CN106477563A - A kind of method that Graphene and graphene-based material are prepared for raw material with insect wing - Google Patents
A kind of method that Graphene and graphene-based material are prepared for raw material with insect wing Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 53
- 241000238631 Hexapoda Species 0.000 title claims abstract description 29
- 239000002994 raw material Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 229910002804 graphite Inorganic materials 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 8
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 238000006365 thiocyanation reaction Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 241000726128 Aeshna Species 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- 241001290084 Papilio bianor Species 0.000 description 33
- 241000238633 Odonata Species 0.000 description 14
- 241000931705 Cicada Species 0.000 description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 241001112586 Sasakia charonda Species 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 210000003462 vein Anatomy 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 241000933192 Papilio xuthus Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical group N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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Abstract
The invention discloses a kind of prepare Graphene and the preparation method of graphene-based material with insect wing for raw material, first insect wing is carried out hydrothermal treatment consists, again insect wing is mixed with the ethanol solution of slaine after drying, insect wing is 0.001～1000 with the mass ratio of slaine, after lyophilisation or drying, again by mixture in 500～2000 DEG C of high temperature cabonizations, obtain Graphene and graphene-based material.Resulting product of the present invention has high specific surface, and enable N doping, and preparation method be simple and convenient to operate, with low cost, very friendly to environment, for realize graphene-based material functional direction design with performance optimization provide new thinking and strategy.
Description
Technical field
The present invention is with regard to material with carbon element, prepares Graphene and graphene-based with insect wing for raw material particularly to one kind
The method of material.
Background technology
Graphite is by sp2Hydbridized carbon atoms composition hexagonal honeycomb and can infinite expanding laminar crystalline material, have
The high temperature resistant, property such as conduction/excellent heat conductivity, good chemical stability, good thermal shock.And by peeling off what graphite obtained
Graphene, even more with its high electron mobility, high conductance, room-temperature quantum Hall effect and high transmission rate the advantages of, physics,
Chemistry and Material Field have important industrialization prospect.
In recent years, Graphene and the material family based on Graphene be as the important research direction in material with carbon element field, in energy
The aspects such as source, electronic material, biotechnology, catalysis present premium properties.Currently, people mainly develop including Graphene,
The graphite olefinic base material such as graphene-based inorganic nano composite material, graphene polymer, Graphene metal-base composites,
Corresponding preparation means such as mechanical stripping method, chemical vapour deposition technique, nitrogen presoma transformation approach, the pyrolysis of ammonia source, microwave thermal reduction
Method, solvent-thermal method, plasma discharge method etc., the process that exists is complicated, uncontrollable factor is many, Graphene quality is low or yield
Low shortcoming.Therefore, how simple and extensive synthesizing graphite alkene and graphene-based material be still material with carbon element synthesize field one
Big challenge.Based on this, development one kind prepares high-quality Graphene and graphene-based material using insect wing, is this patent
Core concept.
Content of the invention
The purpose of the present invention, be for overcoming that the preparation process of prior art is complicated, uncontrollable factor is many, product quality and product
The shortcomings of measure relatively low, provides a kind of method (high temperature cabonization method) preparing Graphene and graphene-based material using insect wing.
The method preparation process is simple, repeatable strong, yield height, prepared Graphene and graphene-based material specific surface area are big
(776m2/g), quality height, easily transfer, and can achieve original position nitrating, for realizing functionalization and the reality of Graphene and graphite-based material
There is provided new thinking and strategy with changing.
The present invention is achieved by following technical solution：
The present invention, with slaine as catalyst, with insect wing as carbon source, carries out high temperature cabonization process in an inert atmosphere,
Obtain Graphene and graphene-based material；Described slaine is the salt of the metal having catalytic action to graphene growth, such as ferrum
Race's slaine etc., the wing of the wing that described insect wing is originated as common insecticide, such as butterfly, Aeschna melanictera and Cicadae；Described part
Nitrogen substance in insect wing composition realizes situ Nitrogen Doping at high temperature；Obtained product is Graphene, Graphene and stone
The complex of ink, the Graphene doped with nitrogen and the Graphene-graphite composite doped with nitrogen etc..
Concrete preparation method is as follows：
(1) take insect wing, put into equipped with the container of deionized water, in baking oven more than room temperature, heat 0.5- with water
48 hours, after being cooled to room temperature, take out insect wing, put in baking oven and be dried；
(2) insect wing weighing the drying of step (1) is immersed in the ethanol solution being dissolved with slaine, insecticide wing
Wing is 0.001～1000 with the mass ratio of slaine, puts in lyophilizing instrument, lyophilisation 24-72 hour；
(3) by the good insect wing of lyophilizing in step (2), put in crucible, in inert atmosphere, in tube furnace in
500～2000 DEG C of calcining 1-10 hour, is subsequently cooled to room temperature；
(4) product in step (3) is taken out from tube furnace, that is, obtain Graphene and graphene-based material.
