、环境等诸多领域具有广泛应用。多孔碳材料的合成方法包括凝胶法、模板法、活化法等。凝胶法虽然可以方便控制工艺,得到不同孔径的多孔碳,但制备周期较长并且工艺复杂,无法大规模使用。模板法能够大规模生产并且工艺稳定,所制备多孔碳孔径均一、结构有序,但需要去除模板,工艺复杂并且制备出的多孔碳孔径单一,因而其应用受到局限。活化法原料来源广泛并且制备工艺简单,适合大批量工业化生产,但所制备多孔碳以微孔为主,并且孔径范围分布较宽,从而限制了其在催化、吸附和锂电方面等背景下的应用。多孔材料按照孔径大小可以分为微孔(直径小于2nm),中孔(直径大于2nm而小于50nm)和大孔(直径大于50nm)。微孔碳材料由于孔道过小,直径稍大的分子无法进入孔道发生反应并且在孔道内反应产物中的大分子无法及时逸出,从而无法在吸附、催化等行业的应用;介孔碳材料由于孔径适中,并且具有较高的热稳定性和化学稳定性而在分离提取、催化以及吸附各个方面有广泛应用,但溶液流通性不足;大孔碳材料能够为溶液的流通提供有效通道,但其机械稳定性差、比表面积太低,在电化学应用领域受限。Porous carbon can maintain chemical inertness in acid and alkali, developed pore structure, high specific surface area, strong surface activity and convenient functional modification due to its good thermodynamic stability and high chemical stability. It has a wide range of applications in many fields such as the environment. The synthesis methods of porous carbon materials include gel method, template method, activation method, etc. Although the gel method can easily control the process and obtain porous carbons with different pore sizes, the preparation cycle is long and the process is complicated, so it cannot be used on a large scale. The template method can be produced on a large scale and has a stable process. The prepared porous carbon has a uniform pore size and an orderly structure, but the template needs to be removed, the process is complicated, and the prepared porous carbon has a single pore size, so its application is limited. The activation method has a wide range of raw material sources and a simple preparation process, which is suitable for large-scale industrial production. However, the prepared porous carbon is mainly micropores and has a wide distribution of pore sizes, which limits its application in the background of catalysis, adsorption and lithium batteries. . Porous materials can be divided into micropores (diameter less than 2nm), mesopores (diameter greater than 2nm but less than 50nm) and macropores (diameter greater than 50nm) according to the pore size. Because the pores of microporous carbon materials are too small, molecules with slightly larger diameters cannot enter the pores to react, and the macromolecules in the reaction products in the pores cannot escape in time, so they cannot be used in adsorption, catalysis and other industries. The pore size is moderate, and it has high thermal and chemical stability, and is widely used in separation, extraction, catalysis and adsorption, but the solution has insufficient fluidity; macroporous carbon materials can provide an effective channel for the circulation of the solution, but its The mechanical stability is poor and the specific surface area is too low, which is limited in the field of electrochemical applications.
大量研究表明多孔碳的表面官能团对其电化学性能有着显著影响,多孔碳因表面活性强很容易引入其他杂元素进行修饰,从而形成功能性官能团。N、P、S、F、B等杂原子的引入可以提高多孔碳的润湿性和反应催化活性,还能产生附加赝电容并提高其电容量,因此杂原子掺杂多孔碳的研究近年来引起了人们的兴趣。杂原子的主要来源有两种,一种是在制备过程中加入含杂原子的材料进行反应而掺杂进去的杂原子,另一种是原料前驱体自身所携带的杂原子。制备多孔碳的原料主要有石油、沥青、煤炭、废弃高分子材料、生物质材料等。生物质资源丰富、成本低廉,富含多种杂元素且属于可再生资源,用生物质材料作为前驱体制备自掺杂多孔碳,不仅方法简单、节约成本,还可以缓解化石燃料的短缺和环境污染问题。除此之外,自然界的植物由于呼吸和代谢作用,本身便具有发达的分级多孔结构,以保障气体交换和营养物质流通等生命活动,有利于形成分级多孔碳材料。目前,常用于制备多孔碳的生物质有秸秆类、农业废渣、木材、果皮果壳等。但相比之下用海洋生物作为多孔碳原材料的报道很少。众所周知,海洋拥有巨大的藻类植物资源,但海藻产品加工利用率低、产能过剩现象严重。