技术领域technical field
本发明属于纳米材料领域，涉及一种元素掺杂多孔碳材料，具体涉及一种杂元素掺杂多孔碳材料、制备方法及其应用。The invention belongs to the field of nanometer materials and relates to an element-doped porous carbon material, in particular to a heteroelement-doped porous carbon material, a preparation method and an application thereof.
背景技术Background technique
杂原子掺杂能提高碳材料的表面润湿性、导电性等，使其在电化学方面有更好的应用。多孔杂原子掺杂的碳材料由于具有高导电性、高的比表面积、高化学稳定性、可调控的孔径，能够在气体吸附分离储存、催化剂、能量存储、传感器等领域应用广泛，在材料科学领域方面有着很好的前景。Heteroatom doping can improve the surface wettability and electrical conductivity of carbon materials, making them better in electrochemical applications. Porous heteroatom-doped carbon materials can be widely used in gas adsorption and separation storage, catalysts, energy storage, sensors and other fields due to their high conductivity, high specific surface area, high chemical stability, and adjustable pore size. There are good prospects in the field.
β-环糊精（β-CD）是直链淀粉在由芽孢杆菌产生的环糊精葡萄糖基转移酶作用下生成的含有7个D-吡喃葡萄糖单元的环状低聚糖，其具有来源丰富、价格便宜等特性。另外，β-环糊精不仅是超分子化学中主体的一员，而且也在碳材料的先驱体占着一席之地。然而，现有的有机小分子和离子液体在碳化过程中，基本挥发或者被分解成气体，碳产率极低，所以不能广泛地应用于碳材料的制备。需要制备出碳产率高的前驱体，以提高其实际应用范围。β-cyclodextrin (β-CD) is a cyclic oligosaccharide containing 7 D-glucopyranose units produced by amylose under the action of cyclodextrin glucosyltransferase produced by Bacillus, which has a source Rich, cheap and other characteristics. In addition, β-cyclodextrin is not only a member of the main body in supramolecular chemistry, but also occupies a place as a precursor of carbon materials. However, the existing organic small molecules and ionic liquids are basically volatilized or decomposed into gases during the carbonization process, and the carbon yield is extremely low, so they cannot be widely used in the preparation of carbon materials. Precursors with high carbon yields need to be prepared to increase their range of practical applications.
发明内容Contents of the invention
本发明目的是为了克服现有技术的不足而提供一种杂元素掺杂多孔碳材料。The object of the present invention is to provide a heteroelement-doped porous carbon material in order to overcome the deficiencies of the prior art.
为达到上述目的，本发明采用的技术方案是：一种杂元素掺杂多孔碳材料，它由主体材料和客体材料进行水热反应后，再进行煅烧制得，所述主体材料为β-环糊精，所述客体材料分子可套入所述主体材料分子的空穴中。In order to achieve the above-mentioned purpose, the technical solution adopted in the present invention is: a heteroelement-doped porous carbon material, which is obtained by calcining the host material and the guest material after hydrothermal reaction, and the host material is β-ring In dextrin, the molecules of the guest material can nest into the cavities of the molecules of the host material.
优化地，所述客体材料为下列化学结构式中的一种或几种组成的混合物：、、和，式中，n为1~12的整数，m、o独立地为1~6的整数，X为Cl、Br、I、PF6或BF4。Optimally, the guest material is one or a mixture of several of the following chemical structural formulas: , , and , in the formula, n is an integer of 1 to 12, m and o are independently an integer of 1 to 6, and X is Cl, Br, I, PF6 or BF4 .
进一步地，所述客体材料为下列化学结构式中的一种或几种组成的混合物：、、、和。Further, the guest material is one or a mixture of several of the following chemical structural formulas: , , , and .
优化地，所述主体材料和所述客体材料的摩尔比为1：1~3：1。Optimally, the molar ratio of the host material to the guest material is 1:1-3:1.
