CN105752969A - Method for preparing polyatomic self-doped graphene by using natural porous and laminated vegetables - Google Patents
Method for preparing polyatomic self-doped graphene by using natural porous and laminated vegetables Download PDFInfo
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Abstract
The invention relates to a method for preparing polyatomic self-doped graphene by using natural porous and laminated vegetables. The method comprises the following steps: soaking treated vegetables in a KOH solution, performing freeze drying and heating activation, then performing acid pickling and drying to obtain the polyatomic self-doped graphene. According to the method, the vegetables are selected as raw materials which are rich in source and low in price, are reproducible, and meet requirements of sustainable development. The vegetables contain rich carbon sources, the C content after preparation of graphene can reach 80.0-95.0at.%, and as the vegetables contain rich amino acid and minerals, polyatomic self-doped multifunctional graphene can be formed to a certain extent, wherein the content of N is 0.5-6.0at.%, the content of P is 0.1-3.0at.%, the polyatomic doping of N, P and the like can open a band gap, regulate the conduction type, change an electronic structure of graphene, and effectively improve the free carrier density of the graphene, thereby improving the electrical conductivity and stability of the graphene, increasing edge defects of the graphene at the same time, exposing more active sites, and enabling the prepared graphene to have relatively high activity.
Description
Technical field
The present invention relates to a kind of method utilizing natural porous and layer structure vegetable to prepare polyatom auto-dope Graphene, belong to grapheme material preparation field.
Background technology
Graphene (G) be planar monolayer carbon atom be closely linked formed two dimension (2D) lattice material, it is believed that be build every other dimension graphite material (be rolled into fullerene, roll into CNT and pile integrated graphite) elementary cell.The thickness of Graphene is only about 0.35nm, is two-dimensional material the thinnest in the world.Stablize regular hexagon lattice structure and give the performance of the many uniquenesses of Graphene, if hot strength is up to 130Gpa, be the highest in known materials；Carrier mobility is up to 15000～25000cm2/ Vs (exceedes commercial silicon chip 10 times)；It is 3 times of diamond that thermal conductivity reaches 5000W/mK, also has the special natures such as room-temperature quantum Hall effect and room-temperature ferromagnetic.Additionally, electronics traverse Graphene is almost without any resistance, the heat of generation is few, and electrical efficiency is high, is be currently known the material that electric conductivity is the most excellent.
The method preparing Graphene at present can be divided into physical method (the direct stripping method of micromechanics stripping method, liquid phase or gas phase) and chemical method (chemical vapour deposition technique, crystal epitaxy method and oxidation-reduction method).Micromechanics stripping method is the method preparing Graphene that [Science, 2004,306 (5696): 666-669] such as Geim reports the earliest.This method wastes time and energy and is difficult to accurate control, poor repeatability, it is difficult to prepare on a large scale.Liquid phase or the direct stripping method of gas phase, as Coleman etc. peels off the mode of CNT by graphite dispersion in N-methyl-pyrrolidon [Nat.Nanotechnol, 2008,3 (9): 563-568] with reference to liquid phase, can prepare Graphene.But this method to prepare Graphene productivity relatively low, be only a few percent, significantly limit its business promotion.Chemical vapour deposition technique (CVD) is a kind of effective ways of present stage preparation quality height, large-area graphene, as Kim etc. adds nickel [Nature one layer very thin on a silicon substrate, 2009,457 (7230): 706-710], methane, hydrogen and argon stream are calcined, nickel dam deposits relatively large 6～10 layer graphenes.This method preparation cost is high, be difficult to accurately control processing conditions, constrains its development.Crystal epitaxy method, removes Si [Nat.Mater, 2008,7 (5): 406-411] such as Sutter etc. by heating monocrystalline 6H-SiC, thus obtaining the Graphene in surface of SiC extension.This method is very big by the impact of substrate, and synthesis condition is harsh, and Graphene not easily separates from substrate, it is difficult to manufacture Graphene in a large number.Oxidation-reduction method is the method preparing Graphene the most frequently used at present, such as the hydrazine hydrate reduction agent [C argon bon, 2011,49 (9): 3019-3023] such as P argon k, success reduced graphene.But this method frequently with reducing agent there is toxicity so that preparation process is dangerous and unstability, and the Graphene that this reduction is prepared all can exist an aggregation procedure, causes Graphene specific surface area less than normal, is usually less than 900m2/g.Therefore, the approach preparing Graphene that a kind of safe and efficient, low cost of invention, environmental protection are friendly it is badly in need of.
