WO2019119460A1 - Method for preparing nitrogen-doped graphene from furazan derivatives as nitrogen source - Google Patents
Method for preparing nitrogen-doped graphene from furazan derivatives as nitrogen source Download PDFInfo
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- WO2019119460A1 WO2019119460A1 PCT/CN2017/118140 CN2017118140W WO2019119460A1 WO 2019119460 A1 WO2019119460 A1 WO 2019119460A1 CN 2017118140 W CN2017118140 W CN 2017118140W WO 2019119460 A1 WO2019119460 A1 WO 2019119460A1
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- the invention belongs to the technical field of material preparation, and in particular relates to a method for preparing nitrogen-doped graphene as a nitrogen source.
- Graphene (G) is a two-dimensional honeycomb lattice material formed by the close combination of planar single-layer carbon atoms. It has a thickness of about 0.35 nm and is the world's thinnest two-dimensional material.
- Graphene has many unique properties, such as: tensile strength up to 130GPa; carrier mobility up to 15000-25000 cm 2 /Vs (square centimeters per volt second), can exceed 10 times the silicon wafer; thermal conductivity Up to 5000 W/mK (watt per watt thermal conductivity), which is three times that of diamond; it also has room temperature quantum Hall effect and room temperature ferromagnetism. Due to these unique properties, graphene electrons pass through without any resistance, generate less heat, and have high electrical conductivity. Therefore, graphene is the most excellent material with known conductivity.
- the invention provides a preparation method of nitrogen-doped graphene as a nitrogen source, and aims to solve the problem that the graphene material is not easily compounded with other materials, resulting in limited application range.
- the invention provides a method for preparing nitrogen-doped graphene as a nitrogen source, which comprises:
- the mass ratio of graphene to furfuran derivatives is 1:6-10, and the furazan derivatives are diaminofurazan (DAF), diamino azofuran (DAAzF) and 3-amino At least one of -4-nitrofurazan (ANF) or the like;
- DAF diaminofurazan
- DAAzF diamino azofuran
- NAF 3-amino At least one of -4-nitrofurazan
- the graphene-coated furazan derivative eutectic is ground into a powder and heated to 500-800 ° C for 3 to 5 hours to obtain nitrogen-doped graphene.
- the method for preparing nitrogen-doped graphene as a nitrogen source uses a furazan derivative to react with graphene to obtain a graphene material having a high nitrogen doping content.
- the graphene is uniformly coated on the surface of the furazan derivative crystal, and the surface properties of the furazan derivative crystal are completely maintained, so that no additives such as an adhesive are needed, and the finally obtained nitrogen-doped graphite
- the olefinic material is easily compounded with other materials, expanding the range of application of graphene.
- FIG. 1 is a flow chart showing a method for preparing a nitrogen-doped graphene using a furfuran derivative as a nitrogen source according to an embodiment of the present invention
- FIG. 2 is a schematic diagram showing the physical flow of a method for preparing nitrogen-doped graphene using a furfuran derivative as a nitrogen source according to an embodiment of the present invention
- Example 3 is a scanning electron microscope test chart of nitrogen-doped graphene prepared in Example 1 of the present invention.
- Example 4 is a X-ray photoelectron spectroscopy test chart of nitrogen-doped graphene prepared in Example 1 of the present invention
- Example 5 is a N1s X-ray photoelectron spectroscopy test chart of the nitrogen-doped graphene prepared in Example 1 of the present invention
- Fig. 6 is a X-ray photoelectron spectroscopy test chart of C1s of nitrogen-doped graphene prepared in Example 1 of the present invention.
- FIG. 1 is a flow chart of a method for preparing nitrogen-doped graphene as a nitrogen source according to an embodiment of the present invention, the method comprising:
- Step 101 Dispersing graphene in water to obtain an aqueous graphene solution.
- the number of layers of the graphene is 1-3 layers.
- Step 102 adding a furfural derivative to the aqueous graphene solution, heating and stirring at 50 to 70 ° C for 30 to 60 minutes, cooling to 20 to 40 ° C, and drying at a constant temperature to obtain a graphene-coated furazan derivative. Eutectic.
- the mass ratio of graphene to furazan derivative is 1:6-10; and the furazan derivative is diaminofurazan (DAF), diamino azofuran (DAAzF) and 3-amino- At least one of 4-nitrofurazan (ANF) and the like.
- the furfuran derivative has a nitrogen content of 43 to 58 wt%.
- DAF is a nitrogen heterocyclic compound having a nitrogen content of 56%.
- Step 103 Grinding the graphene-coated furazan derivative eutectic into a powder, heating to 500-800 ° C, and maintaining the temperature for 3-5 h to obtain nitrogen-doped graphene.
- the method for preparing nitrogen-doped graphene as a nitrogen source uses a furazan derivative to react with graphene to obtain a graphene material having a high nitrogen doping content.