A large number of studies have shown that the surface functional groups of porous carbon have a significant impact on its electrochemical performance. Porous carbon can easily be modified by introducing other heteroelements due to its strong surface activity, thereby forming functional functional groups. The introduction of heteroatoms such as N, P, S, F, and B can improve the wettability and catalytic activity of porous carbon, and can also generate additional pseudocapacitance and improve its capacitance. aroused interest. There are two main sources of heteroatoms, one is the heteroatom doped by adding a heteroatom-containing material to react during the preparation process, and the other is the heteroatom carried by the raw material precursor itself. The raw materials for preparing porous carbon mainly include petroleum, asphalt, coal, waste polymer materials, biomass materials, etc. Biomass is rich in resources, low in cost, rich in various heteroelements and belongs to renewable resources. Using biomass materials as precursors to prepare self-doped porous carbon is not only simple and cost-effective, but also can alleviate the shortage of fossil fuels and the environment. pollution problem. In addition, natural plants have developed hierarchical porous structures due to their respiration and metabolism to ensure life activities such as gas exchange and nutrient circulation, which is conducive to the formation of hierarchical porous carbon materials. At present, the biomass commonly used to prepare porous carbon includes straw, agricultural waste residue, wood, fruit peel and husk. However, there are few reports on the use of marine organisms as porous carbon raw materials. As we all know, the ocean has huge algae plant resources, but the processing utilization rate of seaweed products is low and the overcapacity is serious.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种自掺杂多孔碳的制备方法,解决了现有技术中存在的海藻产品加工利用率低的问题。The purpose of the present invention is to provide a preparation method of self-doped porous carbon, which solves the problem of low processing utilization rate of seaweed products in the prior art.
本发明所采用的技术方案是,一种自掺杂多孔碳的制备方法,包括以下步骤:The technical scheme adopted in the present invention is, a preparation method of self-doping porous carbon, comprising the following steps:
步骤1、将预处理后的海带粉末置于坩埚中进行碳化处理,得到碳化物;Step 1, placing the pretreated kelp powder in a crucible for carbonization to obtain carbide;
步骤2、将碳化物与氢氧化钾粉末按照1:2~1:4的比例进行混合研磨,然后将混合物置于坩埚中活化处理,得到多孔碳;Step 2, mixing and grinding the carbide and potassium hydroxide powder in a ratio of 1:2 to 1:4, and then placing the mixture in a crucible for activation treatment to obtain porous carbon;
步骤3、采用HCL溶液对多孔碳浸泡后,加入去离子水稀释;然后进行抽滤,并多次加入稀释剂清洗至中性;最后加入去离子水进行离心分离、干燥,得到自掺杂的分级多孔碳材料。Step 3. After soaking the porous carbon with HCL solution, add deionized water to dilute; then perform suction filtration, and add diluent for several times to clean until neutral; finally add deionized water for centrifugal separation and drying to obtain self-doped carbon. Hierarchical porous carbon materials.
本发明的特点还在于:The feature of the present invention also lies in:
步骤1的预处理过程为:将海带粉末置于温度为80~100℃的烘箱中干燥30~60min。The pretreatment process of step 1 is as follows: drying the kelp powder in an oven with a temperature of 80-100° C. for 30-60 minutes.
步骤1的碳化过程为:将坩埚中置于管式炉中,在100~300ml/min氮气气流保护下,以5~10℃/min的速度升温至600~1000℃,保温90~120min后自然冷却至室温。The carbonization process in step 1 is as follows: place the crucible in a tube furnace, and under the protection of 100-300ml/min nitrogen gas flow, heat up to 600-1000°C at a speed of 5-10°C/min, keep the temperature for 90-120min and then naturally. Cool to room temperature.
步骤2的活化过程为:将坩埚加盖放入管式炉中,在100~300ml/min氮气气流保护下,以5~10℃/min的速度升温至600~800℃,保温60~120min后自然冷却至室温。The activation process of step 2 is as follows: put the crucible into a tube furnace with a cover, under the protection of 100-300ml/min nitrogen gas flow, heat up to 600-800°C at a speed of 5-10°C/min, and keep the temperature for 60-120min. Cool naturally to room temperature.
步骤3中HCL溶液的浓度为0.5~1mol/L。The concentration of the HCL solution in step 3 is 0.5-1 mol/L.
稀释剂为去离子水和乙醇的混合物。The diluent is a mixture of deionized water and ethanol.
