CN105731446B - The preparation method and product of a kind of sulfur and nitrogen co-doped porous graphene of superhigh specific surface area - Google Patents

The preparation method and product of a kind of sulfur and nitrogen co-doped porous graphene of superhigh specific surface area Download PDF

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CN105731446B
CN105731446B CN201610268582.0A CN201610268582A CN105731446B CN 105731446 B CN105731446 B CN 105731446B CN 201610268582 A CN201610268582 A CN 201610268582A CN 105731446 B CN105731446 B CN 105731446B
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nitrogen
sulfur
surface area
specific surface
graphene
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CN105731446A (en
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黄云辉
张建
胡培
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NANJING TONGNING NEW MATERIAL RESEARCH INSTITUTE Co.,Ltd.
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Huazhong University of Science and Technology
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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
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • 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
    • 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

Abstract

The invention discloses a kind of preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area and product, this method includes：It is raw material from the biological material containing keratin, using it simultaneously as solid carbon, nitrogen, sulfur feedstock, carbonization preliminary first, then adsorbed by alkaline solution decompression, then by high-temperature activation processing, then pickling vacuum drying obtains graphene.Using the special chain of keratin and cyclic structure, biomass keratin is converted into the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area.The nitrogen content of graphene may be up to more than 5.0at.%, and sulfur content reaches more than 1.0at.%, and specific surface area is up to 1500m2/ more than g, and in porous foam shape structure.The raw material sources that the present invention is used are extensively, cheap, are prepared as graphene, not only lift its application value, also efficiently solve these wastes and abandon brought environmental problem, with the simple efficient, low cost and other advantages of preparation.

Description

The preparation method and product of a kind of sulfur and nitrogen co-doped porous graphene of superhigh specific surface area
Technical field
It is sulfur and nitrogen co-doped more particularly, to a kind of superhigh specific surface area the invention belongs to grapheme material preparation field The preparation method and product of porous graphene.
Background technology
In many Carbon Materials, the focus that graphene is studied due to its special structure and property as current people.Stone The two-dimensional periodic structure that black alkene is made up of carbon hexatomic ring, this special structure makes it have many peculiar properties, such as Room-temperature quantum Hall effect, ferromagnetism, superconductivity and giant magnetoresistance effect etc..In addition, graphene also have excellent thermal property, Electric property, mechanical property and very high chemical stability and thermodynamic stability, make it in nano-device, battery/super The field such as capacitor, composite and hydrogen storage material, catalyst shows potential application prospect.However, due to graphene There is no band gap so that its electrical conductance can not completely be controlled as traditional semiconductor, and graphenic surface it is smooth and It is inert, be unfavorable for it is compound with other materials, so as to hinder the extensive use of graphene to a certain extent.
In recent years, researcher has found to carry out chemical doping to graphene, can effectively its structure of modulation and performance, and then Realize the function of graphene and its associated materials more horn of plenty and wide application.The member procatarxis such as N, S can effectively open graphene Band gap, can adjust its conduction type (conversion between p-type and n-type semiconductor is realized by doping), change its electronics Structure, so as to improve its free carrier density, increases its electric conductivity and stability.It is traditional main with vapour deposition process (CVD) N, S doping and its S and N codope graphenes are prepared, but its preparation process is very cumbersome, not only needs metallic catalyst and silicon chip Etc. template, in addition it is also necessary to complicated vacuum systems, mass produce with high costs, it is difficult to realize that it is commercialized.In addition, directly High-temperature calcination mixing containing the macromolecule such as N, S and its polymer precursor (melamine, ammoniacal liquor etc.) and graphene/graphene oxide Compound, and by graphene-based derivative in the (NH of gas containing hetero atom3, H2S, HCN) etc. be heat-treated under atmosphere, can also obtain To monatomic doping or diatomic doped graphene.But graphene specific surface