技术领域technical field
本发明涉及一种利用天然多孔及层状结构蔬菜制备多原子自掺杂石墨烯的方法，属于石墨烯材料制备领域。The invention relates to a method for preparing polyatomic self-doping graphene by using natural porous and layered vegetables, and belongs to the field of graphene material preparation.
背景技术Background technique
石墨烯(G)是平面单层碳原子紧密结合在一起形成的二维(2D)晶格材料，被认为是构建所有其他维数石墨材料(包裹成富勒烯、卷制成碳纳米管和堆集成石墨)的基本单元。石墨烯的厚度仅为0.35nm左右,是世界上最薄的二维材料。稳定正六边形晶格结构赋予石墨烯许多独特的性能，如拉伸强度高达130Gpa，是已知材料中最高的；载流子迁移率高达15000～25000cm2/Vs(超过商用硅片10倍)；热导率达5000W/mK是金刚石的3倍，还具有室温量子霍尔效应及室温铁磁性等特殊性质。此外，电子穿过石墨烯几乎没有任何阻力，产生的热量少，导电效率高，是目前已知导电性能最优异的材料。Graphene (G) is a two-dimensional (2D) lattice material formed by a flat single layer of carbon atoms tightly bound together, and is considered to be the building block for all other dimensional graphitic materials (wrapped into fullerenes, rolled into carbon nanotubes and stacks). The basic unit of integrated graphite). The thickness of graphene is only about 0.35nm, which is the thinnest two-dimensional material in the world. The stable regular hexagonal lattice structure endows graphene with many unique properties, such as tensile strength up to 130Gpa, which is the highest among known materials; carrier mobility as high as 15000-25000cm2 /Vs (10 times higher than commercial silicon wafers) ; Thermal conductivity of 5000W/mK is three times that of diamond, and it also has special properties such as room temperature quantum Hall effect and room temperature ferromagnetism. In addition, there is almost no resistance for electrons to pass through graphene, which generates less heat and has high conductivity. It is currently the most excellent conductive material known.
目前制备石墨烯的方法可分为物理方法(微机械剥离法、液相或气相直接剥离法)与化学方法(化学气相沉积法、晶体外延生长法和氧化-还原法)。微机械剥离法是Geim等[Science,2004,306(5696):666-669]最早报道的制备石墨烯的方法。这种方法费时费力且难以精确控制，重复性差，难以大规模制备。液相或气相直接剥离法，如Coleman等参照液相剥离碳纳米管的方式将石墨分散在N-甲基-吡咯烷酮中[Nat.Nanotechnol,2008,3(9):563-568]，可制得石墨烯。然而该法制备石墨烯产率较低，仅为百分之几，大大限制其商业推广。化学气相沉积法(CVD)是现阶段制备质量高、大面积石墨烯的一种有效方法，如Kim等在硅衬底上添加一层非常薄的镍[Nature,2009,457(7230):706-710]，在甲烷、氢气与氩气气流中煅烧，在镍层上沉积出较大块6～10层石墨烯。这种方法制备成本高、难以精确控制加工条件，制约了其发展。晶体外延生长法，如Sutter等通过加热单晶6H-SiC脱除Si[Nat.Mater,2008,7(5):406-411]，从而得到在SiC表面外延的石墨烯。此法受衬底的影响很大，合成条件苛刻，石墨烯不易从衬底上分离，难以大量制造石墨烯。氧化还原法是目前最常用的制备石墨烯的方法，如P氩k等用水合肼还原剂[C氩bon,2011,49(9):3019-3023]，成功还原石墨烯。但此法常采用的还原剂具有毒性，使得制备过程存在危险和不稳定性，且这种还原制备出的石墨烯都会存在一个团聚过程，造成石墨烯比表面积偏小，通常低于900m2/g。因此，急需发明一种安全高效、低成本、环保友好的制备石墨烯的途径。The current methods for preparing graphene can be divided into physical methods (micromechanical exfoliation method, liquid phase or gas phase direct exfoliation method) and chemical methods (chemical vapor deposition method, crystal epitaxial growth method and oxidation-reduction method). The micromechanical exfoliation method is the earliest method for preparing graphene reported by Geim et al. [Science, 2004, 306(5696): 666-669]. This method is time-consuming, laborious, difficult to precisely control, poor in repeatability, and difficult to prepare on a large scale. Liquid phase or gas phase direct stripping method, such as Coleman etc. refer to the mode of liquid phase stripping carbon nanotubes to disperse graphite in N-methyl-pyrrolidone [Nat.Nanotechnol, 2008,3 (9): 563-568], can produce Get graphene. However, the yield of graphene prepared by this method is low, only a few percent, which greatly limits its commercial promotion. Chemical vapor deposition (CVD) is an effective method for preparing high-quality, large-area graphene at this stage. For example, Kim et al. add a very thin layer of nickel on the silicon substrate [Nature, 2009, 457(7230): 706 -710], calcined in methane, hydrogen and argon gas flow, deposited larger pieces of 6-10 layers of graphene on the nickel layer. This method is expensive to prepare and difficult to precisely control the processing conditions, which restricts its development. Crystal epitaxial growth method, such as Sutter et al., removes Si by heating single crystal 6H-SiC [Nat. Mater, 2008, 7(5):406-411], thereby obtaining graphene epitaxial on the SiC surface. This method is greatly affected by the substrate, the synthesis conditions are harsh, graphene is not easy to separate from the substrate, and it is difficult to produce graphene in large quantities. Oxidation-reduction method is currently the most commonly used method for preparing graphene. For example, P argon k etc. can successfully reduce graphene with hydrazine hydrate reducing agent [C argon bon, 2011,49(9):3019-3023]. However, the reducing agent commonly used in this method is toxic, which makes the preparation process dangerous and unstable, and the graphene produced by this reduction will have an agglomeration process, resulting in a relatively small specific surface area of graphene, usually lower than 900m2 / g. Therefore, it is urgent to invent a safe, efficient, low-cost, and environmentally friendly way to prepare graphene.