离心分离过程的参数为:转速为5000~1000rpm,时间为10~15min。The parameters of the centrifugal separation process are: the rotation speed is 5000-1000 rpm, and the time is 10-15 min.
本发明的有益效果是:The beneficial effects of the present invention are:
本发明自掺杂多孔碳的制备方法,选取海带作为碳的前驱体,因为海带价格低廉、来源广泛、产量高、繁殖快,且海带本身含氮、磷、硫杂原子,经过碳化活化处理后可直接得到含氮磷硫的分级多孔碳材料,无需添加其他试剂来掺杂杂原子;方法操作简单、经济环保,得到的自掺杂分级多孔碳材料具有高的比表面积、优良的导电性,作为超级电容器的电极材料具有广阔的应用前景;不仅能提高海带产品利用率,赋予其较高的附加值,还能有效缓解能源短缺问题。The preparation method of the self-doped porous carbon of the present invention selects kelp as the carbon precursor, because the kelp has low price, wide sources, high yield and fast reproduction, and the kelp itself contains nitrogen, phosphorus and sulfur heteroatoms. After carbonization activation treatment The hierarchical porous carbon material containing nitrogen, phosphorus and sulfur can be directly obtained without adding other reagents to dope heteroatoms; the method is simple to operate, economical and environmentally friendly, and the obtained self-doped hierarchical porous carbon material has high specific surface area and excellent electrical conductivity. As an electrode material for supercapacitors, it has broad application prospects; it can not only improve the utilization rate of kelp products, endow them with higher added value, but also effectively alleviate the problem of energy shortage.
附图说明Description of drawings
图1是本发明一种自掺杂多孔碳的制备方法中实施例1得到的自掺杂分级孔碳材料的扫描电镜图;1 is a scanning electron microscope image of the self-doping graded porous carbon material obtained in Example 1 in a method for preparing self-doping porous carbon of the present invention;
图2是本发明一种自掺杂多孔碳的制备方法中实施例2得到自掺杂分级孔碳材料的扫描电镜图;2 is a scanning electron microscope image of the self-doping graded porous carbon material obtained in Example 2 in a method for preparing self-doping porous carbon of the present invention;
图3是本发明一种自掺杂多孔碳的制备方法中实施例3得到的自掺杂分级孔碳材料的扫描电镜图。3 is a scanning electron microscope image of the self-doping hierarchical porous carbon material obtained in Example 3 in a method for preparing self-doping porous carbon of the present invention.
具体实施方式Detailed ways
下面结合附图和具体实施方式对本发明进行详细说明。The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
一种自掺杂多孔碳的制备方法,如图1所示,包括以下步骤:A preparation method of self-doped porous carbon, as shown in Figure 1, includes the following steps:
步骤1、先将海带粉末置于温度为80~100℃的烘箱中干燥30~60min,然后海带粉末置于坩埚中,将坩埚加盖中置于管式炉中进行碳化处理,100~300ml/min氮气气流保护下,以5~10℃/min的速度升温至600~1000℃,保温90~120min后自然冷却至室温,得到碳化物;选择氮气作为保护气相比于其他保护气体如氩气成本较低;碳化温度选择600~1000℃,是由于碳化产物后续还要进行活化,如果步骤1碳化温度太低,碳化产物形成的孔隙较少且孔径很小,不利于活化剂与碳材料的充分接触,达不到良好的活化效果;如果碳化温度过高,碳化产物的石墨化程度较高,不利于活化剂与碳材料的反应,从而难以创造新的孔结构;除此之外温度过高导致碳化物结构破碎塌陷,若活化剂进一步与之反应腐蚀会更加破坏原有的孔结构;Step 1. First, place the kelp powder in an oven with a temperature of 80 to 100°C for 30 to 60 minutes, then place the kelp powder in a crucible, put the crucible in a lid and place it in a tube furnace for carbonization, 100 to 300ml/ Under the protection of nitrogen gas flow, the temperature is raised to 600 to 1000 °C at a rate of 5 to 10 °C/min, and the temperature is kept for 90 to 120 minutes, and then naturally cooled to room temperature to obtain carbides; the cost of choosing nitrogen as the protective gas is compared to other protective gases such as argon. Lower; the carbonization temperature is 600-1000°C, because the carbonized product needs to be activated later. If the carbonization temperature in step 1 is too low, the carbonized product will form fewer pores and a small pore size, which is not conducive to the sufficient activator and carbon material. If the carbonization temperature is too high, the degree of graphitization of the carbonized product is high, which is not conducive to the reaction between the activator and the carbon material, so it is difficult to create a new pore structure; in addition, the temperature is too high Cause the carbide structure to be broken and collapsed, and if the activator reacts with it further, the corrosion will further damage the original pore structure;