area prepared by both approaches is not universal high< 900m2/ g, and preparation process is complex is mixed again, it is necessary to first prepare graphene oxide, or need complicated organic gas Body environment, this is all unfavorable for its popularization, and how poisonous and harmful polymer precursor and organic gas be, seriously threatens health. In addition, CN201510201085.4 discloses a kind of Animal Bone base class graphene lithium ion battery negative material and preparation method thereof, It uses Animal Bone as raw material, and by carbonization, activation and graphitization, graphite is made with reference to the heat treatment under certain temperature Alkene, this method needs to need pyrolytic conversion to be graphene after high-temperature activation, and activation, and preparation technology is complicated, and cost is high, the stone of acquisition Black alkene is commonly undoped, and in the graphene of layer structure.Therefore, a kind of new mild condition is invented simply to prepare High-specific surface area doped graphene MATERIALS METHODS, particularly prepares complex sulphur nitrogen diatomic doping, very with reality Value.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, it is co-doped with the invention provides a kind of superhigh specific surface area sulphur nitrogen The preparation method and product of miscellaneous porous graphene, wherein using the special chain and cyclic structure of keratin, by biomass angle egg The white sulfur and nitrogen co-doped porous graphene for being converted into superhigh specific surface area, the nitrogen content of gained graphene may be up to More than 5.0at.%, sulfur content reaches more than 1.0at.%, and specific surface area is up to 1500m2/ more than g, and show porous bubble Foam shape graphene-structured, its raw material sources used are extensively, cheap, are prepared as graphene, and not only lifting it should With value, also efficiently solve these wastes and abandon brought environmental problem, it is low excellent with simple and environmentally-friendly, cost is prepared Point.
To achieve the above object, according to one aspect of the present invention, it is proposed that a kind of superhigh specific surface area is sulfur and nitrogen co-doped The preparation method of porous graphene, this method comprises the following steps：
1) biological material containing keratin is cleaned and dried, sample needed for being obtained as carbonization in tube furnace inert atmosphere Product, the biological material simultaneously as solid carbon source, nitrogen source and sulphur source, wherein, the concrete technology of carbonization is set to temperature 200 ~300 DEG C, 1~5h of soaking time, 1~2 DEG C of min of heating rate-1。
2) by step 1) in obtained sample be placed in progress decompression absorption in vacuum glove box alkaline solution, then dried It is dry, sample needed for obtaining；
3) by step 2) in drying sample as in the tube furnace of inert atmosphere, being tentatively warming up to 200~350 DEG C, and 0.5~3h of insulation, is then warming up to 600~900 DEG C again, is incubated 0.5~2h, to carry out activation process, then natural cooling；
4) by step 3) obtained by sample grind rear pickling, suction filtration, and add water and be washed till neutrality；
5) by step 4) obtained by sample be placed in vacuum drying chamber dry, obtain superhigh specific surface area sulfur and nitrogen co-doped Porous graphene.
As it is further preferred that the step 1) in the inert atmosphere that uses for argon gas or nitrogen.
As it is further preferred that the step 2) in used alkaline solution be 0.5~1.0molL-1KOH or NaOH solution.
As it is further preferred that the step 2) in the air pressure that is kept of vacuum glove box be 0~50pa, decompression absorption Time is 1~6h.
As it is further preferred that the step 2) in the temperature of drying be 80 DEG C~100 DEG C, time of drying is 10h ~12h.
As it is further preferred that the step 3) in inert atmosphere be argon gas or nitrogen, step 3) in whole heating Speed is 3~7 DEG C of min-1。
As it is further preferred that the step 4) in pickling be impregnated in pickling 4 in 60~90 DEG C of acid solution~ 10h, acid solution is specially 0.2~0.6molL-1H2SO4, HCl or HNO3。
As it is further preferred that the step 5) in vacuum drying carried out under the conditions of 5Pa~50Pa, drying temperature is 60 DEG C~90 DEG C, drying time is 10h~12h.
As it is further preferred that the biological material containing abundant keratin be animal hair, hoof nail or angle, it is excellent Elect pig hair, ox hair, wool, chicken feather, drake feather, goose feather, pig nail, ox hoof, mountain ebony, ox horn or goat's horn as.
It is another aspect of this invention to provide that sulfur and nitrogen co-doped there is provided a kind of superhigh specific surface area prepared by methods described Porous graphene, the sulfur and nitrogen co-doped porous graphene is in porous foam shape structure, and its specific surface area is more than 1500m2/ g, nitrogen member Cellulose content reaches more than 5.0at.%, and sulfur content reaches more than 1.0at.%.
