CN105752969B - The method for preparing polyatom auto-dope graphene using natural porous and layer structure vegetables - Google Patents

The method for preparing polyatom auto-dope graphene using natural porous and layer structure vegetables Download PDF

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CN105752969B
CN105752969B CN201610113576.8A CN201610113576A CN105752969B CN 105752969 B CN105752969 B CN 105752969B CN 201610113576 A CN201610113576 A CN 201610113576A CN 105752969 B CN105752969 B CN 105752969B
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graphene
vegetables
polyatom
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layer structure
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CN105752969A (en
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木士春
周煌
张晨雨
张建
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Wuhan University of Technology WUT
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    • C01B2204/00—Structure or properties of graphene
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Abstract

It the present invention relates to the use of natural porous and the method that layer structure vegetables prepare polyatom auto-dope graphene.Step is as follows：It is soaked in KOH solution after vegetables are handled, after the activation process that is freeze-dried, heats up, then pickling is dried and obtained.It is raw material that the present invention, which selects vegetables, and material source enriches, inexpensively, renewable, meets the requirement of sustainable development.Contain abundant carbon source in vegetables, C content is up to 80.0~95.0at.% after graphene is made, again due to containing abundant amino acid and minerals in vegetables, polyatom auto-dope multifunctional graphite vinyl can be formed to a certain extent, wherein N content is 0.5~6.0at.%, the content of P is 0.1~3.0at.%, N, the doping of the polyatoms such as P can open band gap and adjust conduction type, change the electronic structure of graphene, effectively improve the free carrier density of graphene, so as to improve the electric conductivity of graphene and stability, increase the edge defect of graphene simultaneously, the more active sites of exposure, make prepared graphene that there is greater activity.

Description

Polyatom auto-dope graphene is prepared using natural porous and layer structure vegetables Method
Technical field
The present invention relates to a kind of method for preparing polyatom auto-dope graphene using natural porous and layer structure vegetables, Belong to grapheme material preparation field.
Background technology
Graphene (G) is that planar monolayer carbon atom is closely linked the two dimension to be formed (2D) lattice material, is considered It is the substantially single of the every other dimension graphite material of structure (be rolled into fullerene, roll into carbon nanotube and heap integrates graphite) Member.The thickness of graphene is only 0.35nm or so, is two-dimensional material most thin in the world.Stablize regular hexagon lattice structure to assign The many unique performances of graphene are highest in known materials if tensile strength is up to 130Gpa；Carrier mobility is up to 15000~25000cm2/ Vs (being more than commercial 10 times of silicon chip)；Thermal conductivity is up to 3 times that 5000W/mK is diamond, also with room temperature The special natures such as quantum hall effect and room-temperature ferromagnetic.In addition, electronics passes through graphene almost without any resistance, generation Heat is few, and electrical efficiency is high, is to be currently known the most excellent material of electric conductivity.