本发明的又一目的在于提供一种上述杂元素掺杂多孔碳材料的制备方法，它包括以下步骤：Another object of the present invention is to provide a method for preparing the above-mentioned heteroelement-doped porous carbon material, which comprises the following steps:
（a）将所述客体材料分子套入所述主体材料分子的空穴中得混合材料；(a) a mixed material obtained by inserting the molecules of the guest material into the cavities of the molecules of the host material;
（b）向所述混合材料中加入去离子水，随后置于反应釜中进行水热反应得黑色固体；(b) adding deionized water to the mixed material, and then placing it in a reaction kettle for hydrothermal reaction to obtain a black solid;
（c）将所述黑色固体研磨后进行煅烧即可。(c) The black solid may be ground and then calcined.
优化地，所述步骤（a）为：将所述客体材料和所述主体材料溶于溶剂中，在40~60℃反应5~20小时，随后旋转蒸发除去溶剂得所述混合材料。Preferably, the step (a) is: dissolving the guest material and the host material in a solvent, reacting at 40-60° C. for 5-20 hours, and then removing the solvent by rotary evaporation to obtain the mixed material.
优化地，步骤（b）中，所述水热反应为在150~200℃反应15~25小时。Optimally, in step (b), the hydrothermal reaction is carried out at 150-200°C for 15-25 hours.
优化地，步骤（c）中，所述煅烧为以5~15℃/分钟的速度升温至700~1000℃保温0.5~2小时。Optimally, in step (c), the calcination is to raise the temperature to 700-1000° C. at a rate of 5-15° C./min and keep the temperature for 0.5-2 hours.
优化地，它还包括步骤（d）研磨煅烧后的黑色固体，用稀盐酸洗涤，再用去离子水洗涤至中性，烘干即可。Optimally, it also includes the step (d) of grinding the calcined black solid, washing it with dilute hydrochloric acid, washing it with deionized water until neutral, and then drying it.
本发明的再一目的在于提供一种上述杂元素掺杂多孔碳材料在超级电容器电极中的应用。Another object of the present invention is to provide an application of the above-mentioned heteroelement-doped porous carbon material in supercapacitor electrodes.
由于上述技术方案运用，本发明与现有技术相比具有下列优点：本发明杂元素掺杂多孔碳材料，通过将主体材料和客体材料进行水热反应后，再进行煅烧制得，使得客体材料分子可套入β-环糊精分子的空穴中，不但可以有效提高碳产率，还可以引入杂元素并形成多孔结构，从而改善碳材料的性能。Due to the application of the above-mentioned technical solutions, the present invention has the following advantages compared with the prior art: the heteroelement-doped porous carbon material of the present invention is obtained by subjecting the host material and the guest material to hydrothermal reaction and then calcining, so that the guest material Molecules can be nested in the cavities of β-cyclodextrin molecules, which can not only effectively increase the carbon yield, but also introduce heteroelements and form a porous structure, thereby improving the performance of carbon materials.
附图说明Description of drawings
附图1为实施例1中杂元素掺杂多孔碳材料的SEM图；Accompanying drawing 1 is the SEM figure of heteroelement-doped porous carbon material in embodiment 1;
附图2为实施例1中杂元素掺杂多孔碳材料的TEM图；Accompanying drawing 2 is the TEM picture of heteroelement-doped porous carbon material in embodiment 1;
图3为客体材料的热重分析(TGA)图；Fig. 3 is the thermogravimetric analysis (TGA) figure of guest material;
图4为主体材料和客体材料复合物的热重分析(TGA)图。Figure 4 is a thermogravimetric analysis (TGA) graph of a composite of host material and guest material.
具体实施方式detailed description
本发明杂元素掺杂多孔碳材料，它由主体材料和客体材料进行水热反应后，再进行煅烧制得，所述主体材料为β-环糊精，所述客体材料分子可套入所述主体材料分子的空穴中。通过将主体材料和客体材料进行水热反应后，再进行煅烧制得，使得客体材料分子可套入β-环糊精分子的空穴中，不但可以有效提高碳产率，还可以引入杂元素并形成多孔结构，从而改善碳材料的性能。The heteroelement-doped porous carbon material of the present invention is obtained by calcining the host material and the guest material after hydrothermal reaction, the host material is β-cyclodextrin, and the guest material molecules can be inserted into the in the cavities of the host material molecules. It is obtained by subjecting the host material and the guest material to a hydrothermal reaction, followed by calcination, so that the molecules of the guest material can be inserted into the cavities of the β-cyclodextrin molecules, which can not only effectively increase the carbon yield, but also introduce heteroelements And form a porous structure, thereby improving the performance of carbon materials.