- the graphene is uniformly coated on the surface of the furazan derivative crystal, and the surface properties of the furazan derivative crystal are completely maintained, so that no additives such as an adhesive are needed, and the finally obtained nitrogen-doped graphite
- the olefinic material is easily compounded with other materials, greatly expanding the application range of graphene.
- the nitrogen-doped graphene material prepared by the method opens the band gap, adjusts the conductivity type, changes the electronic structure, improves the free carrier density, improves the conductivity and stability, and introduces the nitrogen-containing
- the functional group increases the active site of the surface-adsorbed metal particles and enhances the interaction between the metal particles and the graphene, thereby expanding the application of graphene.
- step S101 the graphene is added to the deionized water, stirred for 30 to 90 minutes, and ultrasonically shaken for 30 to 60 minutes, wherein the mass ratio of the graphene to the deionized water is 1:20 to 30, and the graphene aqueous solution is The concentration is 1 to 5 mg/mL, and the number of layers of graphene is 1 to 3 layers, preferably a single layer, and the chip diameter is 0.2 to 100 ⁇ m.
- the graphene is placed in a beaker containing ionized water, and the graphene and the ionized water are magnetically stirred at a preset rotation speed.
- the beaker After magnetic stirring, the beaker is placed in an ultrasonic disperser, and the ultrasonic disperser is used.
- the magnetically stirred solution was subjected to ultrasonic shaking treatment to obtain an aqueous graphene solution (aqueous solution of graphene oxide).
- the magnetic stirring can be carried out for 30 ⁇ 90min according to the different rotation speed, and the ultrasonic shaking treatment time is 30 ⁇ 60min.
- step S102 the furfural derivative is added to a beaker containing an aqueous solution of graphene, and then the beaker is placed on a heating table with stirring, heated (heating temperature is 50-70 ° C) and stirred for 30-60 min. , to obtain a dispersion; when the dispersion is cooled to 20 to 40 ° C, the beaker containing the dispersion is placed in an ultrasonic disperser, and a heating device is placed above the ultrasonic disperser, and the dispersion is performed by an ultrasonic disperser.
- the ultrasonic vibration treatment is performed, and the dispersion liquid is subjected to constant temperature drying treatment by using a heating device (or the constant temperature drying treatment is performed on the dispersion liquid by a constant temperature drying oven) to finally obtain a graphene-coated furazan derivative eutectic.
- the constant temperature drying treatment time is 48 h
- the preferred constant temperature is 25 ° C
- the mass ratio of graphene to furfural derivative in the graphene aqueous solution is 1:1 to 10, preferably 1:6 to 10, more It is preferably 1:8.
- the heating temperature of the graphene-coated furazan derivative eutectic is 500-700 ° C, preferably 600 ° C, and the heating time is 3-6 h, preferably 4 h, and the nitrogen content is obtained. 5.16% nitrogen-doped graphene.
- 0.1 g of graphene with a diameter of 0.2 ⁇ m was added to 25 ml of deionized water, magnetically stirred at 600 r/min for 60 minutes, then placed in an ultrasonic disperser, and ultrasonically shaken for 60 minutes. 4 mg/ml graphene solution.
- the DAF eutectic was ground into a powder, heated in a tube furnace to 600 ° C, and kept for 4 h to obtain nitrogen-doped graphene having a nitrogen content of 5.16%.
- FIG. 3 a scanning electron microscope schematic of nitrogen-doped graphene prepared by using DAF as a nitrogen source is shown. It can be seen from Fig. 3 that among the nitrogen-doped graphene obtained by the experiment, graphene is uniformly coated on the surface of the DAF crystal, and the surface properties of the DAF crystal are completely maintained without using an auxiliary agent such as an adhesive.
- X-ray photoelectron spectroscopy test chart of nitrogen-doped graphene prepared by using DAF as a nitrogen source compared with pure graphene, it can be seen that the binding energy shows a sharp peak at 398-403 eV, indicating that DAF as a nitrogen source can effectively combine DAF with graphene to obtain nitrogen-doped graphene. It can be explained that DAF is a nitrogen source for preparing nitrogen-doped graphene.
- FIG. 5 a schematic diagram of N1s XPS of nitrogen-doped graphene prepared by using DAF as a nitrogen source is shown.
- graphene nitrogen (N) plays a key role in expanding the application of graphene.
- three types of bonding are usually formed in the crystal lattice of carbon atoms: pyridin N, pyrrolic N, and graphitic N.
- Graphene nitrogen doping has the following advantages: (1) opening the band gap and adjusting the conductivity type, changing its electronic structure; (2) increasing the free carrier density, thereby improving its conductivity and stability; (3) introducing The nitrogen functional group can increase the active site of the metal particles adsorbed on the surface thereof, thereby enhancing the interaction between the metal particles and the graphene. Therefore, NG is widely used in the fields of lithium ion batteries, lithium air batteries and supercapacitor electrode materials, and fuel cell redox catalysts. As can be seen from Fig.