步骤2、将碳化物与氢氧化钾粉末按照1:2~1:4的比例进行混合研磨,然后将混合物置于坩埚中,加盖放入管式炉中活化处理,在100~300ml/min氮气气流保护下,以5~10℃/min的速度升温至600~800℃,保温60~120min后自然冷却至室温,得到多孔碳;Step 2. The carbide and potassium hydroxide powder are mixed and ground in a ratio of 1:2 to 1:4, then the mixture is placed in a crucible, covered and placed in a tube furnace for activation treatment at 100 to 300 ml/min. Under the protection of nitrogen gas flow, the temperature is raised to 600-800°C at a rate of 5-10°C/min, and the temperature is kept for 60-120min and then cooled to room temperature naturally to obtain porous carbon;
步骤3、采用浓度为0.5~1mol/LHCL溶液对多孔碳浸泡,磁力搅拌2~5h后加入去离子水稀释;然后进行抽滤,并多次加入稀释剂清洗至中性;之后加入去离子水进行离心分离转速为5000~10000rpm,时间为10~15min,最后将离心后的产物置于烘箱中干燥12h,温度80~100℃,得到自掺杂的分级多孔碳材料。盐酸溶液、去离子水、乙醇用于洗去多孔碳材料中的杂质。Step 3. Soak the porous carbon with a concentration of 0.5-1mol/L HCL solution, stir magnetically for 2-5 hours, add deionized water to dilute; then perform suction filtration, and add diluent for several times to clean until neutral; then add deionized water The centrifugal separation speed is 5000-10000 rpm, and the time is 10-15 min. Finally, the centrifuged product is dried in an oven for 12 hours at a temperature of 80-100° C. to obtain a self-doped hierarchical porous carbon material. Hydrochloric acid solution, deionized water, and ethanol are used to wash away impurities in the porous carbon material.
本发明的海带干燥后作为碳源,同时也作为氮磷硫杂原子的来源,通过碳化得到自掺杂碳化物;采用KOH作为活化剂,其与碳化产物的反应活性较大、产生的孔隙较多,KOH活化法是制备高比表面积多孔碳最有效的方法,不同比例氢氧化钾活化剂,活化效果不同,活化时碳材料与KOH的最佳质量比为1:2~1:4。因此本发明采用氢氧化钾粉末作为活化剂,碳材料与KOH的质量比为1:2~1:4,活化后得到自掺杂分级多孔碳。The kelp of the present invention is used as a carbon source after drying, and also serves as a source of nitrogen, phosphorus, and sulfur heteroatoms to obtain self-doped carbides through carbonization; KOH is used as an activator, and its reaction activity with the carbonized product is relatively large, and the generated pores are relatively large. KOH activation method is the most effective method to prepare porous carbon with high specific surface area. Different ratios of potassium hydroxide activator have different activation effects. The optimal mass ratio of carbon material to KOH during activation is 1:2 to 1:4. Therefore, in the present invention, potassium hydroxide powder is used as the activator, the mass ratio of the carbon material to KOH is 1:2-1:4, and the self-doped hierarchical porous carbon is obtained after activation.
通过以上方式,本发明自掺杂多孔碳的制备方法,选取海带作为碳的前驱体,因为海带价格低廉、来源广泛、产量高、繁殖快,且海带本身含氮、磷、硫杂原子,经过碳化活化处理后可直接得到含氮磷硫的分级多孔碳材料,无需添加其他试剂来掺杂杂原子;方法操作简单、经济环保,得到的自掺杂分级多孔碳材料具有高的比表面积、优良的导电性,作为超级电容器的电极材料具有广阔的应用前景;不仅能提高海带产品利用率,赋予其较高的附加值,还能有效缓解能源短缺问题。Through the above method, the preparation method of self-doped porous carbon of the present invention selects kelp as the precursor of carbon, because kelp has low price, wide source, high yield, fast reproduction, and kelp itself contains nitrogen, phosphorus and sulfur heteroatoms, After the carbonization activation treatment, the hierarchical porous carbon material containing nitrogen, phosphorus and sulfur can be directly obtained without adding other reagents to dope heteroatoms; the method is simple to operate, economical and environmentally friendly, and the obtained self-doped hierarchical porous carbon material has high specific surface area, excellent The conductivity of kelp has broad application prospects as an electrode material for supercapacitors; it can not only improve the utilization rate of kelp products, endow it with higher added value, but also effectively alleviate the problem of energy shortage.