In general, possess following compared with prior art, mainly by the contemplated above technical scheme of the present invention Technological merit：
1. the present invention is from the biomass for enriching keratin is contained such as animal hair, hoof nail as raw material, by it As unique presoma, while as solid carbon source, nitrogen source and sulphur source, directly preparing sulfur and nitrogen co-doped with high-specific surface area Porous graphene, the raw material sources are extensive, environmental protection is friendly, cost is low, realize animal hair, the recycling of hoof nail, reduce Environmental pollution, is not only to prepare Heteroatom doping porous graphene there is provided a kind of new way, improves biological material Application value, also there is certain promotion meaning to optimizing the environment.The presoma selected compared to conventional method, the forerunner that the present invention is selected Body is single, without the mixing of traditional multiple material, greatlys save raw material, reduction graphene prepares cost, and raw material are nontoxic, It is beneficial to large-scale production.
2. the present invention is studied and set to the technique and parameter of each step, obtained by continuous development test Technological parameter most preferably is obtained, by the mutual cooperation of each technique, obtained sulfur and nitrogen co-doped porous graphene has superelevation Specific surface area, up to 1500m2/ more than g, is twice or even several times of the graphene specific surface area that conventional method is prepared；And Heteroatom doping is very efficient in graphene, and wherein nitrogen element content reaches more than 5.0at.%, reach as high as 8.0at.% with On, sulfur content reaches more than 1.0at.%, much higher than with conventional method doping gained, in addition, the graphene prepared has Traditional preparation methods are difficult to obtained graphene blister pattern, and the graphene with the pattern has excellent meso-hole structure, energy Enough it is effectively promoted the transmission of three phase boundary reactive material.
3. the present invention adsorbs hybrid technique in preparation from decompression, highly efficient compared to mixed methods such as tradition stirrings, Mixing is more uniformly distributed；In high-temperature process, without special vacuum environment and complicated organic gas environment, technique is simple, Running cost is low.
4. selected biomass hair of the invention etc. prepares graphene, low-temperature carbonization and 900 DEG C and its temperature below are only needed Activation can be converted into graphene, and graphene directly can be converted into activation step, and preparation technology is more simple, More, energy is saved, reduction prepares cost.
Brief description of the drawings
Fig. 1 (a) is the transmission electron microscope of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the gained of the embodiment of the present invention 1 (TEM) figure；
Fig. 1 (b) is the high power transmission of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the gained of the embodiment of the present invention 1 Electronic Speculum (HR-TEM) figure；
Fig. 2 is the nitrogen adsorption desorption of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the gained of the embodiment of the present invention 1 Figure；
Fig. 3 is the Raman (Raman) of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the gained of the embodiment of the present invention 1 Figure；
Fig. 4 is the x-ray photoelectron of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the gained of the embodiment of the present invention 1 Power spectrum (XPS) figure.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below Not constituting conflict each other can just be mutually combined.
The invention provides a kind of side that biomass keratin is converted into the sulfur and nitrogen co-doped graphene of superhigh specific surface area Method.Animal hair, hoof nail, angle in biology etc. contain the members such as abundant sulphur, nitrogen and carbon containing abundant keratin, keratin Element.The characteristics of present invention is using biomass, is raw material from common animal nails, angle, hair etc., using it simultaneously as solid Body carbon, nitrogen, sulfur feedstock, carbonization treatment preliminary first, then by depressurizing absorption mixing KOH or NaOH alkaline solutions, in tube furnace Middle low temperature further goes water process and high-temperature activation to handle, and then pickling vacuum drying obtains graphene.Utilize the spy of keratin Different chain and cyclic structure, sulfur and nitrogen co-doped graphene is converted into by this natural biomass keratin.Due in height In warm activation process, keratin this special chain and its ring molecule, it is easy to acted synergistically and reset by K, Na etc., connected again Connect to form graphene-structured, and because of metal potassium ion and the H of generation2O、H2、CO、CO2Deng gas during high-temperature activation in material Non-directional shuttles in material, can form substantial amounts of hole, greatly increase the surface area of graphene.Therefore, with biomass angle egg It is in vain presoma, the sulfur and nitrogen co-doped porous graphene of high-specific surface area can be translated into by the experimental program of setting.