The method for preparing graphene at present can be divided into physical method (micromechanics stripping method, liquid phase or the direct stripping method of gas phase) With chemical method (chemical vapour deposition technique, crystal epitaxy method and oxidation-reduction method).Micromechanics stripping method is Geim etc. [Science,2004,306(5696):666-669] method for preparing graphene reported earliest.This method it is time-consuming and laborious and It is difficult to accurately control, poor repeatability, it is difficult to extensive to prepare.Liquid phase or the direct stripping method of gas phase, such as Coleman is with reference to liquid phase The mode of stripping carbon nanotube [Nat.Nanotechnol, 2008,3 (9) in N- methyl-pyrrolidons by graphite dispersion: 563-568], graphene can be made.However to prepare graphene yield relatively low for the method, only a few percent, limits its business significantly It promotes.Chemical vapour deposition technique (CVD) is to prepare that quality is high, a kind of effective ways of large-area graphene, such as Kim at this stage One layer of very thin nickel [Nature, 2009,457 (7230) are added on a silicon substrate:706-710], in methane, hydrogen and argon gas It is calcined in air-flow, relatively large 6~10 layer graphene is deposited on nickel layer.This method manufacturing cost is high, is difficult to accurately control Processing conditions constrains its development.Crystal epitaxy method, such as Sutter remove Si by heating monocrystalline 6H-SiC [Nat.Mater,2008,7(5):406-411], so as to obtain the graphene in surface of SiC extension.This method is influenced by substrate Very big, synthesis condition is harsh, and graphene is not easy to detach from substrate, it is difficult to largely manufacture graphene.Oxidation-reduction method is current The most common method for preparing graphene, such as P argons k hydrazine hydrate reduction agent [C argons bon, 2011,49 (9):3019-3023], Success reduced graphene.But this method frequently with reducing agent there is toxicity so that preparation process is dangerous and unstability, and This graphene prepared that restores all can cause graphene specific surface area less than normal, usually less than there are an aggregation procedure 900m2/g.Therefore, it is badly in need of inventing a kind of approach for preparing graphene of safe and efficient, inexpensive, environmentally friendly close friend.
Biological material have many advantages, such as it is sustainable, environmental friendly regenerated, abundance, it is all in agricultural, medicine, chemistry etc. It is multi-field to have extensive use.As the vegetables on meal seat, nutrition and energy are being provided to the mankind containing abundant amino acid and minerals Immense value is played in amount, with special construction it is often ignored (with porous and its layer structure).Vegetables are in work Application in industry is considerably less, therefore its application industrially still needs to deeply probe into.
Invention content
It is an object of the invention to be directed to the existing deficiency and shortcoming for preparing graphene technology, a kind of simple utilization is provided The method that natural porous and layer structure vegetables prepare polyatom auto-dope graphene.
For achieving the above object, the technical solution adopted by the present invention is：
The method of the present invention for preparing polyatom auto-dope graphene using natural porous and layer structure vegetables, by vegetable It is soaked in KOH solution after dish processing, after the activation process that is freeze-dried, heats up, then pickling is dried and obtained, and step is such as Under：
1) fresh vegetables are eluted with water, after simple process, stripping and slicing is placed in the KOH solution being configured, and is impregnated；
2) resulting materials in step 1) are taken out, vacuum freeze drying obtains dry porous fluffy block structure material；
3) the dry porous fluffy block structure material of gained in step 2) is claimed to be placed in tube furnace, in inert gas shielding Heat up activation under atmosphere, cools；
4) after products therefrom is ground, pickling is simultaneously filtered, and is washed with water to neutrality；
5) sample obtained by step 4) is placed in vacuum drying to get polyatom auto-dope graphene.
By said program, the step 1) simple process is：Fruit vegetables peeling is handled, at leaf vegetables defoliation Reason.
By said program, a concentration of 0.3~1.0mol/L of the step 1) KOH.
By said program, the step 1) soaking time is 24~72h.
By said program, freeze-drying is carried out under the conditions of -50~0 DEG C, 5~30Pa in the step 2), when dry Between be 12~70h.
By said program, heating rate is 5~10 DEG C/min in the step 3).
By said program, 600~900 DEG C of activation temperature in the step 3)；Soak time is 0.5~3h.
By said program, the pickling in the step 4) is is placed in 60 DEG C~100 DEG C 6~18h of water-bath pickling in acid solution.
By said program, acid solution is the H of 0.1~0.5mol/L in the step 4)2SO4Or HCl solution.
By said program, vacuum drying temperature is 60~100 DEG C in the step 5).
By said program, the vegetables of natural porous and layer structure mainly include eggplant, cucumber, asparagus lettuce, celery, potato, Ternip, Chinese cabbage, muskmelon, lotus rhizome, sponge gourd, pumpkin, edible gourd, cucurbit etc..