生物质材料具有可持续、环保再生、来源丰富的诸多优点，在农业、医药、化学等诸多领域有广泛用。作为餐座上的蔬菜，含有丰富的氨基酸和矿物质在给人类提供营养和能量上发挥着巨大价值，其具有的特殊结构(具有多孔及其层状结构)往往被忽视。蔬菜在工业上的应用却非常少，因此其在工业上的应用仍需深入探究。Biomass materials have many advantages such as sustainability, environmental protection and regeneration, and abundant sources, and are widely used in many fields such as agriculture, medicine, and chemistry. As a vegetable on the dining table, it is rich in amino acids and minerals and plays a huge role in providing nutrition and energy to human beings. Its special structure (porous and layered structure) is often overlooked. There are very few industrial applications of vegetables, so their industrial applications still need to be further explored.
发明内容Contents of the invention
本发明的目的在于针对现有制备石墨烯技术的不足和缺点，提供一种简单的利用天然多孔及层状结构蔬菜制备多原子自掺杂石墨烯的方法。The purpose of the present invention is to provide a simple method for preparing polyatomic self-doped graphene by using natural porous and layered vegetables for the deficiencies and shortcomings of the existing graphene preparation technology.
为实现上述发明目的，本发明采用的技术方案为：For realizing above-mentioned purpose of the invention, the technical scheme that the present invention adopts is:
本发明所述利用天然多孔及层状结构蔬菜制备多原子自掺杂石墨烯的方法，将蔬菜处理后浸泡于KOH溶液中，经过冷冻干燥、升温活化处理后，然后酸洗烘干而得，步骤如下：The method for preparing polyatomic self-doped graphene by using natural porous and layered vegetables according to the present invention is obtained by soaking the vegetables in KOH solution, freeze-drying, heating and activating, and then pickling and drying. Proceed as follows:
1)将新鲜的蔬菜用水洗净，简单处理后，切块，置于配置好的KOH溶液中，浸泡；1) Wash the fresh vegetables with water, after simple treatment, cut into pieces, place them in the prepared KOH solution, and soak;
2)将步骤1)中所得材料取出，真空冷冻干燥得到干燥多孔蓬松块状结构材料；2) taking out the material obtained in step 1), and vacuum freeze-drying to obtain a dry porous fluffy massive structure material;
3)将步骤2)中所得干燥多孔蓬松块状结构材料称置于管式炉中，在惰性气体保护气氛下升温活化，冷却降温；3) Place the dry porous fluffy block structure material obtained in step 2) in a tube furnace, heat up and activate under an inert gas protective atmosphere, and cool down;
4)所得产物磨碎后，酸洗并进行抽滤，用水洗至中性；4) After the obtained product is ground, pickle and carry out suction filtration, and wash with water until neutral;
5)将步骤4)所得样品置于真空烘干，即得多原子自掺杂石墨烯。5) The sample obtained in step 4) is placed in vacuum drying, that is, multi-atom self-doped graphene.
按上述方案，所述步骤1)简单处理为：果菜类蔬菜去皮处理，叶菜类蔬菜去叶处理。According to the above scheme, the simple treatment in step 1) is as follows: peeling the fruit vegetables and removing leaves from the leafy vegetables.
按上述方案，所述步骤1)KOH的浓度为0.3～1.0mol/L。According to the above scheme, the step 1) the concentration of KOH is 0.3-1.0 mol/L.
按上述方案，所述步骤1)浸泡时间为24～72h。According to the above scheme, the step 1) soaking time is 24-72h.
按上述方案，所述步骤2)中冷冻干燥是在-50～0℃、5～30Pa条件下进行，干燥时间为12～70h。According to the above scheme, the freeze-drying in the step 2) is carried out under the conditions of -50-0° C. and 5-30 Pa, and the drying time is 12-70 hours.
按上述方案，所述步骤3)中升温速率为5～10℃/min。According to the above scheme, the heating rate in the step 3) is 5-10° C./min.
按上述方案，所述步骤3)中活化温度600～900℃；活化时间为0.5～3h。According to the above scheme, the activation temperature in the step 3) is 600-900°C; the activation time is 0.5-3h.