A kind of method for preparing the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the present invention, specifically includes following step Suddenly：
1) by the biological material containing abundant keratin such as animal hair, hoof nail or angle, preferably pig hair, ox hair, Wool, chicken feather, drake feather, goose feather, pig nail, ox hoof, mountain ebony, ox horn or goat's horn, clean and dry, then lazy as tube furnace Property atmosphere in preliminary carbonization obtain needed for sample, the biological material is used as solid carbon source, nitrogen source and sulphur source simultaneously.
Wherein, the inert atmosphere used is argon gas or nitrogen, and preliminary carburizing temperature is 200 DEG C~300 DEG C, and soaking time is 1h~5h, heating rate is 1 DEG C of min-1~2 DEG C of min-1.In the process, using temperature increasing schedule at a slow speed, be conducive to pair Raw material carry out preexpanding, remove the crystallization water in raw material, enough ducts and gap are provided for follow-up mixed active material.
2) by step 1) in obtained sample be placed in vacuum glove box alkaline solution, decompression absorption some hours, then Dried as in common drying box.Decompression is adsorbed with the deep layer duct for entering material beneficial to solution, beneficial to activation；And in drying box Remove solvent.
Wherein, alkaline solution used is 0.5molL-1~1.0molL-1KOH or NaOH solution；Vacuum glove The air pressure that case is kept is 0~50pa, and decompression adsorption time is 1h~6h；The drying temperature of drying box is 80 DEG C~100 DEG C, is dried The dry time is 10h~12h.
3) by step 2) in drying sample as in the tube furnace of inert atmosphere, being tentatively warming up to certain temperature and protect Temperature, then it is warming up to activation temperature insulation a period of time, to carry out activation process, then natural cooling.Inert atmosphere (argon gas or Nitrogen) processing front section primarily to further removing the crystallization water in material, follow-up processing is mainly to sample Effectively activated.
Wherein, inert atmosphere be argon gas or nitrogen, the temperature for tentatively heating up and keeping be 200 DEG C~350 DEG C, soaking time For 0.5h~3h；The activation temperature of activation process is 600 DEG C~900 DEG C, and soaking time is 0.5h~2h；Whole heating rate is 3℃·min-1~7 DEG C of min-1。
4) by step 3) obtained by sample grind rear pickling, suction filtration, and add water and be washed till neutrality.
Wherein, pickling is specially to be impregnated in pickling 4h~10h in 60 DEG C~90 DEG C of acid solution, and acid solution is specially 0.2mol·L-1~0.6molL-1H2SO4, HCl or HNO3.Suction filtration instrument uses water circulating pump, and pressure is 10Pa or so. And deionized water rinsing is used repeatedly 3-5 times, impurity and soluble substance inside removal.Sample can effectively be removed by said process In alkali metal (K and Na) compound and soluble impurity, obtain the sample of higher degree.
5) by step 4) obtained by sample be placed in vacuum drying chamber dry, obtain superhigh specific surface area sulfur and nitrogen co-doped Porous graphene.
Wherein, vacuum drying is carried out under the conditions of 5Pa~50Pa, and drying temperature is 60 DEG C~90 DEG C, and drying time is 10h ~12h.
Certainly, the preparation method of sulfur and nitrogen co-doped high specific surface area porous graphene of the invention, be not only applicable to Upper listed animal hair and hoof nail etc., and apply to all materials containing keratin.
It is below the specific embodiment of the present invention.
Embodiment 1
1) pig hair is cleaned and dried, is tentatively carbonized as in tube furnace argon gas atmosphere, being warming up to 300 DEG C, soaking time is 2h, heating rate is 1 DEG C of min-1；
2) by step 1) in obtained sample be placed in vacuum glove box 0.5molL-1In KOH, decompression absorption 2h, air pressure is set 10pa is set to, and as 80 DEG C of drying 12h in common drying box；
3) by step 2) in sample as in tube furnace, keep argon gas atmosphere, be warming up to 350 DEG C, be incubated 0.5h, then heat up To 800 DEG C, 1h is incubated, heating rate is 5 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom is impregnated in 0.5molL after grinding-1H2SO480 DEG C of constant temperature pickling 8h in solution Afterwards, suction filtration, and add water and be washed till neutrality；
5) by step 4) gained sample is placed in vacuum drying chamber (pressure is 5pa, temperature be 60 DEG C) and dries 12h and surpassed The sulfur and nitrogen co-doped porous graphene of high-specific surface area.