Biological material has plurality of advantages sustainable, environmental friendly regenerated, abundance, has extensive use at the numerous areas such as agriculture, medical, chemical.As the vegetable on meal seat, playing immense value containing abundant aminoacid and mineral providing to the mankind on nutrition and energy, it is often out in the cold that its special construction having (has porous and layer structure thereof).Vegetable application industrially is considerably less, and therefore its application industrially still needs to deeply probe into.
Summary of the invention
Present invention aims to the existing deficiency preparing Graphene technology and shortcoming, it is provided that a kind of method simply utilizing natural porous and layer structure vegetable to prepare polyatom auto-dope Graphene.
For achieving the above object, the technical solution used in the present invention is:
The method utilizing natural porous and layer structure vegetable to prepare polyatom auto-dope Graphene of the present invention, is soaked in KOH solution after being processed by vegetable, and after lyophilization, intensification activation processing, then pickling is dried and obtained, and step is as follows:
1) fresh vegetable is washed, after simple process, stripping and slicing, it is placed in the KOH solution configured, soaks；
2) by step 1) in resulting materials take out, vacuum lyophilization obtains dry porous fluffy block structure material；
3) by step 2) in the dry porous fluffy block structure material of gained claim to be placed in tube furnace, heat up activation under inert gas shielding atmosphere, cools；
4), after products therefrom grinds, pickling also carries out sucking filtration, washes with water to neutrality；
5) by step 4) gained sample is placed in vacuum drying, obtains polyatom auto-dope Graphene.
By such scheme, described step 1) simple process is: fruit vegetables peeling processes, and leaf vegetables defoliation processes.
By such scheme, described step 1) concentration of KOH is 0.3～1.0mol/L.
By such scheme, described step 1) soak time is 24～72h.
By such scheme, described step 2) in lyophilization be-50～0 DEG C, 5～30Pa when carry out, drying time is 12～70h.
By such scheme, described step 3) in heating rate be 5～10 DEG C/min.
By such scheme, described step 3) in activation temperature 600～900 DEG C；Soak time is 0.5～3h.
By such scheme, described step 4) in pickling for being placed in acid solution 60 DEG C～100 DEG C of water-bath pickling 6～18h.
By such scheme, described step 4) in acid solution be the H of 0.1～0.5mol/L2SO4Or HCl solution.
By such scheme, described step 5) in vacuum drying temperature be 60～100 DEG C.
Fructus Solani melongenae, Fructus Cucumidis sativi, Caulis et Folium Lactucae sativae, Herba Apii graveolentis, Rhizoma Solani tuber osi, white turnip, Chinese cabbage, Fructus Melo, Rhizoma Nelumbinis, Fructus Luffae, Fructus Cucurbitae moschatae, Pericarpium Lagenariae hispidae, calabash etc. are mainly included by the vegetable of such scheme, natural porous and layer structure.
How out in the cold the internal substantial amounts of cellulose such as natural porous and layer structure vegetable and special mesh structural porous and layer structure be, significantly hinders its application industrially.It is based on this herein, utilizes the internal abundant cellulose of vegetable material and mesh structural porous and stratiform special construction, be allowed to adsorb voluntarily KOH solution.Additionally, vegetable material simultaneously can serve as carbon source (C), through high-temperature activation, and its composition cellulose and microcosmic is netted and the easily decomposes restructuring of carbon atom in solid carbon source in layer structure, formed lower than 10 layers, the particularly special construction of few layer graphene of 3～4 layers；Again due to its internal abundant aminoacid and mineral etc., may act as nitrogenous source (N), phosphorus source (P) etc., polyatom auto-dope Graphene can be generated.This process is simple, and cost is low, nontoxic, is beneficial to large-scale production, Graphene is promoted and economic development is significant.