按上述方案，所述步骤4)中的酸洗为置于酸溶液中60℃～100℃水浴酸洗6～18h。According to the above scheme, the pickling in step 4) is pickling in an acid solution in a water bath at 60° C. to 100° C. for 6 to 18 hours.
按上述方案，所述步骤4)中酸溶液为0.1～0.5mol/L的H2SO4或HCl溶液。According to the scheme above, the acid solution in step 4) is 0.1-0.5 mol/L H2 SO4 or HCl solution.
按上述方案，所述步骤5)中真空干燥温度为60～100℃。According to the above scheme, the vacuum drying temperature in step 5) is 60-100°C.
按上述方案，天然多孔及层状结构的蔬菜主要包括茄子、黄瓜、莴笋、芹菜、土豆、白萝卜、白菜、香瓜、莲藕、丝瓜、南瓜、瓠子、葫芦等。According to the above scheme, the vegetables with natural porous and layered structure mainly include eggplant, cucumber, lettuce, celery, potato, white radish, cabbage, muskmelon, lotus root, loofah, pumpkin, gourd, gourd and so on.
天然多孔及层状结构蔬菜等内部大量的纤维素和特殊的网状多孔及层状结构多被忽视，大大阻碍了其在工业上的应用。本文正是基于此，利用蔬菜材料内部丰富的纤维素和网状多孔及层状的特殊结构，任其自行吸附KOH溶液。另外，蔬菜材料同时可以充当碳源(C)，经过高温活化，其组成纤维素和微观网状及层状结构上的固体碳源中的碳原子易于分解重组，形成低于10层，特别是3～4层的少层石墨烯的特殊结构；又由于其内部丰富的氨基酸及矿物质等，可充当氮源(N)、磷源(P)等，可生成多原子自掺杂石墨烯。该工艺方法简单，成本低，无毒无害，利于大规模生产，对石墨烯推广和经济发展具有重要意义。The large amount of cellulose and the special net-like porous and layered structure in natural porous and layered vegetables have been neglected, which greatly hinders its industrial application. This article is based on this, using the rich cellulose and the special structure of the network porous and layered inside the vegetable material, allowing it to adsorb KOH solution by itself. In addition, the vegetable material can also act as a carbon source (C). After high-temperature activation, the carbon atoms in the cellulose and the solid carbon source on the microscopic network and layered structure are easy to decompose and recombine, forming less than 10 layers, especially The special structure of few-layer graphene with 3 to 4 layers; and because of the rich amino acids and minerals inside it, it can act as a nitrogen source (N), phosphorus source (P), etc., and can generate polyatomic self-doped graphene. The process method is simple, low in cost, non-toxic and harmless, beneficial to large-scale production, and has great significance for graphene popularization and economic development.
与背景技术相比，本发明具有以下优点：Compared with background technology, the present invention has the following advantages:
1)本发明选用生活中餐桌上的蔬菜为原料，材料来源丰富，廉价，可再生，符合可持续发展的要求。蔬菜中含有丰富的碳源，制成石墨烯后C含量可达80.0～95.0at.％，又由于蔬菜内含有丰富的氨基酸和矿物质，可在一定程度上形成多原子自掺杂多功能石墨烯，其中N含量为0.5～6.0at.％，P的含量为0.1～3.0at.％，N、P等多原子掺杂可以打开能带隙并调整导电类型，改变石墨烯的电子结构，有效提高石墨烯的自由载流子密度，从而提高石墨烯的导电性能(阻抗小于70Ω)和稳定性，同时增加石墨烯的边缘缺陷，暴露更多的活性位点，使得所制备的石墨烯具有较高活性，可用于燃料电池催化剂、锌空电池、锂空电池等领域。与普通方法制得的石墨烯相比，本发明制得的石墨烯有更广泛的应用；与传统制作多原子石墨烯方法相比，本发明采用一种廉价易得的蔬菜为原材料，大大降低成本，同时简化掺杂工艺，且导电性相比要好。1) The present invention selects the vegetables on the dining table in daily life as raw materials, and the material sources are abundant, cheap, renewable, and meet the requirements of sustainable development. Vegetables are rich in carbon sources, and the C content after making graphene can reach 80.0-95.0 at.%, and because vegetables are rich in amino acids and minerals, polyatomic self-doping multifunctional graphite can be formed to a certain extent Graphene, in which the N content is 0.5-6.0 at.%, and the P content is 0.1-3.0 at.%. N, P and other polyatomic doping can open the energy band gap and adjust the conductivity type, change the electronic structure of graphene, and effectively Improve the free carrier density of graphene, thereby improve the electrical conductivity (impedance is less than 70Ω) and stability of graphene, increase the edge defect of graphene at the same time, expose more active sites, make the prepared graphene have more High activity, can be used in fuel cell catalysts, zinc-air batteries, lithium-air batteries and other fields. Compared with the graphene obtained by ordinary methods, the graphene obtained by the present invention has a wider range of applications; compared with the traditional method of making polyatomic graphene, the present invention uses a cheap and easy-to-get vegetable as raw material, which greatly reduces the Cost, while simplifying the doping process, and better conductivity.