The insect wing of described step (1) is the wing of common butterfly, Aeschna melanictera and Cicadae.
The slaine of described step (2) is the salt of the metal having catalytic action to graphene growth：Iron chloride, nitric acid falls,
Thiocyanation ferrum, iron sulfate or haemachrome.
The lyophilisation of described step (2) can also be dried.
The inert atmosphere of described step (3) is nitrogen or argon gas atmosphere.
Graphene-based material is complex, the Graphene doped with nitrogen and the graphite doped with nitrogen of Graphene and graphite
Alkene-graphite composite.
The invention has the beneficial effects as follows：This preparation method is simple, the response time is short, slaine low toxicity used, danger are little,
Easy to operate, very friendly to environment；The product being obtained mostly is multi-layer graphene and graphene-based material, sprawls uniformly, and
Combine closely with carbon backbone structure；Due to containing N element in biomass, therefore can achieve situ Nitrogen Doping, simplify synthesis technique road
Line；Graphene, the adjustment graphite of the different numbers of plies by regulating and controlling the conditions such as carburizing temperature, the species of iron salt, response time, can be obtained
Change degree, control nitrating type and content, realize the controllable standby of Graphene/graphite-based material.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph of the original scale structure of the optical photograph of greenbelt Papilio bianor and greenbelt Papilio bianor wing
(SEM).
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of scale structure after high temperature cabonization for the greenbelt Papilio bianor wing.
Fig. 3 is the transmission electron microscope picture (TEM) of scale structure after high temperature cabonization for the greenbelt Papilio bianor wing.
Fig. 4 is the high power transmission electron microscope picture (HRTEM) of the wing of greenbelt Papilio bianor shown in Fig. 3 sample after high temperature cabonization.
Fig. 5 is the scattergram of different number of plies Graphenes in the wing sample after high temperature cabonization of greenbelt Papilio bianor shown in Fig. 2.
Fig. 6 is the x-ray photoelectron energy spectrum diagram of carbon in the Papilio bianor wing sample after high temperature cabonization of greenbelt
(XPS).
Fig. 7 is the x-ray photoelectron energy spectrum diagram of nitrogen in the Papilio bianor wing sample after high temperature cabonization of greenbelt
(XPS).
Fig. 8 is the x-ray photoelectron energy spectrum diagram of ferrum element in the Papilio bianor wing sample after high temperature cabonization of greenbelt
(XPS).
Fig. 9 is the greenbelt Papilio bianor wing specific surface of sample and graph of pore diameter distribution after high temperature cabonization.
Figure 10 is the wing of greenbelt Papilio bianor shown in Fig. 1 under haemachrome catalysis, and after high temperature cabonization, the high power of sample is saturating
Penetrate electron microscope (HRTEM).
Figure 11 is the optical photograph of Japanese Sasakia charonda and the scanning electron microscope (SEM) photograph (SEM) of original scale structure on wing.
Figure 12 is the optical photograph of black cicada and the scanning electron microscope (SEM) photograph (SEM) of original scale structure on wing.
Figure 13 is the high power transmission electron microscope picture (HRTEM) of the sample after high temperature cabonization of black cicada wing shown in Figure 12.
Figure 14 is the optical photograph of russet ash dragonfly and the scanning electron microscope (SEM) photograph (SEM) of original scale structure on wing.
Figure 15 is the high power transmission electron microscope picture (HRTEM) of russet ash dragonfly wing sample after high temperature cabonization shown in Figure 14.
Specific embodiment
Further illustrate the present invention by following examples.Embodiment is merely exemplary, and nonrestrictive.
Embodiment 1
Caste is greenbelt Papilio bianor, and slaine is iron chloride, and nitrogen content is 2.7at%.
Comprise the following steps that：
(1) take eight greenbelt Papilio bianor wings (about 0.14g), put into equipped with the deionized water heating kettle of 40mL, 100
Hydro-thermal reaction 2 hours in DEG C baking oven, after being cooled to room temperature, takes out wing, puts in 60 DEG C of baking ovens and be dried 12 hours；
(2) eight greenbelt Papilio bianor wings being dried in step (1) are taken to be immersed in the ethanol having dissolved 0.84g iron chloride
In solution, put in lyophilizing instrument, in subzero 80 DEG C of lyophilisation 48 hours；
(3) by the good wing of lyophilizing in step (2), put in crucible, in nitrogen atmosphere, in 1000 DEG C of tube furnace
Middle calcining 2 hours, is then cooled to room temperature；
(4) product in step (3) is taken out from tube furnace, that is, obtain Graphene/graphite composite.