The internal a large amount of cellulose such as natural porous and layer structure vegetables and special mesh structural porous and layer structure are more It is ignored, its application industrially is hindered significantly.It is based on this herein, utilizes cellulose abundant inside vegetable material With mesh structural porous and stratiform special construction, it is allowed to voluntarily adsorb KOH solution.In addition, vegetable material can serve as carbon source simultaneously (C), it by high-temperature activation, forms the carbon atom in the solid carbon source in cellulose and microcosmic netted and layer structure and is easy to point Solution recombination forms the special construction of few layer graphene less than 10 layers, particularly 3~4 layer；Again due to its internal abundant amino Acid and minerals etc., may act as nitrogen source (N), phosphorus source (P) etc., can generate polyatom auto-dope graphene.The process is simple, It is at low cost, it is nontoxic, conducive to large-scale production, graphene is promoted and economic development is of great significance.
Compared with background technology, the present invention has the following advantages：
1) it is raw material that the present invention, which selects the vegetables in life on dining table, and material source enriches, inexpensively, renewable, and meeting can The requirement of sustainable development.Containing abundant carbon source in vegetables, after graphene is made C content up to 80.0~95.0at.%, and by In containing abundant amino acid and minerals in vegetables, polyatom auto-dope multifunctional graphite vinyl can be formed to a certain extent, Wherein N content is 0.5~6.0at.%, and the content of P is 0.1~3.0at.%, and the doping of the polyatoms such as N, P can open band gap And conduction type is adjusted, change the electronic structure of graphene, the free carrier density of graphene is effectively improved, so as to improve stone The electric conductivity (impedance is less than 70 Ω) and stability of black alkene, while increase the edge defect of graphene, the more activity of exposure Site so that prepared graphene has greater activity, available for fuel-cell catalyst, zinc and air cell, lithium sky battery etc. Field.Compared with graphene made from commonsense method, graphene produced by the present invention has wider application；It is more with traditional fabrication Atom graphene method is compared, and the present invention uses a kind of vegetables cheap and easy to get to substantially reduce cost for raw material, is simplified simultaneously Doping process, and electric conductivity is compared and to be got well.
2) present invention takes full advantage of its material by handling, and be immersed in KOH solution vegetables peeling or defoliation The characteristics of mesh structural porous and its layer structure is easily adsorbed and then by carrying out high-temperature activation processing to it, using contained in its material Carbon atom on some celluloses and microcosmic reticular structure is easily decomposes and recombinates, in the particular surroundings of this high-temperature activation, Voluntarily form graphene-structured.Compared with tradition prepares graphene method, this method prepare graphene have it is three big technologic excellent Point：First, the characteristics of easily being adsorbed using material natural porous and layer structure, is voluntarily adsorbed, is mixed, on hybrid technique It greatly simplifies；Second is that the present invention prepares graphene without preliminary carbonization technique, a step high-temperature activation can be prepared by graphene, significantly Reduce production cost；Third, voluntarily serving as carbon source, nitrogen source, phosphorus source etc. using vegetables, raw material are nontoxic so that preparation process It is more safe and reliable, the basic demand of large-scale production is fully complied with, the commercialization for being advantageous to graphene is promoted.
3) the graphene specific surface area prepared by the present invention is up to 1000m2g-1More than, which is gone back far above numerous with oxidation Graphene prepared by former method.And the graphene number of plies being prepared is less, and only 3~4 layers, better than much preparing graphene Conventional method.High-specific surface area, the graphene-structured of low layer number and its polyatom auto-dope, make it can be widely applied to heat conduction The numerous areas such as material, ultracapacitor, biological devices, sea water desalination, cell catalyst and its positive and negative anodes.
Description of the drawings
Fig. 1 is the SEM figures of 1 eggplant internal structure of embodiment and graphene prepared therefrom；Wherein：Fig. 1 a are embodiments 1 Eggplant internal structure SEM schemes；Fig. 1 b are the SEM figures of 1 made graphene of embodiment.
Fig. 2 is the TEM figures of 1 gained graphene of embodiment.