2)本发明通过对蔬菜去皮或者去叶处理，并浸泡在KOH溶液中，充分利用了其材料网状多孔及其层状结构易吸附的特点进而通过对其进行高温活化处理，利用其材料中所含有的纤维素和微观网状结构上的碳原子易于分解和重组，在这种高温活化的特殊环境中，自行形成石墨烯结构。与传统制备石墨烯方法相比，该方法制备石墨烯有三大工艺上的优点：一是利用材料天然多孔及层状结构易吸附的特点，自行吸附，进行混合，在混合工艺上大大简化；二是本发明制备石墨烯无需初步碳化工艺，一步高温活化即可制得石墨烯，大大降低生产成本；三是利用蔬菜自行充当碳源、氮源、磷源等，原材料无毒无害，使得制备过程更加安全可靠，充分符合大规模生产的基本要求，十分有利于石墨烯的商业化推广。2) The present invention makes full use of the characteristics of its material mesh porous and layered structure which is easy to adsorb by peeling or removing leaves of vegetables and soaking them in KOH solution, and then by performing high-temperature activation treatment on them, utilizing its material The carbon atoms contained in the cellulose and the microscopic network structure in the fiber are easy to decompose and recombine, and in this special environment of high temperature activation, the graphene structure is formed by itself. Compared with the traditional method of preparing graphene, this method has three advantages in the preparation of graphene: one is to use the characteristics of the material's natural porous and layered structure, which is easy to adsorb, to self-adsorb and mix, which greatly simplifies the mixing process; The preparation of graphene in the present invention does not require a preliminary carbonization process, and graphene can be obtained by one-step high-temperature activation, which greatly reduces production costs; the third is to use vegetables as carbon sources, nitrogen sources, phosphorus sources, etc., and the raw materials are non-toxic and harmless, making the preparation The process is safer and more reliable, fully meets the basic requirements of large-scale production, and is very conducive to the commercialization of graphene.
3)本发明所制备的石墨烯比表面积可达1000m2g-1以上，该值远高于众多用氧化还原法所制备的石墨烯。且制备得到的石墨烯层数较少，仅为3～4层，优于很多制备石墨烯的传统方法。高比表面积、低层数的石墨烯结构以及其多原子自掺杂，使其可广泛应用于导热材料、超级电容器、生物器件、海水淡化、电池催化剂及其正负极等诸多领域。3) The graphene prepared by the present invention has a specific surface area of more than 1000 m2 g-1 , which is much higher than many graphenes prepared by redox methods. And the number of prepared graphene layers is less, only 3 to 4 layers, which is better than many traditional methods for preparing graphene. The graphene structure with high specific surface area, low number of layers and its polyatomic self-doping make it widely used in many fields such as thermal conductive materials, supercapacitors, biological devices, seawater desalination, battery catalysts and their positive and negative electrodes.
附图说明Description of drawings
图1是实施例1茄子内部结构和由其制备的石墨烯的SEM图；其中：图1a是实施例1茄子内部结构SEM图；图1b是实施例1所制石墨烯的SEM图。Fig. 1 is the SEM figure of embodiment 1 eggplant internal structure and the graphene prepared therefrom; Wherein: Fig. 1 a is the SEM figure of embodiment 1 eggplant internal structure; Fig. 1 b is the SEM figure of the graphene produced in embodiment 1.
图2是实施例1所得石墨烯的TEM图。Fig. 2 is the TEM picture of the graphene obtained in embodiment 1.
图3是实施例1所得石墨烯的Raman图。Fig. 3 is the Raman figure of the graphene obtained in embodiment 1.
图4是实施例1所得石墨烯的BET图。Fig. 4 is the BET diagram of the graphene obtained in embodiment 1.
图5是实施例1所得石墨烯XPS图。Fig. 5 is the graphene XPS figure obtained in embodiment 1.
图6是实施例1所得石墨烯EIS图。Fig. 6 is the graphene EIS figure obtained in embodiment 1.
具体实施方式Detailed ways
下面通过具体实施例对本发明利用蔬菜制备多原子自掺杂石墨烯的方法作进一步说明。The method for preparing polyatomic self-doped graphene by using vegetables in the present invention will be further described below through specific examples.
实施例1Example 1
1)将新鲜的茄子用水洗净，去皮，切块，置于配置好的0.5M KOH溶液中，任其浸泡24h；1) Wash the fresh eggplant with water, peel it, cut it into pieces, place it in the prepared 0.5M KOH solution, and allow it to soak for 24 hours;
2)将步骤1)中所得材料取出置于冷冻干燥箱中-50℃、10Pa中冷冻干燥36h得到干燥多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -50°C and 10Pa for 36 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下升温以5℃每分钟升温至800℃保温1h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, raise the temperature at 5°C per minute to 800°C for 1 hour under an argon protective atmosphere, and then cool down;
4)将步骤3)所得产物手工磨碎后，置于250ml 0.5M H2SO4溶液中恒温水浴80℃酸洗9h，并进行抽滤，用水洗至中性；4) After manually grinding the product obtained in step 3), place it in 250 ml of 0.5M H2 SO4 solution, pickle it in a constant temperature water bath at 80°C for 9 hours, perform suction filtration, and wash it with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中80℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 80° C. to obtain graphene.