Compared with background technology, the invention have the advantages that
1) vegetable that the present invention selects in life on dining table is raw material, and material source enriches, inexpensively, renewable, meets the requirement of sustainable development.Containing abundant carbon source in vegetable, after making Graphene, C content is up to 80.0～95.0at.%, again owing to vegetable is contained within the aminoacid and the mineral that enrich, 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 polyatom doping such as P can be opened band gap and adjust conduction type, change the electronic structure of Graphene, it is effectively improved the free carrier density of Graphene, thus improving electric conductivity (impedance is less than 70 Ω) and the stability of Graphene, increase the edge defect of Graphene simultaneously, expose more avtive spot, prepared Graphene is made to have greater activity, can be used for fuel-cell catalyst, zinc and air cell, the fields such as lithium sky battery.Compared with the Graphene that commonsense method prepares, the Graphene that the present invention prepares has wider application；Compared with traditional fabrication polyatom Graphene method, the present invention adopts a kind of vegetable cheap and easy to get to be raw material, is substantially reduced cost, simplifies doping process simultaneously, and electric conductivity is compared and to be got well.
2) present invention is by processing vegetable peeling or defoliation, and it is immersed in KOH solution, take full advantage of its material network porous and feature that layer structure is easily adsorbed and then by it is carried out high-temperature activation process, utilize the carbon atom in cellulose contained in its material and microcosmic network structure easily decomposes and restructuring, in the special environment of this high-temperature activation, form graphene-structured voluntarily.Prepare compared with Graphene method with tradition, the method prepares Graphene three big technologic advantages: one is the feature utilizing material natural porous and layer structure easily to adsorb, and adsorbs voluntarily, mixes, is greatly simplified on hybrid technique；Two is that the present invention prepares Graphene without preliminary carbonization technique, and a step high-temperature activation can be prepared by Graphene, is substantially reduced production cost；Three is utilize vegetable to serve as carbon source, nitrogenous source, phosphorus source etc. voluntarily, and raw material is nontoxic so that preparation process is more safe and reliable, fully complies with the basic demand of large-scale production, and the commercialization being advantageous to Graphene is promoted.
3) the Graphene specific surface area prepared by the present invention is up to 1000m2g-1Above, this value is far above the Graphene prepared by numerous oxidation-reduction methodes.And the Graphene number of plies for preparing is less, is only 3～4 layers, is better than much preparing the traditional method of Graphene.High-specific surface area, the graphene-structured of the low number of plies and its polyatom auto-dope so that it is can be widely applied to the numerous areas such as Heat Conduction Material, ultracapacitor, biological devices, desalinization, cell catalyst and both positive and negative polarity thereof.
Accompanying drawing explanation
Fig. 1 is the SEM figure of embodiment 1 Fructus Solani melongenae internal structure and Graphene prepared therefrom；Wherein: Fig. 1 a is embodiment 1 Fructus Solani melongenae internal structure SEM figure；Fig. 1 b is the SEM figure of the made Graphene of embodiment 1.
Fig. 2 is the TEM figure of embodiment 1 gained Graphene.
Fig. 3 is the Raman figure of embodiment 1 gained Graphene.
Fig. 4 is the BET figure of embodiment 1 gained Graphene.
Fig. 5 is embodiment 1 gained Graphene XPS figure.
Fig. 6 is embodiment 1 gained Graphene EIS figure.
Detailed description of the invention
The method that vegetable prepares polyatom auto-dope Graphene is utilized to be described further the present invention below by specific embodiment.
Embodiment 1
1) fresh Fructus Solani melongenae is washed, peeling, stripping and slicing, be placed in the 0.5MKOH solution configured, be allowed to soak 24h；
2) by step 1) in resulting materials take out be placed in freeze drying box-50 DEG C, lyophilization 36h obtains dry porous fluffy block structure in 10Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, heat up under argon atmosphere with 5 DEG C per minute be warming up to 800 DEG C of insulation 1h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 250ml0.5MH2SO480 DEG C of pickling 9h of water bath with thermostatic control in solution, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 80 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1102m2g-1, wherein the content of N element is 1.04at.%, and the content of P element is 0.15at.%, and impedance is 54 Ω.
Fig. 1 a is scanning electron microscope (SEM) picture of Fructus Solani melongenae, it can be seen that Fructus Solani melongenae itself is containing the mesh structural porous and layer structure being conducive to absorption, and wherein numeral 1 and 2 indications are layer structure.
Fig. 1 b is that scanning electron microscope (SEM) picture of gained Graphene is it can be seen that the typical graphene-structured of the transparent accordion of Graphene.
Fig. 2 is transmission electron microscope (TEM) picture of gained Graphene, it can be seen that lamellar structure that Graphene is stacking and Graphene lattice fringe.