实施例1Example 1
步骤1、先将4g海带粉末置于温度为80℃的烘箱中干燥60min,然后海带粉末置于坩埚中,将坩埚加盖中置于管式炉中进行碳化处理,100ml/min氮气气流保护下,以5℃/min的速度升温至600℃,保温120min后自然冷却至室温,得到碳化物;Step 1. First, 4g of kelp powder was placed in an oven with a temperature of 80 ° C to dry for 60min, then the kelp powder was placed in a crucible, and the crucible was covered and placed in a tube furnace for carbonization treatment, under the protection of 100ml/min nitrogen gas flow , heated to 600°C at a rate of 5°C/min, kept for 120min and then naturally cooled to room temperature to obtain carbide;
步骤2、将碳化物与氢氧化钾粉末按照1:4的比例进行混合研磨,然后将混合物置于坩埚中,加盖放入管式炉中活化处理,在200ml/min氮气气流保护下,以5℃/min的速度升温至800℃,保温120min后自然冷却至室温,得到多孔碳;Step 2. The carbide and potassium hydroxide powder are mixed and ground at a ratio of 1:4, then the mixture is placed in a crucible, covered and placed in a tube furnace for activation treatment, under the protection of 200ml/min nitrogen gas flow, with The temperature was raised to 800°C at a rate of 5°C/min, and the temperature was kept for 120 min, and then cooled to room temperature naturally to obtain porous carbon;
步骤3、采用浓度为1mol/LHCL溶液对多孔碳浸泡,磁力搅拌5h后加入去离子水稀释;然后进行抽滤,并多次加入稀释剂清洗至中性;之后加入去离子水进行离心分离转速为6000rpm,时间为15min,最后将离心后的产物置于烘箱中干燥12h,温度80℃,得到自掺杂的分级多孔碳材料。本实施例的自掺杂的分级多孔碳材料扫描电镜图见图1,从图1可看出本实施例得到的分级多孔碳呈形状不规则的块状疏松结构,具有非常发达的孔隙结构,孔径为几到几百纳米不等,多为微孔和较小的中孔结构。Step 3. Soak the porous carbon with a concentration of 1mol/L HCL solution, stir magnetically for 5 hours, and then add deionized water for dilution; then perform suction filtration, and add diluent for several times to clean to neutrality; then add deionized water for centrifugal separation. The temperature was 6000 rpm and the time was 15 min. Finally, the centrifuged product was dried in an oven for 12 h at a temperature of 80° C. to obtain a self-doped hierarchical porous carbon material. The SEM image of the self-doped hierarchical porous carbon material in this example is shown in Fig. 1. It can be seen from Fig. 1 that the hierarchical porous carbon obtained in this example has an irregular block-like loose structure and has a very developed pore structure. The pore size ranges from several to several hundreds of nanometers, and most of them are micropores and smaller mesoporous structures.
实施例2Example 2
步骤1、先将6g海带粉末置于温度为90℃的烘箱中干燥45min,然后海带粉末置于坩埚中,将坩埚加盖中置于管式炉中进行碳化处理,200ml/min氮气气流保护下,以6℃/min的速度升温至800℃,保温120min后自然冷却至室温,得到碳化物;Step 1. First put 6g of kelp powder in an oven with a temperature of 90 ° C to dry for 45min, then place the kelp powder in a crucible, put the crucible in a cover and place it in a tube furnace for carbonization, under the protection of 200ml/min nitrogen gas flow , heated to 800°C at a rate of 6°C/min, kept for 120min and then naturally cooled to room temperature to obtain carbide;
步骤2、将碳化物与氢氧化钾粉末按照1:3的比例进行混合研磨,然后将混合物置于坩埚中,加盖放入管式炉中活化处理,在200ml/min氮气气流保护下,以6℃/min的速度升温至700℃,保温90min后自然冷却至室温,得到多孔碳;Step 2. The carbide and potassium hydroxide powder are mixed and ground in a ratio of 1:3, then the mixture is placed in a crucible, covered and placed in a tube furnace for activation treatment, under the protection of 200ml/min nitrogen gas flow, with The temperature was raised to 700°C at a rate of 6°C/min, and then cooled to room temperature naturally after being kept for 90 minutes to obtain porous carbon;
步骤3、采用浓度为0.8mol/LHCL溶液对多孔碳浸泡,磁力搅拌4h后加入去离子水稀释;然后进行抽滤,并多次加入稀释剂清洗至中性;之后加入去离子水进行离心分离转速为7000rpm,时间为10min,最后将离心后的产物置于烘箱中干燥12h,温度90℃,得到自掺杂的分级多孔碳材料。Step 3. Soak the porous carbon with a concentration of 0.8mol/L HCL solution, stir magnetically for 4 hours, and then add deionized water for dilution; then perform suction filtration, and add diluent for several times to clean to neutrality; then add deionized water for centrifugal separation The rotating speed was 7000 rpm and the time was 10 min. Finally, the centrifuged product was dried in an oven for 12 h at a temperature of 90° C. to obtain a self-doped hierarchical porous carbon material.