所制得石墨烯的比表面积可达1102m2g-1，其中N元素的含量为1.04at.％，P元素的含量为0.15at.％，阻抗为54Ω。The specific surface area of the prepared graphene can reach 1102m2 g-1 , the content of N element is 1.04at.%, the content of P element is 0.15at.%, and the impedance is 54Ω.
图1a为茄子的扫描电镜(SEM)图片，可以看到茄子本身含有利于吸附的网状多孔及层状结构，其中数字1和2所指为层状结构。Figure 1a is a scanning electron microscope (SEM) picture of eggplant. It can be seen that the eggplant itself contains a mesh-like porous and layered structure that is conducive to adsorption, and the numbers 1 and 2 refer to the layered structure.
图1b为所得石墨烯的扫描电镜(SEM)图片可以看到石墨烯透明褶皱状的典型的石墨烯结构。Figure 1b is a scanning electron microscope (SEM) picture of the obtained graphene, and the typical graphene structure of graphene transparent wrinkle can be seen.
图2为所得石墨烯的透射电镜(TEM)图片，可以看到石墨烯堆叠的片层结构和石墨烯晶格条纹。Figure 2 is a transmission electron microscope (TEM) picture of the obtained graphene, where the graphene stacked sheet structure and graphene lattice fringes can be seen.
图3为所得石墨烯的拉曼光谱(Raman)图，在2675cm-1处出现尖锐的石墨烯2D峰，表明有石墨烯结构的存在。Fig. 3 is the Raman spectrum (Raman) figure of obtained graphene, and sharp graphene 2D peak appears at 2675cm-1 place, shows the existence of graphene structure.
图4为所得石墨烯的氮气吸脱附等温曲线，由氮气吸脱附等温曲线得到此产物的比表面积(BET)为1102m2g-1。Fig. 4 is the nitrogen adsorption-desorption isotherm curve of the obtained graphene, and the specific surface area (BET) of the product obtained from the nitrogen adsorption-desorption isotherm curve is 1102 m2 g-1 .
图5为所得石墨烯的X射线光电子能谱(XPS)图，从图中可以看出该产物主要含有C、N、O、P四种元素，其中N元素的含量为1.04at.％，P元素的含量为0.22at.％。Fig. 5 is the X-ray photoelectron spectrum (XPS) figure of gained graphene, can find out from the figure that this product mainly contains four elements of C, N, O, P, wherein the content of N element is 1.04at.%, P The element content is 0.22 at.%.
图6为所得石墨烯的EIS(阻抗)图，从图中可以看出该石墨烯的阻抗较小，仅为54Ω。Fig. 6 is the EIS (impedance) figure of obtained graphene, it can be seen from the figure that the impedance of the graphene is small, only 54Ω.
实施例2Example 2
1)将新鲜的黄瓜用水洗净，去皮，切块，置于配置好的0.3M KOH溶液中，任其浸泡48h；1) Wash the fresh cucumber with water, peel it, cut it into pieces, place it in the prepared 0.3M KOH solution, and allow it to soak for 48 hours;
2)将步骤1)中所得材料取出置于冷冻干燥箱中-20℃、15Pa中冷冻干燥40h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -20°C and 15Pa for 40 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料，置于管式炉中，在氮气保护气氛下以7℃每分钟升温至700℃保温1.5h后，并冷却降温；3) Place the material obtained in step 2) in a tube furnace, raise the temperature from 7°C per minute to 700°C for 1.5 hours under a nitrogen protective atmosphere, and then cool down;
4)将步骤3)所得产物手工磨碎后，置于250ml 0.3M HCl溶液中恒温水浴80℃酸洗9h，并进行抽滤，用水洗至中性；4) After the product obtained in step 3) was manually ground, it was placed in 250 ml of 0.3M HCl solution and acid-washed at 80°C for 9 hours in a constant temperature water bath, then filtered with suction, and washed with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中60℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 60° C. to obtain graphene.
所制得石墨烯的比表面积可达1221m2g-1，其中N元素的含量为1.58at.％，P元素的含量为0.62at.％，阻抗为57Ω。The specific surface area of the prepared graphene can reach 1221m2 g-1 , the content of N element is 1.58at.%, the content of P element is 0.62at.%, and the impedance is 57Ω.
实施例3Example 3
1)将新鲜的莴笋用水洗净，去皮，切块，置于配置好的0.6M KOH溶液中，任其浸泡36h；1) Wash the fresh lettuce with water, peel it, cut it into pieces, place it in the prepared 0.6M KOH solution, and allow it to soak for 36 hours;
2)将步骤1)所得材料取出置于冷冻干燥箱中-10℃、10Pa中冷冻干燥65h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -10°C and 10Pa for 65 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下以6℃每分钟升温至700℃保温0.5h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, raise the temperature from 6°C per minute to 700°C for 0.5h under an argon protective atmosphere, and then cool down;
4)将步骤3)所得产物手工磨碎后，置于200ml 0.3M HCl溶液中恒温水浴70℃酸洗6h，并进行抽滤，用水洗至中性；4) After the product obtained in step 3) was manually ground, it was placed in 200ml of 0.3M HCl solution and acid-washed at 70°C for 6 hours in a constant-temperature water bath, then suction-filtered, and washed with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中70℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum drying oven at 70° C. to obtain graphene.