所述客体材料优选为下列化学结构式中的一种或几种组成的混合物：、、和，式中，n为1~12的整数，m、o独立地为1~6的整数，X为Cl、Br、I、PF6或BF4，这些材料中含有较高的N含量，从而进一步改善碳材料的性能。这些客体材料优选为下列化学结构式中的一种或几种组成的混合物：、、、和，这些物质与β-环糊精的结合力最好，有利于提高碳材料的得率。所述主体材料和所述客体材料的摩尔比优选为1：1~3：1，主体材料需要过量，从而节约成本。The guest material is preferably one or a mixture of several of the following chemical structural formulas: , , and , where n is an integer from 1 to 12, m and o are independently an integer from 1 to 6, and X is Cl, Br, I, PF6 or BF4 , these materials contain higher N content, thus further Improve the performance of carbon materials. These guest materials are preferably one or a mixture of several of the following chemical structural formulas: , , , and , these substances have the best binding force with β-cyclodextrin, which is beneficial to increase the yield of carbon materials. The molar ratio of the host material to the guest material is preferably 1:1-3:1, and the host material needs to be in excess, thereby saving costs.
上述杂元素掺杂多孔碳材料的制备方法，它包括以下步骤：（a）将所述客体材料分子套入所述主体材料分子的空穴中得混合材料；（b）向所述混合材料中加入去离子水，随后置于反应釜中进行水热反应得黑色固体；（c）将所述黑色固体研磨后进行煅烧即可。该方法现将混合材料进行水热反应后再进行煅烧，这样既能够使得客体材料和主体材料能够精密均匀结合并进行预碳化，从而确保碳材料的均匀；而且工艺简单、成本低，适于大规模生产。所述步骤（a）为：将所述客体材料和所述主体材料溶于溶剂中，在40~60℃反应5~20小时，随后旋转蒸发除去溶剂得所述混合材料。步骤（b）中，所述水热反应为在150~200℃反应15~25小时。步骤（c）中，所述煅烧为以5~15℃/分钟的速度升温至700~1000℃保温0.5~2小时。它还包括步骤（d）研磨煅烧后的黑色固体，用稀盐酸洗涤，再用去离子水洗涤至中性，烘干即可。上述杂元素掺杂多孔碳材料在超级电容器电极中的应用，具体可参考现有技术，主要是将制得的碳材料与粘结剂、碳黑等制作成超级电容器电极。The preparation method of the above-mentioned heteroelement-doped porous carbon material comprises the following steps: (a) inserting the molecules of the guest material into the cavities of the molecules of the host material to obtain a mixed material; (b) adding Adding deionized water, then placing it in a reactor for hydrothermal reaction to obtain a black solid; (c) calcining the black solid after grinding. In this method, the mixed material is hydrothermally reacted and then calcined, so that the guest material and the host material can be precisely and uniformly combined and pre-carbonized, thereby ensuring the uniformity of the carbon material; moreover, the process is simple and the cost is low, suitable for large-scale mass production. The step (a) is: dissolving the guest material and the host material in a solvent, reacting at 40-60° C. for 5-20 hours, and then removing the solvent by rotary evaporation to obtain the mixed material. In step (b), the hydrothermal reaction is carried out at 150-200° C. for 15-25 hours. In step (c), the calcination is to raise the temperature to 700-1000° C. at a rate of 5-15° C./min and keep the temperature for 0.5-2 hours. It also includes the step (d) of grinding the calcined black solid, washing it with dilute hydrochloric acid, washing it with deionized water until it is neutral, and then drying it. For the application of the above-mentioned heteroelement-doped porous carbon materials in supercapacitor electrodes, specific reference can be made to the prior art, which mainly involves making the prepared carbon materials, binders, carbon black, etc. into supercapacitor electrodes.