- FIG. 6 an X-ray photoelectron spectroscopy test chart of C1s of nitrogen-doped graphene prepared by using DAF as a nitrogen source is shown.
- 0.1 g of graphene with a diameter of 0.5 ⁇ m was added to 25 ml of deionized water, magnetically stirred at 600 r/min for 70 minutes, then placed in an ultrasonic disperser, and ultrasonically shaken for 40 minutes. 4 mg/ml graphene solution.
- the DAAzF eutectic was ground into a powder, heated in a tube furnace to 700 ° C, and kept for 5 h to obtain nitrogen-doped graphene having a nitrogen content of 6.12%.
- 0.1 g of graphene with a diameter of 1.0 ⁇ m was added to 25 ml of deionized water, magnetically stirred at 600 r/min for 50 minutes, then placed in an ultrasonic disperser, and ultrasonically shaken for 40 minutes. 4 mg/ml graphene solution.
- the ANF eutectic was ground into a powder, heated in a tube furnace to 800 ° C, and kept for 5 h to obtain nitrogen-doped graphene having a nitrogen content of 7.15%.
Abstract
Provided is a method for preparing nitrogen-doped graphene from furazan derivatives as a nitrogen source. The method comprises: dispersing graphene in water to obtain a graphene aqueous solution; adding furazan derivatives to the graphene aqueous solution, heating and stirring at a temperature of 50-70°C for 30-60 min, cooling to 20-40°C, and drying at a constant temperature to obtain a graphene-coated furazan derivative eutectic crystal; grinding the graphene-coated furazan derivative eutectic crystal into powder, and heating the powder to 500-800°C and keeping at the constant temperature for 3-5 h to obtain nitrogen-doped graphene. The surface of the furazan derivative crystal is uniformly coated with the graphene in the nitrogen-doped graphene without using an auxiliary such as an adhesive, so that the surface performance of the furazan derivative crystal is completely maintained.
Description
本发明属于材料制备技术领域，尤其涉及一种呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法。The invention belongs to the technical field of material preparation, and in particular relates to a method for preparing nitrogen-doped graphene as a nitrogen source.
石墨烯（G）是平面单层碳原子紧密结合在一起形成的二维蜂窝晶格材料，厚度为0.35 nm 左右，是世界上最薄的二维材料。Graphene (G) is a two-dimensional honeycomb lattice material formed by the close combination of planar single-layer carbon atoms. It has a thickness of about 0.35 nm and is the world's thinnest two-dimensional material.
石墨烯具有很多独特的性能，例如：拉伸强度可达130GPa；载流子迁移率可达15000-25000 cm2/Vs（平方厘米每伏秒），可超过硅片的10 倍；热导率可达5000 W/mK（瓦每毫导热系数），是金刚石的3倍；它还具有室温量子霍尔效应及室温铁磁性等。由于这些独特性能，使得石墨烯的电子穿过没有任何阻力、产生的热量少、导电效率高，因此，石墨烯是已知导电性能最优异的材料。Graphene has many unique properties, such as: tensile strength up to 130GPa; carrier mobility up to 15000-25000 cm 2 /Vs (square centimeters per volt second), can exceed 10 times the silicon wafer; thermal conductivity Up to 5000 W/mK (watt per watt thermal conductivity), which is three times that of diamond; it also has room temperature quantum Hall effect and room temperature ferromagnetism. Due to these unique properties, graphene electrons pass through without any resistance, generate less heat, and have high electrical conductivity. Therefore, graphene is the most excellent material with known conductivity.
然而，由于石墨烯没有能带隙，其电导性不能像传统的半导体一样完全被控制，而且它表面光滑呈惰性，不利于与其它材料复合。以上缺点限制了石墨烯的应用。However, since graphene has no band gap, its electrical conductivity cannot be completely controlled like a conventional semiconductor, and its surface is smooth and inert, which is not conducive to recombination with other materials. The above disadvantages limit the application of graphene.
本发明提供一种呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法，旨在解决石墨烯材料不容易与其它材料复合，导致应用范围受限制的问题。The invention provides a preparation method of nitrogen-doped graphene as a nitrogen source, and aims to solve the problem that the graphene material is not easily compounded with other materials, resulting in limited application range.