Fig. 3 is the Raman figures of 1 gained graphene of embodiment.
Fig. 4 is the BET figures of 1 gained graphene of embodiment.
Fig. 5 is 1 gained graphene XPS of embodiment figures.
Fig. 6 is 1 gained graphene EIS of embodiment figures.
Specific embodiment
The present invention is made using the method that vegetables prepare polyatom auto-dope graphene into one below by specific embodiment Walk explanation.
Embodiment 1
1) fresh eggplant is eluted with water, removed the peel, stripping and slicing is placed in the 0.5M KOH solutions being configured, is allowed to impregnate 24h；
2) by resulting materials taking-up in step 1) is placed in freeze drying box -50 DEG C, freeze-drying 36h is done in 10Pa Dry porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, heated up under argon atmosphere every with 5 DEG C After minute is warming up to 800 DEG C of heat preservation 1h, and cool；
4) by after step 3) products therefrom hand ground, 250ml 0.5M H are placed in2SO480 DEG C of acid of water bath with thermostatic control in solution 9h is washed, and is filtered, is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 80 DEG C.
The specific surface area of obtained graphene is up to 1102m2g-1, the wherein content of N element is 1.04at.%, P element Content is 0.15at.%, and impedance is 54 Ω.
Fig. 1 a are scanning electron microscope (SEM) picture of eggplant, it can be seen that eggplant is mesh structural porous containing being conducive to adsorb in itself And layer structure, wherein it is layer structure that number 1 and 2 is signified.
Fig. 1 b are that scanning electron microscope (SEM) picture of gained graphene can see the typical stone of the transparent accordion of graphene Black alkene structure.
Fig. 2 is transmission electron microscope (TEM) picture of gained graphene, it can be seen that the lamellar structure and graphite that graphene stacks Alkene lattice fringe.
Fig. 3 is Raman spectrum (Raman) figure of gained graphene, in 2675cm-1There is sharp graphene 2D peaks, table in place The bright presence for having graphene-structured.
Fig. 4 is the nitrogen adsorption desorption isothermal curve of gained graphene, this product is obtained by nitrogen adsorption desorption isothermal curve Specific surface area (BET) is 1102m2g-1。
Fig. 5 is x-ray photoelectron spectroscopy (XPS) figure of gained graphene, and as can be seen from the figure the product mainly contains C, tetra- kinds of elements of N, O, P, the wherein content of N element are 1.04at.%, and the content of P element is 0.22at.%.
Fig. 6 is EIS (impedance) figure of gained graphene, and as can be seen from the figure the impedance of the graphene is smaller, only 54 Ω。
Embodiment 2
1) fresh cucumber is eluted with water, removed the peel, stripping and slicing is placed in the 0.3M KOH solutions being configured, is allowed to impregnate 48h；
2) by resulting materials taking-up in step 1) is placed in freeze drying box -20 DEG C, freeze-drying 40h is done in 15Pa Dry porous fluffy block structure；
3) it by resulting materials in step 2), is placed in tube furnace, per minute is warming up to 7 DEG C under nitrogen protection atmosphere After 700 DEG C of heat preservation 1.5h, and cool；
4) 80 DEG C of pickling of water bath with thermostatic control in 250ml 0.3M HCl solutions will after step 3) products therefrom hand ground, be placed in 9h, and filtered, it is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 60 DEG C.
The specific surface area of obtained graphene is up to 1221m2g-1, the wherein content of N element is 1.58at.%, P element Content is 0.62at.%, and impedance is 57 Ω.
Embodiment 3
1) fresh asparagus lettuce is eluted with water, removed the peel, stripping and slicing is placed in the 0.6M KOH solutions being configured, is allowed to impregnate 36h；
2) by the taking-up of step 1) resulting materials is placed in freeze drying box -10 DEG C, freeze-drying 65h obtains drying in 10Pa Porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 6 DEG C under argon atmosphere After being warming up to 700 DEG C of heat preservation 0.5h, and cool；
4) 70 DEG C of pickling of water bath with thermostatic control in 200ml 0.3M HCl solutions will after step 3) products therefrom hand ground, be placed in 6h, and filtered, it is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 70 DEG C.