所制得石墨烯的比表面积可达1233m2g-1，其中N元素的含量为0.99at.％，P元素的含量为0.21at.％，阻抗为52Ω。The specific surface area of the prepared graphene can reach 1233m2 g-1 , the content of N element is 0.99at.%, the content of P element is 0.21at.%, and the impedance is 52Ω.
实施例4Example 4
1)将新鲜的芹菜用水洗净，去皮，切块，置于配置好的1M KOH溶液中，任其浸泡24h；1) Wash the fresh celery with water, peel it, cut it into pieces, put it in the prepared 1M KOH solution, and let it soak for 24 hours;
2)将步骤1)中所得材料取出置于冷冻干燥箱中-30℃、20Pa中冷冻干燥35h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -30°C and 20Pa for 35 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下以6℃每分钟升温至600℃保温1.5h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, heat it up to 600 °C at 6 °C per minute for 1.5 h under an argon protective atmosphere, and cool it down;
4)将步骤3)所得产物手工磨碎后，置于200ml 0.3M H2SO4溶液中恒温水浴60℃酸洗15h，并进行抽滤，用水洗至中性；4) After manually grinding the product obtained in step 3), place it in 200ml of 0.3MH2 SO4 solution, pickle it in a constant temperature water bath at 60°C for 15 hours, perform suction filtration, and wash it with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中90℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 90° C. to obtain graphene.
所制得石墨烯的比表面积可达1500m2g-1，其中N元素的含量为1.33at.％，P元素的含量为0.31at.％，阻抗为46Ω。The specific surface area of the prepared graphene can reach 1500m2 g-1 , the content of N element is 1.33at.%, the content of P element is 0.31at.%, and the impedance is 46Ω.
实施例5Example 5
1)将新鲜的土豆用水洗净，去皮，切块，置于配置好的0.7M KOH溶液中，任其浸泡24h；1) Wash the fresh potatoes with water, peel them, cut them into pieces, place them in the prepared 0.7M KOH solution, and allow them to soak for 24 hours;
2)将步骤1)中所得材料取出置于冷冻干燥箱中-20℃、15Pa中冷冻干燥40h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -20°C and 15Pa for 40 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下以6℃每分钟升温至700℃保温1.5h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, raise the temperature at 6°C per minute to 700°C for 1.5h under an argon protective atmosphere, and cool down;
4)将步骤3)所得产物手工磨碎后，置于200ml 0.5M H2SO4溶液中恒温水浴60℃酸洗15h，并进行抽滤，用水洗至中性；4) After the product obtained in step 3) was manually ground, it was placed in 200ml of 0.5MH2 SO4 solution and acid-washed at 60°C for 15 hours in a constant-temperature water bath, then filtered with suction, and washed with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中80℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 80° C. to obtain graphene.
所制得石墨烯的比表面积可达1139m2g-1，其中N元素的含量为5.2at.％，P元素的含量为1.03at.％，阻抗为42Ω。The specific surface area of the prepared graphene can reach 1139m2 g-1 , the content of N element is 5.2at.%, the content of P element is 1.03at.%, and the impedance is 42Ω.
实施例6Example 6
1)将新鲜的白萝卜用水洗净，去皮，切块，置于配置好的1M KOH溶液中，任其浸泡24h；1) Wash the fresh white radish with water, peel it, cut it into pieces, put it in the prepared 1M KOH solution, and let it soak for 24 hours;
2)将步骤1)中所得材料取出置于冷冻干燥箱中-30℃、20Pa中冷冻干燥35h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -30°C and 20Pa for 35 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下以6℃每分钟升温至600℃保温2h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, heat it up to 600° C. at 6° C. per minute under an argon protective atmosphere, keep it warm for 2 hours, and cool down;
4)将步骤3)所得产物手工磨碎后，置于200ml 0.4M HCl溶液中恒温水浴60℃酸洗18h，并进行抽滤，用水洗至中性；4) After the product obtained in step 3) was manually ground, it was placed in 200ml of 0.4M HCl solution and acid-washed at 60°C for 18 hours in a constant-temperature water bath, then filtered with suction, and washed with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中90℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 90° C. to obtain graphene.
所制得石墨烯的比表面积可达1148m2g-1，其中N元素的含量为2.4at.％，P元素的含量为0.55at.％，阻抗为57Ω。The specific surface area of the prepared graphene can reach 1148m2 g-1 , the content of N element is 2.4at.%, the content of P element is 0.55at.%, and the impedance is 57Ω.