下面将结合附图实施例对本发明进行进一步说明。The present invention will be further described below in conjunction with the embodiments of the accompanying drawings.
实施例1Example 1
本实施例提供一种氮掺杂多孔碳材料的制备方法，它包括以下步骤：This embodiment provides a method for preparing a nitrogen-doped porous carbon material, which includes the following steps:
（a）将2gβ-CD（1.8mmol）与0.35g对氨基偶氮苯（P-AZO）（1.8mmol）溶于5mlDMF中，在40℃加热搅拌溶解得混合材料；向其中加入100ml水，析出沉淀，过滤得固体；(a) Dissolve 2g of β-CD (1.8mmol) and 0.35g of p-aminoazobenzene (P-AZO) (1.8mmol) in 5ml of DMF, heat and stir at 40°C to obtain a mixed material; add 100ml of water to it, and precipitate Precipitate, filter to get solid;
（b）将步骤（a）得到的固体与10g水加入水热反应釜中并密封，在180℃反应24小时，反应结束后离心得黑色固体；(b) Add the solid obtained in step (a) and 10 g of water into a hydrothermal reaction kettle and seal it, react at 180°C for 24 hours, and centrifuge to obtain a black solid after the reaction;
（c）将步骤（d）黑色固体与KOH以质量比为1：2充分研磨，置于惰性气体气氛中于800℃（升温速率为5℃/分钟）碳化1小时，得到的产物研磨成粉，用1mol/L的盐酸溶液洗涤，再用去离子水洗涤至中性，离心后真空干燥即可；最终产物的比表面积为989.4m2/g，含氮量为4.16%，并进行电镜测试（SEM和TEM），如图1和图2所示。(c) Fully grind the black solid and KOH in step (d) at a mass ratio of 1:2, place in an inert gas atmosphere at 800°C (heating rate: 5°C/min) for 1 hour, and grind the obtained product into powder , washed with 1mol/L hydrochloric acid solution, then washed with deionized water until neutral, centrifuged and dried in vacuum; the specific surface area of the final product is 989.4m2 /g, the nitrogen content is 4.16%, and the electron microscope test is carried out (SEM and TEM), as shown in Fig. 1 and Fig. 2.
实施例2Example 2
本实施例提供一种氮掺杂多孔碳材料的制备方法，它的具体过程与实施例1中的基本一致，不同的是：步骤（a）中，将DMF通过旋转蒸发仪去除得固体。This example provides a method for preparing a nitrogen-doped porous carbon material. Its specific process is basically the same as that in Example 1, except that in step (a), DMF is removed by a rotary evaporator to obtain a solid.
实施例3Example 3
本实施例提供一种氮掺杂多孔碳材料的制备方法，它包括以下步骤：This embodiment provides a method for preparing a nitrogen-doped porous carbon material, which includes the following steps:
（a）将2gβ-CD（1.8mmol）与0.267g金刚烷胺（Ad-NH2）（1.8mmol）溶于10g去离子水中，在60℃加热搅拌溶解得混合材料；(a) 2g of β-CD (1.8mmol) and 0.267g of amantadine (Ad-NH2 ) (1.8mmol) were dissolved in 10g of deionized water, heated and stirred at 60°C to obtain a mixed material;
（b）将混合溶液加入水热反应釜中并密封，在150℃反应25小时，反应结束后离心得黑色固体；(b) Add the mixed solution into the hydrothermal reaction kettle and seal it, react at 150°C for 25 hours, and centrifuge to obtain a black solid after the reaction;
（c）将步骤（b）得到的产物置于惰性气体气氛中于1000℃（升温速率15℃/分钟）碳化0.5小时，将产物研磨成粉，先用0.5mol/L的盐酸溶液洗涤，再用去离子水洗涤至中性，离心后真空干燥即可，最终产物含氮量为4.7%。(c) Carbonize the product obtained in step (b) at 1000°C (heating rate 15°C/min) in an inert gas atmosphere for 0.5 hours, grind the product into powder, wash it with 0.5mol/L hydrochloric acid solution, and then Wash with deionized water until neutral, then vacuum dry after centrifugation, and the nitrogen content of the final product is 4.7%.