本发明提供的一种呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法，包括：The invention provides a method for preparing nitrogen-doped graphene as a nitrogen source, which comprises:
将石墨烯分散于水中，得到石墨烯水溶液；所述石墨烯的层数为1~3层；Dispersing graphene in water to obtain an aqueous graphene solution; the number of layers of the graphene is 1-3 layers;
将呋咱类衍生物加入所述石墨烯水溶液，在50~70℃下加热并搅拌30~60min，降温至20~40℃，恒温干燥，得到石墨烯包覆的呋咱类衍生物共晶物；其中，石墨烯与呋咱类衍生物的质量比为1:6~10，且呋咱类衍生物为二氨基呋咱(DAF)、二氨基氧化偶氮呋咱(DAAzF)和3-氨基-4-硝基呋咱(ANF)等中的至少一种；Adding a furfural derivative to the graphene aqueous solution, heating and stirring at 50 to 70 ° C for 30 to 60 minutes, cooling to 20 to 40 ° C, and drying at a constant temperature to obtain a graphene-coated furazan derivative eutectic Among them, the mass ratio of graphene to furfuran derivatives is 1:6-10, and the furazan derivatives are diaminofurazan (DAF), diamino azofuran (DAAzF) and 3-amino At least one of -4-nitrofurazan (ANF) or the like;
将石墨烯包覆的呋咱类衍生物共晶物研磨成粉末，并加热至500~800℃，恒温3~5h，得到氮掺杂石墨烯。The graphene-coated furazan derivative eutectic is ground into a powder and heated to 500-800 ° C for 3 to 5 hours to obtain nitrogen-doped graphene.
本发明提供的呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法，利用呋咱类衍生物与石墨烯进行反应，得到氮掺杂含量较高的石墨烯材料。该材料中石墨烯均匀包覆在呋咱类衍生物晶体的表面，完整的保持了呋咱类衍生物晶体的表面性能，因此不需要使用胶黏剂等助剂，最终得到的氮掺杂石墨烯材料容易与其它材料复合，拓展了石墨烯的应用范围。The method for preparing nitrogen-doped graphene as a nitrogen source provided by the present invention uses a furazan derivative to react with graphene to obtain a graphene material having a high nitrogen doping content. The graphene is uniformly coated on the surface of the furazan derivative crystal, and the surface properties of the furazan derivative crystal are completely maintained, so that no additives such as an adhesive are needed, and the finally obtained nitrogen-doped graphite The olefinic material is easily compounded with other materials, expanding the range of application of graphene.
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below. Obviously, the drawings in the following description are only It is some embodiments of the invention.
图1是本发明实施例提供的一种呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法的流程图；1 is a flow chart showing a method for preparing a nitrogen-doped graphene using a furfuran derivative as a nitrogen source according to an embodiment of the present invention;
图2是本发明实施例提供的一种呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法的实物流程示意图；2 is a schematic diagram showing the physical flow of a method for preparing nitrogen-doped graphene using a furfuran derivative as a nitrogen source according to an embodiment of the present invention;
图3是本发明实施例1制备得到的氮掺杂石墨烯的扫描电镜测试图；3 is a scanning electron microscope test chart of nitrogen-doped graphene prepared in Example 1 of the present invention;
图4是本发明实施例1制备得到的氮掺杂石墨烯的X射线光电子能谱测试图；4 is a X-ray photoelectron spectroscopy test chart of nitrogen-doped graphene prepared in Example 1 of the present invention;
图5是本发明实施例1制备得到的氮掺杂石墨烯的N1s X射线光电子能谱测试图；5 is a N1s X-ray photoelectron spectroscopy test chart of the nitrogen-doped graphene prepared in Example 1 of the present invention;
图6是本发明实施例1制备得到的氮掺杂石墨烯的C1s的X射线光电子能谱测试图。Fig. 6 is a X-ray photoelectron spectroscopy test chart of C1s of nitrogen-doped graphene prepared in Example 1 of the present invention.
为使得本发明的发明目的、特征、优点能够更加的明显和易懂，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而非全部实施例。基于本发明中的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the drawings in the embodiments of the present invention. The embodiments are merely a part of the embodiments of the invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
请参照图1，图1为本发明实施例提供一种呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法流程图，该方法包括：Please refer to FIG. 1. FIG. 1 is a flow chart of a method for preparing nitrogen-doped graphene as a nitrogen source according to an embodiment of the present invention, the method comprising:
步骤101：将石墨烯分散于水中，得到石墨烯水溶液。其中，所述石墨烯的层数为1~3层。Step 101: Dispersing graphene in water to obtain an aqueous graphene solution. Wherein, the number of layers of the graphene is 1-3 layers.
步骤102：将呋咱类衍生物加入所述石墨烯水溶液，在50~70℃下加热并搅拌30~60min，降温至20~40℃，恒温干燥，得到石墨烯包覆的呋咱类衍生物共晶物。Step 102: adding a furfural derivative to the aqueous graphene solution, heating and stirring at 50 to 70 ° C for 30 to 60 minutes, cooling to 20 to 40 ° C, and drying at a constant temperature to obtain a graphene-coated furazan derivative. Eutectic.