The specific surface area of obtained graphene is up to 1233m2g-1, the wherein content of N element is 0.99at.%, P element Content is 0.21at.%, and impedance is 52 Ω.
Embodiment 4
1) fresh celery is eluted with water, removed the peel, stripping and slicing is placed in the 1M KOH solutions being configured, is allowed to impregnate 24h；
2) by resulting materials taking-up in step 1) is placed in freeze drying box -30 DEG C, freeze-drying 35h is done in 20Pa Dry porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 6 DEG C under argon atmosphere After being warming up to 600 DEG C of heat preservation 1.5h, and cool；
4) by after step 3) products therefrom hand ground, 200ml 0.3M H are placed in2SO460 DEG C of acid of water bath with thermostatic control in solution 15h is washed, and is filtered, is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 90 DEG C.
The specific surface area of obtained graphene is up to 1500m2g-1, the wherein content of N element is 1.33at.%, P element Content is 0.31at.%, and impedance is 46 Ω.
Embodiment 5
1) fresh potato is eluted with water, removed the peel, stripping and slicing is placed in the 0.7M KOH solutions being configured, is allowed to impregnate 24h；
2) by resulting materials taking-up in step 1) is placed in freeze drying box -20 DEG C, freeze-drying 40h is done in 15Pa Dry porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 6 DEG C under argon atmosphere After being warming up to 700 DEG C of heat preservation 1.5h, and cool；
4) by after step 3) products therefrom hand ground, 200ml 0.5M H are placed in2SO460 DEG C of acid of water bath with thermostatic control in solution 15h is washed, and is filtered, is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 80 DEG C.
The specific surface area of obtained graphene is up to 1139m2g-1, the wherein content of N element is 5.2at.%, P element Content is 1.03at.%, and impedance is 42 Ω.
Embodiment 6
1) fresh ternip is eluted with water, removed the peel, stripping and slicing is placed in the 1M KOH solutions being configured, is allowed to impregnate 24h；
2) by resulting materials taking-up in step 1) is placed in freeze drying box -30 DEG C, freeze-drying 35h is done in 20Pa Dry porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 6 DEG C under argon atmosphere After being warming up to 600 DEG C of heat preservation 2h, and cool；
4) 60 DEG C of pickling of water bath with thermostatic control in 200ml 0.4M HCl solutions will after step 3) products therefrom hand ground, be placed in 18h, and filtered, it is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 90 DEG C.
The specific surface area of obtained graphene is up to 1148m2g-1, the wherein content of N element is 2.4at.%, P element Content is 0.55at.%, and impedance is 57 Ω.
Embodiment 7
1) fresh Chinese cabbage is eluted with water, defoliation, stripping and slicing, is placed in the 0.8M KOH solutions being configured, is allowed to impregnate 50h；
2) by the taking-up of step 1) resulting materials is placed in freeze drying box -10 DEG C, freeze-drying 45h obtains drying in 8Pa Porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 10 DEG C under nitrogen protection atmosphere After being warming up to 600 DEG C of heat preservation 2h, and cool；
4) 70 DEG C of pickling of water bath with thermostatic control in 250ml 0.4M HCl solutions will after step 3) products therefrom hand ground, be placed in 6h, and filtered, it is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 70 DEG C.
The specific surface area of obtained graphene is up to 1435m2g-1, the wherein content of N element is 3.2at.%, P element Content is 1.2at.%, and impedance is 65 Ω.