Fig. 3 is Raman spectrum (Raman) figure of gained Graphene, at 2675cm-1There is sharp-pointed Graphene 2D peak in place, it was shown that have the existence of graphene-structured.
Fig. 4 is the nitrogen adsorption desorption isothermal curve of gained Graphene, nitrogen adsorption desorption isothermal curve the specific surface area (BET) obtaining this product is 1102m2g-1。
Fig. 5 is x-ray photoelectron power spectrum (XPS) figure of gained Graphene, and as can be seen from the figure this product mainly contains tetra-kinds of elements of C, N, O, P, and wherein the content of N element is 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 this Graphene is less, is only 54 Ω.
Embodiment 2
1) fresh Fructus Cucumidis sativi is washed, peeling, stripping and slicing, be placed in the 0.3MKOH solution configured, be allowed to soak 48h；
2) by step 1) in resulting materials take out be placed in freeze drying box-20 DEG C, lyophilization 40h obtains the porous fluffy block structure dried in 15Pa；
3) by step 2) in resulting materials, be placed in tube furnace, under nitrogen protection atmosphere with 7 DEG C per minute be warming up to 700 DEG C of insulation 1.5h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 250ml0.3MHCl solution 80 DEG C of pickling 9h of water bath with thermostatic control, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 60 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1221m2g-1, wherein the content of N element is 1.58at.%, and the content of P element is 0.62at.%, and impedance is 57 Ω.
Embodiment 3
1) fresh Caulis et Folium Lactucae sativae is washed, peeling, stripping and slicing, be placed in the 0.6MKOH solution configured, be allowed to soak 36h；
2) by step 1) resulting materials take out be placed in freeze drying box-10 DEG C, lyophilization 65h obtains the porous fluffy block structure dried in 10Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under argon atmosphere with 6 DEG C per minute be warming up to 700 DEG C of insulation 0.5h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 200ml0.3MHCl solution 70 DEG C of pickling 6h of water bath with thermostatic control, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 70 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1233m2g-1, wherein the content of N element is 0.99at.%, and the content of P element is 0.21at.%, and impedance is 52 Ω.
Embodiment 4
1) fresh Herba Apii graveolentis is washed, peeling, stripping and slicing, be placed in the 1MKOH solution configured, be allowed to soak 24h；
2) by step 1) in resulting materials take out be placed in freeze drying box-30 DEG C, lyophilization 35h obtains the porous fluffy block structure dried in 20Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under argon atmosphere with 6 DEG C per minute be warming up to 600 DEG C of insulation 1.5h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 200ml0.3MH2SO460 DEG C of pickling 15h of water bath with thermostatic control in solution, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 90 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1500m2g-1, wherein the content of N element is 1.33at.%, and the content of P element is 0.31at.%, and impedance is 46 Ω.
Embodiment 5
1) fresh Rhizoma Solani tuber osi is washed, peeling, stripping and slicing, be placed in the 0.7MKOH solution configured, be allowed to soak 24h；
2) by step 1) in resulting materials take out be placed in freeze drying box-20 DEG C, lyophilization 40h obtains the porous fluffy block structure dried in 15Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under argon atmosphere with 6 DEG C per minute be warming up to 700 DEG C of insulation 1.5h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 200ml0.5MH2SO460 DEG C of pickling 15h of water bath with thermostatic control in solution, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 80 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1139m2g-1, wherein the content of N element is 5.2at.%, and the content of P element is 1.03at.%, and impedance is 42 Ω.
Embodiment 6
1) fresh white turnip is washed, peeling, stripping and slicing, be placed in the 1MKOH solution configured, be allowed to soak 24h；
2) by step 1) in resulting materials take out be placed in freeze drying box-30 DEG C, lyophilization 35h obtains the porous fluffy block structure dried in 20Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under argon atmosphere with 6 DEG C per minute be warming up to 600 DEG C of insulation 2h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 200ml0.4MHCl solution 60 DEG C of pickling 18h of water bath with thermostatic control, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 90 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1148m2g-1, wherein the content of N element is 2.4at.%, and the content of P element is 0.55at.%, and impedance is 57 Ω.