实施例4Example 4
本实施例提供一种氮掺杂多孔碳材料的制备方法，它包括以下步骤：This embodiment provides a method for preparing a nitrogen-doped porous carbon material, which includes the following steps:
（a）将6gβ-CD（5.4mmol）与0.267g金刚烷胺（Ad-NH2）（1.8mmol）溶于20g去离子水中，在50℃加热搅拌溶解得混合材料；(a) 6g of β-CD (5.4mmol) and 0.267g of amantadine (Ad-NH2 ) (1.8mmol) were dissolved in 20g of deionized water, heated and stirred at 50°C to obtain a mixed material;
（b）将混合溶液加入水热反应釜中并密封，在200℃反应15小时，反应结束后离心得黑色固体；(b) Add the mixed solution into a hydrothermal reaction kettle and seal it, react at 200°C for 15 hours, and centrifuge to obtain a black solid after the reaction;
（c）将步骤（b）得到的产物置于惰性气体气氛中于700℃（升温速率10℃/分钟）碳化2小时，将产物研磨成粉，先用2mol/L的盐酸溶液洗涤，再用去离子水洗涤至中性，离心后真空干燥即可，最终产物含氮量为6.7%。(c) Carbonize the product obtained in step (b) at 700°C (heating rate 10°C/min) for 2 hours in an inert gas atmosphere, grind the product into powder, wash it with 2mol/L hydrochloric acid solution, and then use Wash with deionized water until neutral, centrifuge and dry in vacuum. The nitrogen content of the final product is 6.7%.
实施例5Example 5
本实施例提供一种氮掺杂多孔碳材料的制备方法，其步骤与实施例1中的基本一致，不同的是：加入的为0.417g1-十二烷基咪唑（DIM）（1.8mmol），最终产物含氮量为5.7%。This example provides a method for preparing a nitrogen-doped porous carbon material, the steps of which are basically the same as those in Example 1, except that 0.417g of 1-dodecylimidazole (DIM) (1.8mmol) is added, The nitrogen content of the final product was 5.7%.
实施例6Example 6
本实施例提供一种氮掺杂多孔碳材料的制备方法，其步骤与实施例1中的基本一致，不同的是：加入的为0.5g1–丁基–3–甲基咪唑六氟磷酸盐（BMIPF6），最终产物含氮量为5.1%，含磷量0.6%，含氟量0.2%。This example provides a method for preparing a nitrogen-doped porous carbon material, the steps of which are basically the same as those in Example 1, except that 0.5 g of 1-butyl-3-methylimidazolium hexafluorophosphate ( BMIPF6 ), the final product contains 5.1% nitrogen, 0.6% phosphorus and 0.2% fluorine.
实施例7Example 7
本实施例提供一种氮掺杂多孔碳材料的制备方法，其步骤与实施例1中的基本一致，不同的是：加入的为0.398g1–丁基–3–甲基咪唑四氟硼酸盐（BMIBF4），得到的最终产物含氮量为2.6%，含硼量12.4%，含氟量0.3%。This example provides a method for preparing a nitrogen-doped porous carbon material, the steps of which are basically the same as those in Example 1, except that 0.398g of 1-butyl-3-methylimidazolium tetrafluoroborate is added (BMIBF4 ), the obtained final product contains 2.6% nitrogen, 12.4% boron and 0.3% fluorine.
对比例1Comparative example 1
将实施例1、实施例3、实施例5、实施例6、实施例7中使用的客体材料各自进行热失重测试（TGA），如图3所示；并将实施例1、实施例3、实施例5、实施例6、实施例7中的客体材料和主体材料反应的混合材料各自进行热失重测试（TGA），如图4所示；可以最终的碳产率大幅提高至10%以上。Each of the guest materials used in Example 1, Example 3, Example 5, Example 6, and Example 7 was subjected to a thermogravimetric test (TGA), as shown in Figure 3; and Example 1, Example 3, The mixed materials of the guest material and the host material in Example 5, Example 6, and Example 7 were subjected to thermogravimetric test (TGA), as shown in Figure 4; the final carbon yield can be greatly increased to more than 10%.