Fig. 1 a be the optical photograph of greenbelt Papilio bianor it is known that wing body is black, wing expanse about 11mm；Fig. 1 b is greenbelt Papilio bianor
The low power scanning electron microscope (SEM) photograph (SEM) of wing is it can be seen that wing is to be covered by countless scale structures；Fig. 1 c-d is squama on wing
It can be seen that this scale is the neat network pore space structure of rule, aperture is 0.5- to the high power scanning electron microscope (SEM) photograph (SEM) of chip architecture
1μm.
Fig. 2 a is the low power scanning electron microscope (SEM) photograph (SEM) of scale structure after high temperature cabonization for the greenbelt Papilio bianor wing, can
To find out that the stephanoporate framework obtaining after high temperature cabonization still remains original scale structure；Fig. 2 b is greenbelt Papilio bianor wing
The high power scanning electron microscope (SEM) photograph (SEM) of scale structure after high temperature cabonization for the wing it can be seen that stephanoporate framework surface be coated with thin
Membranaceous material.
Fig. 3 be scale structure after high temperature cabonization for the greenbelt Papilio bianor wing transmission electron microscope picture (TEM) it is known that with sweep
Retouch electron microscope (Fig. 2) observed result consistent.
Fig. 4 is the high power transmission electron microscope picture (HRTEM) of the wing of greenbelt Papilio bianor shown in Fig. 3 sample after high temperature cabonization,
It is clearly visible the complex that resulting materials are Graphene-graphite.
Fig. 5 is the scattergram of different number of plies Graphenes in the wing sample after high temperature cabonization of greenbelt Papilio bianor shown in Fig. 3,
Understand that the Graphene ratio in prepared Graphene/graphite composite has reached 66%.
Fig. 6 is the x-ray photoelectron energy spectrum diagram of carbon in the Papilio bianor wing sample after high temperature cabonization of greenbelt
(XPS) it is known that the combination of carbon is the C=C key of Graphene.
Fig. 7 is the x-ray photoelectron energy spectrum diagram of nitrogen in the Papilio bianor wing sample after high temperature cabonization of greenbelt
(XPS) it is known that the existence form of nitrogen has four kinds, it is pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen and nitrogen oxide respectively；Nitrogen content is
2.7at%.
Fig. 8 is the x-ray photoelectron energy spectrum diagram of ferrum element in the Papilio bianor wing sample after high temperature cabonization of greenbelt
(XPS) it is known that iron determination has+3 and+2, the content of ferrum is 17.2at%.
Fig. 9 a is the nitrogen adsorption desorption curve of greenbelt Papilio bianor wing sample after high temperature cabonization it is known that resulting materials
Specific surface is 776m2/g；Fig. 8 b is the graph of pore diameter distribution of greenbelt Papilio bianor wing sample after high temperature cabonization it is known that gained material
Material micropore diameter concentrates on 0.7 and 1.2nm, mesoporous concentrates on 3.9nm.
Embodiment 2
Caste is greenbelt Papilio bianor, and described slaine is ferric nitrate.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the chlorination in step 2
Ferrum is changed to ferric nitrate.
Embodiment 3
Caste is greenbelt Papilio bianor, and described slaine is iron sulfate.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the chlorination in step 2
Ferrum is changed to iron sulfate.
Embodiment 4
Caste is greenbelt Papilio bianor, and described slaine is thiocyanation ferrum.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the chlorination in step 2
Ferrum is changed to thiocyanation ferrum.
Embodiment 5
Caste is greenbelt Papilio bianor, and described slaine is haemachrome.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the chlorination in step 2
Ferrum is changed to haemachrome, and butterfly's wing is 2.5 with the mass ratio of haemachrome:1.
The high power transmission electron microscope picture of the Graphene/graphite product being obtained is shown in accompanying drawing 10 it is known that under the catalysis of haemachrome,
Wing can also obtain the complex of Graphene-graphite through high temperature cabonization.
Embodiment 6
Caste is greenbelt Papilio bianor, and described slaine is iron chloride.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the freezing in step 2
Drying is changed to drying.
Embodiment 7
Caste is Japanese Sasakia charonda, and described slaine is iron chloride.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the greenbelt in step 1
Papilio bianor is changed to Japanese Sasakia charonda.
The optical photograph of described Japan Sasakia charonda and scanning electron microscope (SEM) photograph (SEM) are as shown in figure 11.Figure 11 a can be seen that wing
In atropurpureuss, there is white dot；Figure 11 b-c can be seen that and covers scale on Japanese Sasakia charonda, but scale structure is green with greenbelt
Papilio xuthus (Linne)． is had any different, and hole shape is rectangle, and aperture is 1-3 μm.
Embodiment 8
Caste is sulphur butterfly, and described slaine is iron chloride.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the greenbelt in step 1
Papilio bianor is changed to sulphur butterfly.