Embodiment 7
1) fresh Chinese cabbage is washed, defoliation, stripping and slicing, be placed in the 0.8MKOH solution configured, be allowed to soak 50h；
2) by step 1) resulting materials take out be placed in freeze drying box-10 DEG C, lyophilization 45h obtains the porous fluffy block structure dried in 8Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under nitrogen protection atmosphere with 10 DEG C per minute be warming up to 600 DEG C of insulation 2h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 250ml0.4MHCl solution 70 DEG C of pickling 6h of water bath with thermostatic control, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 70 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1435m2g-1, wherein the content of N element is 3.2at.%, and the content of P element is 1.2at.%, and impedance is 65 Ω.
Embodiment 8
1) fresh Fructus Melo is washed, peeling, stripping and slicing, be placed in the 0.5MKOH solution configured, be allowed to soak 72h；
2) by step 1) resulting materials take out be placed in freeze drying box-10 DEG C, lyophilization 65h obtains the porous fluffy block structure dried in 10Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under nitrogen protection atmosphere with 10 DEG C per minute be warming up to 900 DEG C of insulation 0.5h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 250ml0.4MH2SO470 DEG C of pickling 6h of water bath with thermostatic control in solution, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 70 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1198m2g-1, wherein the content of N element is 3.5at.%, and the content of P element is 1.6at.%, and impedance is 50 Ω.
Embodiment 9
1) fresh Rhizoma Nelumbinis is washed, peeling, stripping and slicing, be placed in the 0.8MKOH solution configured, be allowed to soak 36h；
2) by step 1) resulting materials take out be placed in freeze drying box-10 DEG C, lyophilization 70h obtains the porous fluffy block structure dried in 5Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under argon atmosphere with 10 DEG C per minute be warming up to 800 DEG C of insulation 1h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 200ml0.2MHCl solution 100 DEG C of pickling 8h of water bath with thermostatic control, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 90 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1326m2g-1, wherein the content of N element is 3.6at.%, and the content of P element is 1.4at.%, and impedance is 61 Ω.
Embodiment 10
1) fresh Fructus Luffae is washed, peeling, stripping and slicing, be placed in the 0.5MKOH solution configured, be allowed to soak 24h；
2) by step 1) resulting materials take out be placed in freeze drying box-25 DEG C, lyophilization 45h obtains the porous fluffy block structure dried in 24Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under argon atmosphere with 7 DEG C per minute be warming up to 700 DEG C of insulation 2h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 200ml0.1MHCl solution 80 DEG C of pickling 12h of water bath with thermostatic control, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 80 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1230m2g-1, wherein the content of N element is 5.3at.%, and the content of P element is 1.0at.%, and impedance is 62 Ω.
Embodiment 11
1) fresh Fructus Cucurbitae moschatae is washed, peeling, stripping and slicing, be placed in the 0.6MKOH solution configured, be allowed to soak 36h；
2) by step 1) resulting materials take out be placed in freeze drying box-40 DEG C, lyophilization 20h obtains the porous fluffy block structure dried in 20Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under nitrogen protection atmosphere with 8 DEG C per minute be warming up to 900 DEG C of insulation 0.5h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 150ml0.3MH2SO470 DEG C of pickling 14h of water bath with thermostatic control in solution, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 100 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1409m2g-1, wherein the content of N element is 4.8at.%, and the content of P element is 0.18at.%, and impedance is 36 Ω.
Embodiment 12
1) fresh Pericarpium Lagenariae hispidae is washed, peeling, stripping and slicing, be placed in the 0.2MKOH solution configured, be allowed to soak 72h；
2) by step 1) resulting materials take out be placed in freeze drying box-30 DEG C, lyophilization 35h obtains the porous fluffy block structure dried in 25Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under argon atmosphere with 6 DEG C per minute be warming up to 800 DEG C of insulation 1h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 250ml0.4MH2SO490 DEG C of pickling 12h of water bath with thermostatic control in solution, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 80 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1285m2g-1, wherein the content of N element is 2.3at.%, and the content of P element is 0.15at.%, and impedance is 51 Ω.
Embodiment 13
1) fresh calabash is washed, peeling, stripping and slicing, be placed in the 0.3MKOH solution configured, be allowed to soak 60h；
2) by step 1) resulting materials take out be placed in freeze drying box-50 DEG C, lyophilization 48h obtains the porous fluffy block structure dried in 10Pa；
3) by step 2) in resulting materials weigh 10g, be placed in tube furnace, under argon atmosphere with 7 DEG C per minute be warming up to 800 DEG C of insulation 1h after, and cool；
4) by step 3) after products therefrom hand ground, it is placed in 200ml0.5MH2SO460 DEG C of pickling 10h of water bath with thermostatic control in solution, and carry out sucking filtration, wash with water to neutrality；
5) by step 4) it is placed in vacuum drying oven 60 DEG C of drying at gained sample, obtain Graphene.