Embodiment 8
1) fresh muskmelon is eluted with water, removed the peel, stripping and slicing is placed in the 0.5M KOH solutions being configured, is allowed to impregnate 72h；
2) by the taking-up of step 1) resulting materials is placed in freeze drying box -10 DEG C, freeze-drying 65h obtains drying in 10Pa Porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 10 DEG C under nitrogen protection atmosphere After being warming up to 900 DEG C of heat preservation 0.5h, and cool；
4) by after step 3) products therefrom hand ground, 250ml 0.4M H are placed in2SO470 DEG C of acid of water bath with thermostatic control in solution 6h is washed, and is filtered, is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 70 DEG C.
The specific surface area of obtained graphene is up to 1198m2g-1, the wherein content of N element is 3.5at.%, P element Content is 1.6at.%, and impedance is 50 Ω.
Embodiment 9
1) fresh lotus rhizome is eluted with water, removed the peel, stripping and slicing is placed in the 0.8M KOH solutions being configured, is allowed to impregnate 36h；
2) by the taking-up of step 1) resulting materials is placed in freeze drying box -10 DEG C, freeze-drying 70h obtains drying in 5Pa Porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 10 DEG C under argon atmosphere After being warming up to 800 DEG C of heat preservation 1h, and cool；
4) 100 DEG C of acid of water bath with thermostatic control in 200ml 0.2M HCl solutions will after step 3) products therefrom hand ground, be placed in 8h is washed, and is filtered, is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 90 DEG C.
The specific surface area of obtained graphene is up to 1326m2g-1, the wherein content of N element is 3.6at.%, P element Content is 1.4at.%, and impedance is 61 Ω.
Embodiment 10
1) fresh sponge gourd is eluted with water, removed the peel, stripping and slicing is placed in the 0.5M KOH solutions being configured, is allowed to impregnate 24h；
2) by the taking-up of step 1) resulting materials is placed in freeze drying box -25 DEG C, freeze-drying 45h obtains drying in 24Pa Porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 7 DEG C under argon atmosphere After being warming up to 700 DEG C of heat preservation 2h, and cool；
4) 80 DEG C of pickling of water bath with thermostatic control in 200ml 0.1M HCl solutions will after step 3) products therefrom hand ground, be placed in 12h, and filtered, it is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 80 DEG C.
The specific surface area of obtained graphene is up to 1230m2g-1, the wherein content of N element is 5.3at.%, P element Content is 1.0at.%, and impedance is 62 Ω.
Embodiment 11
1) fresh pumpkin is eluted with water, removed the peel, stripping and slicing is placed in the 0.6M KOH solutions being configured, is allowed to impregnate 36h；
2) by the taking-up of step 1) resulting materials is placed in freeze drying box -40 DEG C, freeze-drying 20h obtains drying in 20Pa Porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 8 DEG C under nitrogen protection atmosphere After being warming up to 900 DEG C of heat preservation 0.5h, and cool；
4) by after step 3) products therefrom hand ground, 150ml 0.3M H are placed in2SO470 DEG C of acid of water bath with thermostatic control in solution 14h is washed, and is filtered, is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 100 DEG C.
The specific surface area of obtained graphene is up to 1409m2g-1, the wherein content of N element is 4.8at.%, P element Content is 0.18at.%, and impedance is 36 Ω.
Embodiment 12
1) fresh edible gourd is eluted with water, removed the peel, stripping and slicing is placed in the 0.2M KOH solutions being configured, is allowed to impregnate 72h；
2) by the taking-up of step 1) resulting materials is placed in freeze drying box -30 DEG C, freeze-drying 35h obtains drying in 25Pa Porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 6 DEG C under argon atmosphere After being warming up to 800 DEG C of heat preservation 1h, and cool；
4) by after step 3) products therefrom hand ground, 250ml 0.4M H are placed in2SO490 DEG C of acid of water bath with thermostatic control in solution 12h is washed, and is filtered, is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 80 DEG C.
The specific surface area of obtained graphene is up to 1285m2g-1, the wherein content of N element is 2.3at.%, P element Content is 0.15at.%, and impedance is 51 Ω.