Embodiment 9
Caste is black cicada, and described slaine is iron chloride.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to black cicada wing.
The optical photograph of described black cicada wing and scanning electron microscope (SEM) photograph (SEM) are as shown in figure 12.Figure 12 a can be seen that wing is in
Transparent；Figure 12 b can be seen that irregular ridge vein texture on wing；Figure 12 c can be seen that Cicadae wing surface has ridge arteries and veins, no scale
Structure, wing is distributed circular papillary structure.
The transmission electron microscope picture of obtained Graphene/graphite sample sees accompanying drawing 13 it is known that under iron salt catalysis, Cicadae wing can turn
Turn to Graphene-graphite composite.
Embodiment 10
Caste is black cicada, and described slaine is ferric nitrate.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to black cicada wing, and the iron chloride in step 2 is changed to ferric nitrate.
Embodiment 11
Caste is black cicada, and described slaine is iron sulfate.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to black cicada wing, and the iron chloride in step 2 is changed to iron sulfate.
Embodiment 12
Caste is black cicada, and described slaine is thiocyanation ferrum.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to black cicada wing, and the iron chloride in step 2 is changed to thiocyanation ferrum.
Embodiment 13
Caste is black cicada, and described slaine is haemachrome.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to black cicada wing, and the iron chloride in step 2 is changed to haemachrome.
Embodiment 14
Caste is russet ash dragonfly, and described slaine is iron chloride.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to russet ash dragonfly wing.
The optical photograph of described russet ash dragonfly wing and scanning electron microscope (SEM) photograph (SEM) are as shown in figure 14.Figure 14 a can be seen that wing
Transparent；Figure 11 b can be seen that irregular ridge vein texture on wing；Figure 11 c can be seen that wing surface no scale structure, has
The substantial amounts of square papillary structure being vertically arranged.
The transmission electron microscope picture of obtained Graphene/graphite sample see accompanying drawing 15 it is known that iron salt catalysis under, russet ash dragonfly wing
Wing can be converted into Graphene-graphite composite.
Embodiment 15
Caste is russet ash dragonfly, and described slaine is ferric nitrate.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to russet ash dragonfly wing, and the iron chloride in step 2 is changed to ferric nitrate.
Embodiment 16
Caste is russet ash dragonfly, and described slaine is iron sulfate.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to russet ash dragonfly wing, and the iron chloride in step 2 is changed to iron sulfate.
Embodiment 17
Caste is russet ash dragonfly, and described slaine is thiocyanation ferrum.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to russet ash dragonfly wing, and the iron chloride in step 2 is changed to thiocyanation ferrum.
Embodiment 18
Caste is russet ash dragonfly, and described slaine is haemachrome.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is：By the butterfly in step 1
Wing is changed to russet ash dragonfly wing, and the iron chloride in step 2 is changed to haemachrome.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (6)
1. a kind of method preparing Graphene and graphene-based material for raw material with insect wing, has following steps：
(1) take insect wing, put into equipped with the container of deionized water, little with water heating 0.5-48 in baking oven more than room temperature
When, after being cooled to room temperature, take out insect wing, put in baking oven and be dried；
(2) insect wing weighing the drying of step (1) is immersed in the ethanol solution being dissolved with slaine, insect wing with
The mass ratio of slaine is 0.001～1000, puts in lyophilizing instrument, lyophilisation 24-72 hour；
(3) by the good insect wing of lyophilizing in step (2), put in crucible, in inert atmosphere, in 500 in tube furnace
～2000 DEG C of calcining 1-10 hour, is subsequently cooled to room temperature；
(4) product in step (3) is taken out from tube furnace, that is, obtain Graphene and graphene-based material.
2. a kind of method that Graphene and graphene-based material are prepared for raw material with insect wing according to claim 1,
It is characterized in that, the insect wing of described step (1) is the wing of common butterfly, Aeschna melanictera and Cicadae.
3. a kind of method that Graphene and graphene-based material are prepared for raw material with insect wing according to claim 1,
It is characterized in that, the slaine of described step (2) is the salt of the metal having catalytic action to graphene growth：Iron chloride, nitric acid
Fall, thiocyanation ferrum, iron sulfate or haemachrome.
4. a kind of method that Graphene and graphene-based material are prepared for raw material with insect wing according to claim 1,
It is characterized in that, the lyophilisation of described step (2) can also be dried.
5. according to claim 1 a kind of Graphene and the preparation side of graphene-based material are prepared for raw material with insect wing
Method is it is characterised in that the inert atmosphere of described step (3) is nitrogen or argon gas atmosphere.
6. according to claim 1 a kind of Graphene and the preparation side of graphene-based material are prepared for raw material with insect wing
Method it is characterised in that graphene-based material be the complex of Graphene and graphite, the Graphene doped with nitrogen and doped with nitrogen
Graphene-graphite composite.
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