Shown in the structure of the sulfur and nitrogen co-doped porous graphene of gained such as Fig. 1 (a), 1 (b), wherein Fig. 1 (a) is gained stone Transmission electron microscope (TEM) figure of black alkene, it can be seen that graphene balloon-shaped structure and microcellular structure.Fig. 1 (b) is the height of gained graphene Times transmission electron microscope (HR-TEM) figure, graphene stacked and its balloon-shaped structure are high-visible.The sulfur and nitrogen co-doped porous graphite of gained The specific surface area of alkene is as shown in Fig. 2 up to 1799m2/g.Fig. 3 is Raman spectrum (Raman) figure of gained graphene, 2655cm-1Place occurs in that graphene 2D peaks, shows the presence for having graphene-structured.The group of the sulfur and nitrogen co-doped porous graphene of gained Point result is as shown in figure 4, as can be seen from the figure the graphene mainly contains tetra- kinds of elements of C, N, O, N, the wherein content of N element For 8.25at.%, the content of element sulphur is 1.29at.%.
Embodiment 2
1) chicken feather is cleaned and dried, is tentatively carbonized as in tube furnace argon gas atmosphere, being warming up to 250 DEG C, soaking time is 3h, heating rate is 2 DEG C of min-1；
2) by step 1) in obtained sample be placed in glove box 0.7molL-1In NaOH, decompression absorption 1h, air pressure is set 5pa is set to, and as 90 DEG C of drying 11h in common drying box；
3) by step 2) in sample as in tube furnace, keep argon gas atmosphere, be warming up to 200 DEG C, be incubated 1h, then be warming up to 700 DEG C, 1h is incubated, heating rate is 3 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom is impregnated in 0.3molL after grinding-1HCl solution in after 90 DEG C of constant temperature pickling 5h, Suction filtration, and add water and be washed till neutrality；
5) by step 4) gained sample is placed in vacuum drying chamber (pressure is 40pa, temperature be 70 DEG C) and dries 11h and obtain The sulfur and nitrogen co-doped porous graphene of superhigh specific surface area.
The specific surface area of the sulfur and nitrogen co-doped porous graphene of gained is 1622m2/ g, the content of nitrogen is 6.93at.%, The content of element sulphur is 1.67at.%.
Embodiment 3
1) drake feather is cleaned and dried, is tentatively carbonized as in tube furnace argon gas atmosphere, being warming up to 200 DEG C, soaking time is 4h, heating rate is 1.5 DEG C of min-1；
2) by step 1) in obtained sample be placed in glove box 0.8molL-1In KOH, decompression absorption 3h, air pressure is set For 20pa, and as 100 DEG C of drying 10h in common drying box；
3) by step 2) in sample as in tube furnace, keep argon gas atmosphere, be warming up to 300 DEG C, be incubated 1h, then be warming up to 600 DEG C, 0.5h is incubated, heating rate is 4 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom is impregnated in 0.6molL after grinding-1Hydrochloric acid solution in 90 DEG C of constant temperature pickling 10h Afterwards, suction filtration, and add water and be washed till neutrality；
5) by step 4) gained sample is placed in vacuum drying chamber (pressure is 25pa, temperature be 90 DEG C) and dries 10h and obtain The sulfur and nitrogen co-doped porous graphene of superhigh specific surface area.
The specific surface area of the sulfur and nitrogen co-doped porous graphene of gained is 1708m2/ g, the content of nitrogen is 6.65at.%, The content of element sulphur is 1.42at.%.
Embodiment 4
1) goose feather is cleaned and dried, is tentatively carbonized as in tube furnace argon gas atmosphere, being warming up to 275 DEG C, soaking time is 3h, heating rate is 1.7 DEG C of min-1；
2) by step 1) in obtained sample be placed in glove box 0.4molL-1In KOH, decompression absorption 1h, air pressure is set For 10pa, and as drying 11.5h in common 70 DEG C of drying box；
3) by step 2) in sample as in tube furnace, keep nitrogen atmosphere, be warming up to 300 DEG C, be incubated 1.5h, then heat up To 900 DEG C, 1h is incubated, heating rate is 6 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom is impregnated in 0.5molL after grinding-1HNO370 DEG C of constant temperature pickling 11h in solution Afterwards, suction filtration, and add water and be washed till neutrality；
5) by step 4) gained sample is placed in vacuum drying chamber (pressure is 15pa, temperature be 80 DEG C) and dries 10.5h and obtain To the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area.