其中，石墨烯与呋咱类衍生物的质量比为1:6~10；且呋咱类衍生物为二氨基呋咱(DAF)、二氨基氧化偶氮呋咱(DAAzF)和3-氨基-4-硝基呋咱(ANF)等中的至少一种。呋咱类衍生物含氮量为43~58 wt%，例如，DAF即为含氮量为56%的氮杂环化合物。Wherein, the mass ratio of graphene to furazan derivative is 1:6-10; and the furazan derivative is diaminofurazan (DAF), diamino azofuran (DAAzF) and 3-amino- At least one of 4-nitrofurazan (ANF) and the like. The furfuran derivative has a nitrogen content of 43 to 58 wt%. For example, DAF is a nitrogen heterocyclic compound having a nitrogen content of 56%.
步骤103：将石墨烯包覆的呋咱类衍生物共晶物研磨成粉末，并加热至500~800℃，恒温3~5h，得到氮掺杂石墨烯。Step 103: Grinding the graphene-coated furazan derivative eutectic into a powder, heating to 500-800 ° C, and maintaining the temperature for 3-5 h to obtain nitrogen-doped graphene.
本发明提供的呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法，利用呋咱类衍生物与石墨烯进行反应，得到氮掺杂含量较高的石墨烯材料。该材料中石墨烯均匀包覆在呋咱类衍生物晶体的表面，完整的保持了呋咱类衍生物晶体的表面性能，因此不需要使用胶黏剂等助剂，最终得到的氮掺杂石墨烯材料容易与其它材料复合，大大地拓展了石墨烯的应用范围。进一步地，利用该方法制备的氮掺杂石墨烯材料打开了能带隙，调整了导电类型，改变了电子结构；提高了自由载流子密度，提高了导电性能和稳定性；引入含氮的官能团，增加了表面吸附金属粒子的活性位，增强了金属粒子与石墨烯的相互作用，从而扩大了石墨烯的应用。The method for preparing nitrogen-doped graphene as a nitrogen source provided by the present invention uses a furazan derivative to react with graphene to obtain a graphene material having a high nitrogen doping content. The graphene is uniformly coated on the surface of the furazan derivative crystal, and the surface properties of the furazan derivative crystal are completely maintained, so that no additives such as an adhesive are needed, and the finally obtained nitrogen-doped graphite The olefinic material is easily compounded with other materials, greatly expanding the application range of graphene. Further, the nitrogen-doped graphene material prepared by the method opens the band gap, adjusts the conductivity type, changes the electronic structure, improves the free carrier density, improves the conductivity and stability, and introduces the nitrogen-containing The functional group increases the active site of the surface-adsorbed metal particles and enhances the interaction between the metal particles and the graphene, thereby expanding the application of graphene.
步骤S101中：将石墨烯加入到去离子水中，搅拌30~90min，超声抖动30~60min，其中，所述石墨烯与所述去离子水的质量比为1:20~30，石墨烯水溶液的浓度为1~5mg/mL，石墨烯的层数为1~3层，优选为单层，且片径为0.2~100 μm。具体地，将石墨烯放入装有离子水的烧杯中，并在预设转速下对石墨烯及离子水进行磁力搅拌，磁力搅拌后，将烧杯放入超声分散仪中，利用超声分散仪对磁力搅拌后的溶液进行超声抖动处理，得到石墨烯水溶液（氧化石墨烯水溶液）。其中，根据转速的不同可磁力搅拌30~90min，进行超声抖动处理的时间为30~60min。 In step S101, the graphene is added to the deionized water, stirred for 30 to 90 minutes, and ultrasonically shaken for 30 to 60 minutes, wherein the mass ratio of the graphene to the deionized water is 1:20 to 30, and the graphene aqueous solution is The concentration is 1 to 5 mg/mL, and the number of layers of graphene is 1 to 3 layers, preferably a single layer, and the chip diameter is 0.2 to 100 μm. Specifically, the graphene is placed in a beaker containing ionized water, and the graphene and the ionized water are magnetically stirred at a preset rotation speed. After magnetic stirring, the beaker is placed in an ultrasonic disperser, and the ultrasonic disperser is used. The magnetically stirred solution was subjected to ultrasonic shaking treatment to obtain an aqueous graphene solution (aqueous solution of graphene oxide). Among them, the magnetic stirring can be carried out for 30~90min according to the different rotation speed, and the ultrasonic shaking treatment time is 30~60min.