实施例6Example 6
本实施例提供一种实施例1中制备的氮掺杂多孔碳材料的应用，将其制备成超级电容器电极材料，具体制作方法跟现有的方法一致，具体可以参考专利号为201310060380.3的中国发明专利实施例12中的方法；然后将该电极浸于浓度为6mol/L的KOH溶液中进行常规的电化学测试，测得它的比电容值分别为345F/g（电流密度为1A/g）和216F/g（电流密度为30A/g），并且在循环充放电5000次，仍能保留95%的比电容，具有高稳定性和优良的电化学性质。This example provides an application of the nitrogen-doped porous carbon material prepared in Example 1, and prepares it into a supercapacitor electrode material. The specific production method is consistent with the existing method. For details, please refer to the Chinese invention with patent number 201310060380.3 The method in Patent Example 12; then immerse the electrode in a KOH solution with a concentration of 6mol/L for conventional electrochemical tests, and its specific capacitance value is measured to be 345F/g (current density is 1A/g) And 216F/g (the current density is 30A/g), and after 5000 cycles of charging and discharging, it can still retain 95% of the specific capacitance, with high stability and excellent electrochemical properties.
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention. Equivalent changes or modifications made in the spirit shall fall within the protection scope of the present invention.
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| CN201510808363.2ACN105460915B (en) | 2015-11-20 | 2015-11-20 | A heteroelement-doped porous carbon material, preparation method and application thereof |
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| CN201510808363.2ACN105460915B (en) | 2015-11-20 | 2015-11-20 | A heteroelement-doped porous carbon material, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107487766A (en)* | 2017-08-29 | 2017-12-19 | 东华理工大学 | A kind of three-dimensional porous carbon material of Heteroatom doping and preparation method thereof |
| CN108470643A (en)* | 2018-03-29 | 2018-08-31 | 渤海大学 | A kind of preparation method of adamantane amine electrolytic solution for super capacitor |
| CN110911697A (en)* | 2019-11-22 | 2020-03-24 | 深圳大学 | A transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103406096A (en)* | 2013-07-17 | 2013-11-27 | 国家纳米科学中心 | Nitrogen-doped porous carbon material, preparation method and use thereof |
| CN104056556A (en)* | 2014-06-27 | 2014-09-24 | 南京大学 | Modification method for etching surface of membrane-type artificial lung and bonding beta-cyclodextrin by using low-temperature plasma |
| CN104743540A (en)* | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method for nitrogen-doped carbon material |
| CN104979105A (en)* | 2015-07-13 | 2015-10-14 | 苏州大学 | Nitrogen-doped porous carbon material, preparation method and applications |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406096A (en)* | 2013-07-17 | 2013-11-27 | 国家纳米科学中心 | Nitrogen-doped porous carbon material, preparation method and use thereof |
| CN104743540A (en)* | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method for nitrogen-doped carbon material |
| CN104056556A (en)* | 2014-06-27 | 2014-09-24 | 南京大学 | Modification method for etching surface of membrane-type artificial lung and bonding beta-cyclodextrin by using low-temperature plasma |
| CN104979105A (en)* | 2015-07-13 | 2015-10-14 | 苏州大学 | Nitrogen-doped porous carbon material, preparation method and applications |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107487766A (en)* | 2017-08-29 | 2017-12-19 | 东华理工大学 | A kind of three-dimensional porous carbon material of Heteroatom doping and preparation method thereof |
| CN108470643A (en)* | 2018-03-29 | 2018-08-31 | 渤海大学 | A kind of preparation method of adamantane amine electrolytic solution for super capacitor |
| CN110911697A (en)* | 2019-11-22 | 2020-03-24 | 深圳大学 | A transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method |
| CN110911697B (en)* | 2019-11-22 | 2022-06-07 | 深圳大学 | Transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method thereof |
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| CN105460915B (en) | 2017-09-05 |
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