The specific surface area of the sulfur and nitrogen co-doped porous graphene of gained is 1502m2/ g, the content of nitrogen is 5.43at.%, The content of element sulphur is 1.04at.%.
Embodiment 5
1) ox hair is cleaned and dried, is tentatively carbonized as in tube furnace argon gas atmosphere, being warming up to 300 DEG C, soaking time is 3h, heating rate is 1 DEG C of min-1；
2) by step 1) in obtained sample be placed in glove box 0.9molL-1In NaOH, decompression absorption 4h, air pressure is set 40pa is set to, and as 100 DEG C of drying 10h in common drying box；
3) by step 2) in sample as in tube furnace, keep argon gas atmosphere, be warming up to 350 DEG C, be incubated 0.5h, then heat up To 700 DEG C, 2h is incubated, heating rate is 5 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom is impregnated in 0.6molL after grinding-1H2SO460 DEG C of constant temperature pickling 8h in solution Afterwards, suction filtration, and add water and be washed till neutrality；
5) by step 4) gained sample is placed in vacuum drying chamber (pressure is 5pa, temperature be 90 DEG C) and dries 10h and surpassed The sulfur and nitrogen co-doped porous graphene of high-specific surface area.
The specific surface area of the sulfur and nitrogen co-doped porous graphene of gained is 1709m2/ g, the content of nitrogen is 6.65at.%, The content of element sulphur is 1.09at.%.
Embodiment 6
1) wool is cleaned and dried, is tentatively carbonized as in tube furnace argon gas atmosphere, being warming up to 300 DEG C, soaking time is 1h, heating rate is 2 DEG C of min-1；
2) by step 1) in obtained sample be placed in glove box 0.6molL-1In KOH, decompression absorption 4h, air pressure is set For 5pa, and as 90 DEG C of drying 11h in common drying box；
3) by step 2) in sample as in tube furnace, keep nitrogen atmosphere, be warming up to 300 DEG C, be incubated 2h, then be warming up to 800 DEG C, 1.2h is incubated, heating rate is 3 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom is impregnated in 0.5molL after grinding-1HCl solution in after 90 DEG C of constant temperature pickling 6h, Suction filtration, and add water and be washed till neutrality；
5) by step 4) gained sample is placed in vacuum drying chamber (pressure is 10pa, temperature be 90 DEG C) and dries 10h and obtain The sulfur and nitrogen co-doped graphene of superhigh specific surface area.
The specific surface area of the sulfur and nitrogen co-doped graphene of gained is 1584m2/ g, the content of nitrogen is 5.87at.%, sulphur member The content of element is 1.19at.%.
Embodiment 7
1) ox hoof is cleaned and dried, is tentatively carbonized as in tube furnace argon gas atmosphere, being warming up to 300 DEG C, soaking time For 3h, heating rate is 1.2 DEG C of min-1；
2) by step 1) in obtained sample be placed in glove box 1.0molL-1In KOH, decompression absorption 4h, air pressure is set For 3pa, and as 85 DEG C of drying 11.5h in common drying box；
3) by step 2) in sample as in tube furnace, keep nitrogen atmosphere, be warming up to 280 DEG C, be incubated 2h, then be warming up to 800 DEG C, 2h is incubated, heating rate is 6 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom is impregnated in 0.3molL after grinding-1H2SO490 DEG C of constant temperature pickling 12h in solution Afterwards, suction filtration, and add water and be washed till neutrality；
5) by step 4) gained sample is placed in vacuum drying chamber (pressure is 5pa, temperature be 85 DEG C) and dries 10.5h and obtain The sulfur and nitrogen co-doped porous graphene of superhigh specific surface area.
The specific surface area of the sulfur and nitrogen co-doped porous graphene of gained is 1726m2/ g, the content of nitrogen is 5.25at.%, The content of element sulphur is 1.26at.%.