Embodiment 13
1) fresh cucurbit is eluted with water, removed the peel, stripping and slicing is placed in the 0.3M KOH solutions being configured, is allowed to impregnate 60h；
2) by the taking-up of step 1) resulting materials is placed in freeze drying box -50 DEG C, freeze-drying 48h obtains drying in 10Pa Porous fluffy block structure；
3) resulting materials in step 2) are weighed into 10g, be placed in tube furnace, it is per minute with 7 DEG C under argon atmosphere After being warming up to 800 DEG C of heat preservation 1h, and cool；
4) by after step 3) products therefrom hand ground, 200ml 0.5M H are placed in2SO460 DEG C of acid of water bath with thermostatic control in solution 10h is washed, and is filtered, is washed with water to neutrality；
5) step 4) is placed in gained sample in vacuum drying chamber and dried to get graphene for 60 DEG C.
The specific surface area of obtained graphene is up to 1373m2g-1, the wherein content of N element is 3.9at.%, P element Content is 0.45at.%, and impedance is 49 Ω.

Claims (7)

1. the method for preparing polyatom auto-dope graphene using natural porous and layer structure vegetables, it is characterised in that：By vegetable It is soaked in KOH solution after dish processing, after the activation process that is freeze-dried, heats up, then pickling is dried and obtained, and step is such as Under：
Step 1）：Fresh vegetables are eluted with water, after simple process, stripping and slicing is placed in the KOH solution being configured, KOH solution A concentration of 0.3 ~ 1.0 mol/L；Soaking time is 24 ~ 72h, is impregnated；
Step 2）：By step 1）Middle resulting materials take out, and vacuum freeze drying obtains dry porous fluffy block structure material；
Step 3）：By step 2）Middle gained drying porous fluffy block structure material claims to be placed in tube furnace, is protected in inert gas The activation that heats up under atmosphere is protected, is cooled；The step 3）Middle 600 ~ 900 DEG C of activation temperature；Soak time is 0.5 ~ 3h；
Step 4）：After products therefrom is ground, pickling is simultaneously filtered, and is washed with water to neutrality；
Step 5）：By step 4）Gained sample is placed in vacuum drying to get polyatom auto-dope graphene；
The vegetables of the natural porous and layer structure mainly include eggplant, cucumber, asparagus lettuce, celery, potato, ternip, Chinese cabbage, Muskmelon, lotus rhizome, sponge gourd, pumpkin, edible gourd, cucurbit.
2. the side of polyatom auto-dope graphene is prepared using natural porous and layer structure vegetables according to claim 1 Method, it is characterised in that：Step 1）Simple process be：Fruit vegetables peeling is handled, the processing of leaf vegetables defoliation.
3. the side of polyatom auto-dope graphene is prepared using natural porous and layer structure vegetables according to claim 1 Method, it is characterised in that：The step 2）Middle freeze-drying is carried out under the conditions of -50~0 DEG C, 5~30Pa, drying time 12 ~70h.
4. the side of polyatom auto-dope graphene is prepared using natural porous and layer structure vegetables according to claim 1 Method, it is characterised in that：The step 3）Middle heating rate is 5 ~ 10 DEG C/min.
5. the side of polyatom auto-dope graphene is prepared using natural porous and layer structure vegetables according to claim 1 Method, it is characterised in that：The step 4）In pickling to be placed in 60 DEG C ~ 100 DEG C 6 ~ 18h of water-bath pickling in acid solution.
6. the side of polyatom auto-dope graphene is prepared using natural porous and layer structure vegetables according to claim 1 Method, it is characterised in that：The step 4）Middle acid solution is the H of 0.1 ~ 0.5 mol/L2SO4Or HCl solution.
7. the side of polyatom auto-dope graphene is prepared using natural porous and layer structure vegetables according to claim 1 Method, it is characterised in that：The step 5）Middle vacuum drying temperature is 60 ~ 100 DEG C.
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