本实施例的自掺杂的分级多孔碳材料扫描电镜图见图2,由图可知本实施例得到的分级多孔碳仍为不规则的块状蜂窝结构,孔隙结构丰富。较之实施例1得到的产物,本实施例得到的分级多孔碳的平均孔径有所增大。The SEM image of the self-doped hierarchical porous carbon material in this example is shown in FIG. 2 , it can be seen from the figure that the hierarchical porous carbon obtained in this example still has an irregular block honeycomb structure with rich pore structure. Compared with the product obtained in Example 1, the average pore size of the hierarchical porous carbon obtained in this example is increased.
实施例3Example 3
步骤1、先将8g海带粉末置于温度为100℃的烘箱中干燥30min,然后海带粉末置于坩埚中,将坩埚加盖中置于管式炉中进行碳化处理,300ml/min氮气气流保护下,以8℃/min的速度升温至1000℃,保温90min后自然冷却至室温,得到碳化物;Step 1. First put 8g of kelp powder in an oven with a temperature of 100°C for 30 minutes, then place the kelp powder in a crucible, put the crucible in a cover and place it in a tube furnace for carbonization, under the protection of 300ml/min nitrogen gas flow , heat up to 1000°C at a rate of 8°C/min, and cool to room temperature naturally after holding for 90min to obtain carbide;
步骤2、将碳化物与氢氧化钾粉末按照1:2的比例进行混合研磨,然后将混合物置于坩埚中,加盖放入管式炉中活化处理,在200ml/min氮气气流保护下,以8℃/min的速度升温至600℃,保温120min后自然冷却至室温,得到多孔碳;Step 2. Mix and grind the carbide and potassium hydroxide powder according to the ratio of 1:2, then put the mixture in a crucible, put it into a tube furnace with a cover for activation treatment, and under the protection of 200ml/min nitrogen gas flow, with The temperature was raised to 600°C at a rate of 8°C/min, and the temperature was kept for 120 min, and then cooled to room temperature naturally to obtain porous carbon;
步骤3、采用浓度为0.5mol/LHCL溶液对多孔碳浸泡,磁力搅拌2h后加入去离子水稀释;然后进行抽滤,并多次加入稀释剂清洗至中性;之后加入去离子水进行离心分离转速为7000rpm,时间为10min,最后将离心后的产物置于烘箱中干燥12h,温度90℃,得到自掺杂的分级多孔碳材料。Step 3. Soak the porous carbon with a concentration of 0.5mol/L HCL solution, stir magnetically for 2 hours, and then add deionized water for dilution; then perform suction filtration, and add diluent for several times to clean to neutrality; then add deionized water for centrifugal separation The rotating speed was 7000 rpm and the time was 10 min. Finally, the centrifuged product was dried in an oven for 12 h at a temperature of 90° C. to obtain a self-doped hierarchical porous carbon material.
本实施例的自掺杂的分级多孔碳材料扫描电镜图见图3,从图中可看出本实施例得到的分级多孔碳呈蜂窝结构,孔隙发达但大孔数量较多,孔道内壁变薄、临近孔隙相互连通,甚至有些通道破碎。The SEM image of the self-doped hierarchical porous carbon material in this example is shown in Figure 3. It can be seen from the figure that the hierarchical porous carbon obtained in this example has a honeycomb structure with well-developed pores but a large number of macropores, and the inner wall of the pores becomes thinner. , adjacent pores are interconnected, and even some channels are broken.
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