步骤S102中：将呋咱类衍生物加入装有石墨烯水溶液的烧杯中，然后将烧杯置于带有搅拌的加热台上，加热（加热温度为50~70℃）并搅拌反应 30~60 min，得到分散液；待分散液降温至20~40℃，则将装有该分散液的烧杯放入超声分散仪中，并在超声分散仪的上方放置加热装置，利用超声分散仪对分散液进行超声抖动处理，并利用加热装置对分散液进行恒温干燥处理（或利用恒温干燥箱对分散液进行恒温干燥处理），最终得到石墨烯包覆的呋咱类衍生物共晶物。其中，恒温干燥处理时间为48h，优选的恒温温度为25℃，且石墨烯水溶液中的石墨烯与呋咱类衍生物的质量比为1:1~10，优选为1:6~10，更优选为1:8。In step S102, the furfural derivative is added to a beaker containing an aqueous solution of graphene, and then the beaker is placed on a heating table with stirring, heated (heating temperature is 50-70 ° C) and stirred for 30-60 min. , to obtain a dispersion; when the dispersion is cooled to 20 to 40 ° C, the beaker containing the dispersion is placed in an ultrasonic disperser, and a heating device is placed above the ultrasonic disperser, and the dispersion is performed by an ultrasonic disperser. The ultrasonic vibration treatment is performed, and the dispersion liquid is subjected to constant temperature drying treatment by using a heating device (or the constant temperature drying treatment is performed on the dispersion liquid by a constant temperature drying oven) to finally obtain a graphene-coated furazan derivative eutectic. Wherein, the constant temperature drying treatment time is 48 h, the preferred constant temperature is 25 ° C, and the mass ratio of graphene to furfural derivative in the graphene aqueous solution is 1:1 to 10, preferably 1:6 to 10, more It is preferably 1:8.
步骤103中：优选地，石墨烯包覆的呋咱类衍生物共晶物的加热温度为500~700℃，优选为600℃，加热时间为3~6h ，优选为4h，得到含氮量为5.16%的氮掺杂石墨烯。In step 103, preferably, the heating temperature of the graphene-coated furazan derivative eutectic is 500-700 ° C, preferably 600 ° C, and the heating time is 3-6 h, preferably 4 h, and the nitrogen content is obtained. 5.16% nitrogen-doped graphene.
实施例1Example 1
如图2所示，将0.1 g片径为0.2μm的石墨烯加入25 ml去离子水中，在600 r/min转速下磁力搅拌60 分钟，然后置于超声分散仪中，超声抖动60 分钟，得到4 mg/ml的石墨烯溶液。As shown in Fig. 2, 0.1 g of graphene with a diameter of 0.2 μm was added to 25 ml of deionized water, magnetically stirred at 600 r/min for 60 minutes, then placed in an ultrasonic disperser, and ultrasonically shaken for 60 minutes. 4 mg/ml graphene solution.
将0.8 g DAF加入上述25ml的石墨烯溶液，在50℃下加热30 min至DAF完全溶解，降温至25℃，将混合溶液置于恒温干燥箱中干燥48h，得到石墨烯包覆的DAF共晶物。0.8 g of DAF was added to the above 25 ml graphene solution, heated at 50 ° C for 30 min until DAF was completely dissolved, and the temperature was lowered to 25 ° C. The mixed solution was dried in a constant temperature oven for 48 h to obtain graphene-coated DAF eutectic. Things.
将DAF共晶物研磨成粉末，置于管式炉中加热至600℃，保温4h，得到含氮量为5.16%的氮掺杂石墨烯。The DAF eutectic was ground into a powder, heated in a tube furnace to 600 ° C, and kept for 4 h to obtain nitrogen-doped graphene having a nitrogen content of 5.16%.
如图3所示，为DAF作为氮源制备得到的氮掺杂石墨烯的扫描电镜示意图。由图3可知实验得到的氮掺杂石墨烯中，石墨烯均匀包覆在DAF晶体的表面，不需要使用胶黏剂等助剂，完整的保持了DAF晶体的表面性能。As shown in FIG. 3, a scanning electron microscope schematic of nitrogen-doped graphene prepared by using DAF as a nitrogen source is shown. It can be seen from Fig. 3 that among the nitrogen-doped graphene obtained by the experiment, graphene is uniformly coated on the surface of the DAF crystal, and the surface properties of the DAF crystal are completely maintained without using an auxiliary agent such as an adhesive.
如图4所示，为DAF作为氮源制备得到的氮掺杂石墨烯的X射线光电子能谱测试图，对比纯的石墨烯可以看出，结合能在398-403 eV出现一尖峰，说明将DAF做为氮源能够有效的将DAF与石墨烯结合，得到氮掺杂石墨烯，可以说明，DAF作为氮源制备氮掺杂石墨烯是可行的。As shown in Fig. 4, X-ray photoelectron spectroscopy test chart of nitrogen-doped graphene prepared by using DAF as a nitrogen source, compared with pure graphene, it can be seen that the binding energy shows a sharp peak at 398-403 eV, indicating that DAF as a nitrogen source can effectively combine DAF with graphene to obtain nitrogen-doped graphene. It can be explained that DAF is a nitrogen source for preparing nitrogen-doped graphene.