Embodiment 8
1) goat's horn is cleaned and dried, is tentatively carbonized as in tube furnace argon gas atmosphere, being warming up to 300 DEG C, soaking time is 3h, heating rate is 1.8 DEG C of min-1；
2) by step 1) in obtained sample be placed in glove box 1.0molL-1In NaOH, decompression absorption 3h, air pressure is set 10pa is set to, and as 88 DEG C of drying 11.6h in common drying box；
3) by step 2) in sample as in tube furnace, keep argon gas atmosphere, be warming up to 300 DEG C, be incubated 3h, then be warming up to 900 DEG C, 2h is incubated, heating rate is 3 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom is impregnated in 0.5molL after grinding-1HCl acid solutions in 80 DEG C of constant temperature pickling 4h Afterwards, suction filtration, and add water and be washed till neutrality；
5) by step 4) gained sample is placed in vacuum drying chamber (pressure is 5pa, temperature be 90 DEG C) and dries 10h and surpassed The sulfur and nitrogen co-doped porous graphene of high-specific surface area.
The specific surface area of the sulfur and nitrogen co-doped porous graphene of gained is 1656m2/ g, the content of nitrogen is 6.30at.%, The content of element sulphur is 1.06at.%.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include Within protection scope of the present invention.

Claims (11)

1. a kind of preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area, it is characterised in that this method is included such as Lower step：
1) biological material containing keratin is cleaned and dried, be placed in carbonization in tube furnace inert atmosphere and obtain required sample, The biological material simultaneously as solid carbon source, nitrogen source and sulphur source, wherein, the concrete technology of carbonization be set to temperature 200~ 300 DEG C, 1~5h of soaking time, 1~2 DEG C of min of heating rate-1；
2) by step 1) in obtained sample be placed in progress decompression absorption in vacuum glove box alkaline solution, then dried, Sample needed for obtaining；
3) by step 2) in drying sample as in the tube furnace of inert atmosphere, be tentatively warming up to 200~350 DEG C, and be incubated 0.5~3h, is then warming up to 600~900 DEG C again, is incubated 0.5~2h, to carry out activation process, then natural cooling；
4) by step 3) obtained by sample grind rear pickling, suction filtration, and add water and be washed till neutrality；
5) by step 4) obtained by sample be placed in vacuum drying chamber and dry, obtain sulfur and nitrogen co-doped porous of superhigh specific surface area Graphene.
2. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 1, its feature exists In the step 1) in the inert atmosphere that uses for argon gas or nitrogen.
3. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 2, its feature exists In the step 2) in used alkaline solution be 0.5~1.0molL-1KOH or NaOH solution.
4. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 3, its feature exists In the step 2) in the air pressure that is kept of vacuum glove box be 0~50Pa, decompression adsorption time is 1~6h.
5. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 4, its feature exists In the step 2) in the temperature of drying be 80 DEG C~100 DEG C, time of drying is 10h~12h.
6. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 5, its feature exists In the step 3) in inert atmosphere be argon gas or nitrogen, step 3) in whole heating rate be 3~7 DEG C of min-1。
7. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 6, its feature exists In the step 4) in pickling be to be impregnated in 4~10h of pickling in 60~90 DEG C of acid solution, acid solution is specially 0.2~ 0.6mol·L-1H2SO4, HCl or HNO3。
8. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 7, its feature exists In the step 5) in vacuum drying carried out under the conditions of 5Pa~50Pa, drying temperature is 60 DEG C~90 DEG C, and drying time is 10h~12h.
9. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 8, its feature exists In the biological material containing keratin is animal hair, hoof nail or angle.
10. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 9, its feature exists In the biological material containing keratin is pig hair, ox hair, wool, chicken feather, drake feather, goose feather, pig nail, ox hoof, sheep Hoof nail, ox horn or goat's horn.
11. the sulfur and nitrogen co-doped porous graphite of superhigh specific surface area prepared by a kind of method as described in claim any one of 1-10 Alkene, it is characterised in that the sulfur and nitrogen co-doped porous graphene is in porous foam shape structure, its specific surface area is more than 1500m2/ g, Nitrogen element content reaches more than 5.0at.%, and sulfur content reaches more than 1.0at.%.
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