实施例7Example 7
1)将新鲜的白菜用水洗净，去叶，切块，置于配置好的0.8M KOH溶液中，任其浸泡50h；1) Wash the fresh cabbage with water, remove the leaves, cut into pieces, put it in the prepared 0.8M KOH solution, and let it soak for 50 hours;
2)将步骤1)所得材料取出置于冷冻干燥箱中-10℃、8Pa中冷冻干燥45h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -10°C and 8Pa for 45 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氮气保护气氛下以10℃每分钟升温至600℃保温2h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, heat it up to 600° C. at 10° C. per minute for 2 hours under a nitrogen protective atmosphere, and cool it down;
4)将步骤3)所得产物手工磨碎后，置于250ml 0.4M HCl溶液中恒温水浴70℃酸洗6h，并进行抽滤，用水洗至中性；4) After the product obtained in step 3) was manually ground, it was placed in 250 ml of 0.4M HCl solution and acid-washed at 70°C for 6 hours in a constant-temperature water bath, then suction-filtered, and washed with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中70℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum drying oven at 70° C. to obtain graphene.
所制得石墨烯的比表面积可达1435m2g-1，其中N元素的含量为3.2at.％，P元素的含量为1.2at.％，阻抗为65Ω。The specific surface area of the prepared graphene can reach 1435m2 g-1 , the content of N element is 3.2at.%, the content of P element is 1.2at.%, and the impedance is 65Ω.
实施例8Example 8
1)将新鲜的香瓜用水洗净，去皮，切块，置于配置好的0.5M KOH溶液中，任其浸泡72h；1) Wash the fresh muskmelon with water, peel it, cut it into pieces, put it in the prepared 0.5M KOH solution, and let it soak for 72 hours;
2)将步骤1)所得材料取出置于冷冻干燥箱中-10℃、10Pa中冷冻干燥65h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -10°C and 10Pa for 65 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氮气保护气氛下以10℃每分钟升温至900℃保温0.5h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, heat it up to 900° C. at 10° C. per minute for 0.5 hours under a nitrogen protective atmosphere, and cool it down;
4)将步骤3)所得产物手工磨碎后，置于250ml 0.4M H2SO4溶液中恒温水浴70℃酸洗6h，并进行抽滤，用水洗至中性；4) After manually grinding the product obtained in step 3), place it in 250ml 0.4MH2 SO4 solution, pickle it in a constant temperature water bath at 70°C for 6 hours, perform suction filtration, and wash it with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中70℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum drying oven at 70° C. to obtain graphene.
所制得石墨烯的比表面积可达1198m2g-1，其中N元素的含量为3.5at.％，P元素的含量为1.6at.％，阻抗为50Ω。The specific surface area of the prepared graphene can reach 1198m2 g-1 , the content of N element is 3.5 at.%, the content of P element is 1.6 at.%, and the impedance is 50Ω.
实施例9Example 9
1)将新鲜的莲藕用水洗净，去皮，切块，置于配置好的0.8M KOH溶液中，任其浸泡36h；1) Wash the fresh lotus root with water, peel it, cut it into pieces, put it in the prepared 0.8M KOH solution, and let it soak for 36 hours;
2)将步骤1)所得材料取出置于冷冻干燥箱中-10℃、5Pa中冷冻干燥70h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -10°C and 5Pa for 70 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下以10℃每分钟升温至800℃保温1h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, heat it up to 800 °C at 10 °C per minute under an argon protective atmosphere, keep it for 1 h, and cool down;
4)将步骤3)所得产物手工磨碎后，置于200ml 0.2M HCl溶液中恒温水浴100℃酸洗8h，并进行抽滤，用水洗至中性；4) After the product obtained in step 3) was manually ground, it was placed in 200ml of 0.2M HCl solution and acid-washed at 100°C for 8 hours in a constant-temperature water bath, then suction-filtered, and washed with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中90℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 90° C. to obtain graphene.
所制得石墨烯的比表面积可达1326m2g-1，其中N元素的含量为3.6at.％，P元素的含量为1.4at.％，阻抗为61Ω。The specific surface area of the prepared graphene can reach 1326m2 g-1 , the content of N element is 3.6at.%, the content of P element is 1.4at.%, and the impedance is 61Ω.
实施例10Example 10
1)将新鲜的丝瓜用水洗净，去皮，切块，置于配置好的0.5M KOH溶液中，任其浸泡24h；1) Wash the fresh loofah with water, peel it, cut it into pieces, put it in the prepared 0.5M KOH solution, and let it soak for 24 hours;
2)将步骤1)所得材料取出置于冷冻干燥箱中-25℃、24Pa中冷冻干燥45h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -25°C and 24Pa for 45 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下以7℃每分钟升温至700℃保温2h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, heat it up to 700 °C at 7 °C per minute under an argon protective atmosphere, keep it for 2 hours, and cool down;
4)将步骤3)所得产物手工磨碎后，置于200ml 0.1M HCl溶液中恒温水浴80℃酸洗12h，并进行抽滤，用水洗至中性；4) After the product obtained in step 3) was manually ground, it was placed in 200ml of 0.1M HCl solution and acid-washed at 80°C for 12 hours in a constant-temperature water bath, then suction-filtered, and washed with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中80℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 80° C. to obtain graphene.