如图5所示，为DAF作为氮源制备得到的氮掺杂石墨烯的N1s XPS示意图。现代研究表明，石墨烯掺氮（N）在拓展石墨烯的应用领域方面起着关键作用。氮原子掺杂到石墨烯之后，在碳原子的晶格中通常形成三种键合类型：吡啶氮( pyridinic N) 、吡咯氮( pyrrolic N) 和石墨氮( graphitic N)。石墨烯掺氮具备以下优点：(1) 打开了能带隙并调整导电类型，改变其电子结构；(2) 提高自由载流子密度，从而提高其导电性能和稳定性；(3) 引入含氮官能团，可以增加其表面吸附金属粒子的活性位，从而增强金属粒子与石墨烯的相互作用。因此，NG被广泛应用于锂离子电池、锂空电池和超级电容器电极材料以及燃料电池氧化还原催化剂等领域。而参见图5中可以看出，在398.4、400.1、401.2和402.8 eV分别出现了吡啶型N、吡咯型N、石墨型N以及吡啶N氧化物，因此，说明将DAF作为氮源制备氮掺杂石墨烯是可行的。As shown in FIG. 5, a schematic diagram of N1s XPS of nitrogen-doped graphene prepared by using DAF as a nitrogen source is shown. Modern research shows that graphene nitrogen (N) plays a key role in expanding the application of graphene. After nitrogen atoms are doped into graphene, three types of bonding are usually formed in the crystal lattice of carbon atoms: pyridin N, pyrrolic N, and graphitic N. Graphene nitrogen doping has the following advantages: (1) opening the band gap and adjusting the conductivity type, changing its electronic structure; (2) increasing the free carrier density, thereby improving its conductivity and stability; (3) introducing The nitrogen functional group can increase the active site of the metal particles adsorbed on the surface thereof, thereby enhancing the interaction between the metal particles and the graphene. Therefore, NG is widely used in the fields of lithium ion batteries, lithium air batteries and supercapacitor electrode materials, and fuel cell redox catalysts. As can be seen from Fig. 5, pyridine type N, pyrrole type N, graphite type N and pyridine N oxide were respectively observed at 398.4, 404.1, 401.2 and 402.8 eV, and therefore, the preparation of nitrogen doping by using DAF as a nitrogen source was demonstrated. Graphene is feasible.
如图6所示，为DAF作为氮源制备得到的氮掺杂石墨烯的C1s的X射线光电子能谱测试图。在284.4、285.2、286.4和289.2 eV分别出现了C–C、C–N、C–O以及C=O(C=N)键，说明DAF作为氮源制备氮掺杂石墨烯对石墨烯的结构产生作用。As shown in FIG. 6, an X-ray photoelectron spectroscopy test chart of C1s of nitrogen-doped graphene prepared by using DAF as a nitrogen source is shown. The C–C, C–N, C–O, and C=O(C=N) bonds appear at 284.4, 285.2, 286.4, and 289.2 eV, respectively, indicating that DAF is used as a nitrogen source to prepare nitrogen-doped graphene to graphene structure. Have an effect.
实施例２Example 2
如图2所示，将0.1 g片径为0.5μm的石墨烯加入25 ml去离子水中，在600 r/min转速下磁力搅拌70 分钟，然后置于超声分散仪中，超声抖动40 分钟，得到4 mg/ml的石墨烯溶液。As shown in Fig. 2, 0.1 g of graphene with a diameter of 0.5 μm was added to 25 ml of deionized water, magnetically stirred at 600 r/min for 70 minutes, then placed in an ultrasonic disperser, and ultrasonically shaken for 40 minutes. 4 mg/ml graphene solution.
将1.0 g DAAzF加入上述30ml的石墨烯溶液，在50℃下加热30 min至DAAzF完全溶解，降温至25℃，将混合溶液置于恒温干燥箱中干燥48h，得到石墨烯包覆的DAAzF共晶物。Add 1.0 g of DAAzF to the above 30 ml graphene solution, heat at 50 ° C for 30 min until DAAzF is completely dissolved, and cool to 25 ° C. The mixed solution is dried in a constant temperature oven for 48 h to obtain graphene-coated DAAzF eutectic. Things.
将DAAzF共晶物研磨成粉末，置于管式炉中加热至700℃，保温5h，得到含氮量为6.12%的氮掺杂石墨烯。The DAAzF eutectic was ground into a powder, heated in a tube furnace to 700 ° C, and kept for 5 h to obtain nitrogen-doped graphene having a nitrogen content of 6.12%.
经若干次实验得出，将DAAzF作为氮源制备氮掺杂石墨烯是可行的。It has been found in several experiments that it is feasible to prepare nitrogen-doped graphene using DAAzF as a nitrogen source.
实施例3Example 3
如图2所示，将0.1 g片径为1.0μm的石墨烯加入25 ml去离子水中，在600 r/min转速下磁力搅拌50 分钟，然后置于超声分散仪中，超声抖动40 分钟，得到4 mg/ml的石墨烯溶液。As shown in Fig. 2, 0.1 g of graphene with a diameter of 1.0 μm was added to 25 ml of deionized water, magnetically stirred at 600 r/min for 50 minutes, then placed in an ultrasonic disperser, and ultrasonically shaken for 40 minutes. 4 mg/ml graphene solution.