The specific surface area of obtained Graphene is up to 1373m2g-1, wherein the content of N element is 3.9at.%, and the content of P element is 0.45at.%, and impedance is 49 Ω.
Claims (10)
1. the method utilizing natural porous and layer structure vegetable to prepare polyatom auto-dope Graphene of the present invention, it is characterized in that: be soaked in KOH solution after vegetable is processed, after lyophilization, intensification activation processing, then pickling is dried and is obtained, and step is as follows:
1) fresh vegetable is washed, after simple process, stripping and slicing, it is placed in the KOH solution configured, soaks；
2) by step 1) in resulting materials take out, vacuum lyophilization obtains dry porous fluffy block structure material；
3) by step 2) in the dry porous fluffy block structure material of gained claim to be placed in tube furnace, heat up activation under inert gas shielding atmosphere, cools；
4), after products therefrom grinds, pickling also carries out sucking filtration, washes with water to neutrality；
5) by step 4) gained sample is placed in vacuum drying, obtains polyatom auto-dope Graphene.
2. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: described step 1) simple process is: fruit vegetables peeling processes, and leaf vegetables defoliation processes.
3. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: described step 1) concentration of KOH is 0.3～1.0mol/L；Soak time is 24～72h.
4. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: described step 2) in lyophilization be-50～0 DEG C, 5～30Pa when carry out, drying time is 12～70h.
5. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: described step 3) in heating rate be 5～10 DEG C/min.
6. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: described step 3) in activation temperature 600～900 DEG C；Soak time is 0.5～3h.
7. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: described step 4) in pickling for being placed in acid solution 60 DEG C～100 DEG C of water-bath pickling 6～18h.
8. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: described step 4) in acid solution be the H of 0.1～0.5mol/L2SO4Or HCl solution.
9. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: described step 5) in vacuum drying temperature be 60～100 DEG C.
10. utilize the method that natural porous and layer structure vegetable prepare polyatom auto-dope Graphene according to claim 1, it is characterised in that: the vegetable of natural porous and layer structure mainly includes Fructus Solani melongenae, Fructus Cucumidis sativi, Caulis et Folium Lactucae sativae, Herba Apii graveolentis, Rhizoma Solani tuber osi, white turnip, Chinese cabbage, Fructus Melo, Rhizoma Nelumbinis, Fructus Luffae, Fructus Cucurbitae moschatae, Pericarpium Lagenariae hispidae, calabash etc..
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744936A (en) * | 2016-12-05 | 2017-05-31 | 天津大学 | A kind of method that biomass cauline leaf separation prepares absorbent charcoal material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386684A (en) * | 2014-12-16 | 2015-03-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene and graphene |
| JP2015523946A (en) * | 2012-05-07 | 2015-08-20 | バイオジェニック レゲント ベンチャーズ エルエルシー | Biogenic activated carbon and methods of making and using it |
| CN104916446A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院大连化学物理研究所 | Active graphene electrode material for super capacitor and preparation method of active graphene electrode material |
| CN105060289A (en) * | 2015-09-21 | 2015-11-18 | 中南大学 | Method for preparing fewer-layer graphene on basis of biomass waste |
-
2016
- 2016-02-29 CN CN201610113576.8A patent/CN105752969B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015523946A (en) * | 2012-05-07 | 2015-08-20 | バイオジェニック レゲント ベンチャーズ エルエルシー | Biogenic activated carbon and methods of making and using it |
| CN104916446A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院大连化学物理研究所 | Active graphene electrode material for super capacitor and preparation method of active graphene electrode material |
| CN104386684A (en) * | 2014-12-16 | 2015-03-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene and graphene |
| CN105060289A (en) * | 2015-09-21 | 2015-11-18 | 中南大学 | Method for preparing fewer-layer graphene on basis of biomass waste |
Non-Patent Citations (1)
| Title |
|---|
| HIROYUKI MURAMATSU ET AL.: "Rice Husk-Derived Graphene with Nano-Sized Domains and Clean Edges", 《SMALL》 * |
Cited By (11)
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