所制得石墨烯的比表面积可达1230m2g-1，其中N元素的含量为5.3at.％，P元素的含量为1.0at.％，阻抗为62Ω。The specific surface area of the prepared graphene can reach 1230m2 g-1 , the content of N element is 5.3 at.%, the content of P element is 1.0 at.%, and the impedance is 62Ω.
实施例11Example 11
1)将新鲜的南瓜用水洗净，去皮，切块，置于配置好的0.6M KOH溶液中，任其浸泡36h；1) Wash the fresh pumpkin with water, peel it, cut it into pieces, place it in the prepared 0.6M KOH solution, and let it soak for 36 hours;
2)将步骤1)所得材料取出置于冷冻干燥箱中-40℃、20Pa中冷冻干燥20h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -40°C and 20Pa for 20 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氮气保护气氛下以8℃每分钟升温至900℃保温0.5h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, heat it up to 900 °C at 8 °C per minute for 0.5 h under a nitrogen protective atmosphere, and cool it down;
4)将步骤3)所得产物手工磨碎后，置于150ml 0.3M H2SO4溶液中恒温水浴70℃酸洗14h，并进行抽滤，用水洗至中性；4) After manually grinding the product obtained in step 3), place it in 150ml of 0.3MH2 SO4 solution, pickle it in a constant temperature water bath at 70°C for 14 hours, perform suction filtration, and wash it with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中100℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 100° C. to obtain graphene.
所制得石墨烯的比表面积可达1409m2g-1，其中N元素的含量为4.8at.％，P元素的含量为0.18at.％，阻抗为36Ω。The specific surface area of the prepared graphene can reach 1409m2 g-1 , the content of N element is 4.8at.%, the content of P element is 0.18at.%, and the impedance is 36Ω.
实施例12Example 12
1)将新鲜的瓠子用水洗净，去皮，切块，置于配置好的0.2M KOH溶液中，任其浸泡72h；1) Wash the fresh gourd with water, peel it, cut it into pieces, put it in the prepared 0.2M KOH solution, and let it soak for 72 hours;
2)将步骤1)所得材料取出置于冷冻干燥箱中-30℃、25Pa中冷冻干燥35h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -30°C and 25Pa for 35 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下以6℃每分钟升温至800℃保温1h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, raise the temperature at 6°C per minute to 800°C for 1 hour under an argon protective atmosphere, and then cool down;
4)将步骤3)所得产物手工磨碎后，置于250ml 0.4M H2SO4溶液中恒温水浴90℃酸洗12h，并进行抽滤，用水洗至中性；4) After manually grinding the product obtained in step 3), place it in 250ml 0.4MH2 SO4 solution, pickle it in a constant temperature water bath at 90°C for 12 hours, perform suction filtration, and wash it with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中80℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 80° C. to obtain graphene.
所制得石墨烯的比表面积可达1285m2g-1，其中N元素的含量为2.3at.％，P元素的含量为0.15at.％，阻抗为51Ω。The specific surface area of the prepared graphene can reach 1285m2 g-1 , the content of N element is 2.3at.%, the content of P element is 0.15at.%, and the impedance is 51Ω.
实施例13Example 13
1)将新鲜的葫芦用水洗净，去皮，切块，置于配置好的0.3M KOH溶液中，任其浸泡60h；1) Wash the fresh gourd with water, peel it, cut it into pieces, place it in the prepared 0.3M KOH solution, and allow it to soak for 60 hours;
2)将步骤1)所得材料取出置于冷冻干燥箱中-50℃、10Pa中冷冻干燥48h得到干燥的多孔蓬松块状结构；2) The material obtained in step 1) is taken out and placed in a freeze-drying oven at -50°C and 10Pa for 48 hours to obtain a dry porous fluffy block structure;
3)将步骤2)中所得材料称取10g，置于管式炉中，在氩气保护气氛下以7℃每分钟升温至800℃保温1h后，并冷却降温；3) Weigh 10 g of the material obtained in step 2), place it in a tube furnace, raise the temperature from 7°C per minute to 800°C for 1 hour under an argon protective atmosphere, and then cool down;
4)将步骤3)所得产物手工磨碎后，置于200ml 0.5M H2SO4溶液中恒温水浴60℃酸洗10h，并进行抽滤，用水洗至中性；4) Grind the product obtained in step 3) manually, put it in 200ml0.5MH2SO4 solution, pickle it in a constant temperature water bath at 60°C for 10h, perform suction filtration, and wash it with water until neutral;
5)将步骤4)在所得样品置于真空干燥箱中60℃烘干，即得石墨烯。5) Dry the sample obtained in step 4) in a vacuum oven at 60° C. to obtain graphene.
所制得石墨烯的比表面积可达1373m2g-1，其中N元素的含量为3.9at.％，P元素的含量为0.45at.％，阻抗为49Ω。The specific surface area of the prepared graphene can reach 1373m2 g-1 , the content of N element is 3.9 at.%, the content of P element is 0.45 at.%, and the impedance is 49Ω.
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