将1.0 g ANF加入上述30ml的石墨烯溶液，在50℃下加热30 min至ANF完全溶解，降温至25℃，将混合溶液置于恒温干燥箱中干燥48h，得到石墨烯包覆的ANF共晶物。Add 1.0 g of ANF to the above 30 ml graphene solution, heat at 50 ° C for 30 min until ANF is completely dissolved, and cool to 25 ° C. The mixed solution is dried in a constant temperature oven for 48 h to obtain graphene-coated ANF eutectic. Things.
将ANF共晶物研磨成粉末，置于管式炉中加热至800℃，保温5h，得到含氮量为7.15%的氮掺杂石墨烯。The ANF eutectic was ground into a powder, heated in a tube furnace to 800 ° C, and kept for 5 h to obtain nitrogen-doped graphene having a nitrogen content of 7.15%.
经若干次实验得出，将ANF作为氮源制备氮掺杂石墨烯是可行的。It has been found through several experiments that it is feasible to prepare nitrogen-doped graphene using ANF as a nitrogen source.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.
Claims (8)
- 一种呋咱类衍生物作为氮源的氮掺杂石墨烯的制备方法，其特征在于，所述方法包括：
将石墨烯分散于水中，得到石墨烯水溶液；其中，所述石墨烯的层数为1~3层；
将呋咱类衍生物加入所述石墨烯水溶液，在50~70℃下加热并搅拌30~60min，降温至20~40℃，恒温干燥，得到石墨烯包覆的呋咱类衍生物共晶物；其中，所述石墨烯与呋咱类衍生物的质量比为1:6~10，且呋咱类衍生物为二氨基呋咱、二氨基氧化偶氮呋咱和3-氨基-4-硝基呋咱中的至少一种；
将石墨烯包覆的呋咱类衍生物共晶物研磨成粉末，并加热至500~800℃，恒温3~5h，得到氮掺杂石墨烯。A method for preparing nitrogen-doped graphene as a nitrogen source, wherein the method comprises:
Dispersing graphene in water to obtain an aqueous graphene solution; wherein the number of layers of the graphene is 1-3 layers;
Adding a furfural derivative to the graphene aqueous solution, heating and stirring at 50 to 70 ° C for 30 to 60 minutes, cooling to 20 to 40 ° C, and drying at a constant temperature to obtain a graphene-coated furazan derivative eutectic Wherein the mass ratio of the graphene to the furazan derivative is 1:6-10, and the furazan derivative is diaminofurazan, diamino azofuran and 3-amino-4-nitrogen At least one of kiurofurans;
The graphene-coated furazan derivative eutectic is ground into a powder and heated to 500-800 ° C for 3 to 5 hours to obtain nitrogen-doped graphene. - 根据权利要求1所述的方法，其特征在于，所述石墨烯的层数为单层，且片径为0.2~100 μm。The method according to claim 1, wherein the number of layers of the graphene is a single layer and the sheet diameter is 0.2 to 100 μm.
- 根据权利要求1所述的方法，其特征在于，所述石墨烯与所述呋咱类衍生物的质量比为1:6~10。The method according to claim 1, wherein the mass ratio of the graphene to the furazan derivative is 1:6-10.
- 根据权利要求1所述的方法，其特征在于，所述呋咱类衍生物含氮量为43~58 wt%。The method according to claim 1, wherein the furfuran derivative has a nitrogen content of 43 to 58 wt%.
- 根据权利要求1所述的方法，其特征在于，所述将石墨烯分散于水中，得到石墨烯水溶液具体包括：
将所述石墨烯加入到去离子水中，搅拌30~90min，超声抖动30~60min，其中，所述石墨烯与所述去离子水的质量比为1:20~30。The method according to claim 1, wherein the dispersing the graphene in water to obtain the graphene aqueous solution specifically comprises:
The graphene is added to deionized water, stirred for 30 to 90 minutes, and ultrasonically shaken for 30 to 60 minutes, wherein the mass ratio of the graphene to the deionized water is 1:20 to 30. - 根据权利要求1所述的方法，其特征在于，所述石墨烯水溶液的浓度为1~5mg/mL。The method according to claim 1, wherein the concentration of the graphene aqueous solution is 1 to 5 mg/mL.
- 根据权利要求1所述的方法，其特征在于，所述恒温干燥时间为24~48h。The method of claim 1 wherein said constant temperature drying time is between 24 and 48 hours.
- 根据权利要求1所述的方法，其特征在于，所述石墨烯包覆的呋咱类衍生物共晶物的加热温度为500~700℃，加热时间为3~6h。The method according to claim 1, wherein the graphene-coated furazan derivative eutectic has a heating temperature of 500 to 700 ° C and a heating time of 3 to 6 hours.
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| WO2022062836A1 (en) * | 2020-09-27 | 2022-03-31 | 东莞理工学院 | Pyrrolic nitrogen-dominated nitrogen-doped graphene synthesis method and pyrrolic nitrogen-dominated nitrogen-doped graphene prepared by method |
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