CN105731446A - Preparation method and product of ultrahigh-specific-area sulphur-nitrogen-co-doped porous graphene - Google Patents
Preparation method and product of ultrahigh-specific-area sulphur-nitrogen-co-doped porous graphene Download PDFInfo
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Abstract
The invention discloses a preparation method and product of ultrahigh-specific-area sulphur-nitrogen-co-doped porous graphene.The method includes the steps of selecting a keratin-containing biomass material as the raw material, using the biomass material as the solid carbon, nitrogen and sulphur raw material at the same time, conducting preliminary carbonization, conducting pressure reduction adsorption through an alkaline solution, conducting high-temperature activating, conducting acid pickling and vacuum drying to obtain graphene, and directly converting biomass keratin into the ultrahigh-specific-area sulphur-nitrogen-co-doped porous graphene.The nitrogen content of the graphene can reach up to 5.0 at.% or above, the sulphur content reaches 1.0 at.% or above, the specific area reaches up to 1500 m<2>/g or above, and the graphene is of a porous foam-shaped structure.The used raw material is wide in source and low in price, the application of the raw material is improved after the raw material is prepared into the graphene, the environment pollution caused by abandoned waste is effectively solved, and the method has the advantages of being simple and efficient in preparation, low in cost, and the like.
Description
Technical field
The invention belongs to grapheme material preparation field, more particularly, to preparation method and the product of the sulfur and nitrogen co-doped porous graphene of a kind of superhigh specific surface area.
Background technology
In many Carbon Materials, Graphene becomes the focus of current people research due to its special structure and character.The two-dimensional periodic structure that Graphene is made up of carbon hexatomic ring, this special structure makes it have much peculiar character, such as room-temperature quantum Hall effect, ferromagnetism, superconductivity and giant magnetoresistance effect etc..In addition, Graphene also has the thermal property of excellence, electric property, mechanical property and significantly high chemical stability and thermodynamic stability so that it is show potential application prospect in nano-device, battery/ultracapacitor, composite and the field such as hydrogen storage material, catalyst.But, owing to Graphene does not have band gap so that its electrical conductance can not be controlled completely as traditional quasiconductor, and graphenic surface is smooth and inert, is unfavorable for the compound with other materials, thus hindering the extensive use of Graphene to a certain extent.
In recent years, researcher finds Graphene is carried out chemical doping, it is possible to its structure of modulation and performance effectively, and then realizes the function of Graphene and associated materials more horn of plenty thereof and wide application.The unit such as N, S procatarxis can effectively open the band gap of Graphene, its conduction type of adjustable (by the conversion realizing between p-type and n-type semiconductor of adulterating), changing its electronic structure, thus improving its free carrier density, increasing its electric conductivity and stability.Tradition is main prepares N, S doping and S and N codope Graphene thereof with vapour deposition process (CVD), but its preparation process is very loaded down with trivial details, not only need the template such as metallic catalyst and silicon chip, in addition it is also necessary to complicated vacuum systems, large-scale production is with high costs, it is difficult to realize its commercialization.In addition, direct high-temperature calcination is containing the mixture of the macromolecules such as N, S and polymer precursor (tripolycyanamide, ammonia etc.) and graphene/graphene oxide, and by graphene-based derivant containing hetero atom gas (NH3, H2S, HCN) etc. carry out heat treatment under atmosphere, it is possible to obtain monatomic doping or diatomic doped graphene.But the general not high < 900m of Graphene specific surface area prepared by both approaches2/ g, and preparation process is complex, it is necessary to first prepare graphene oxide and mix, or need complicated organic gas environment, this is all unfavorable for that it is promoted, and polymer precursor and the many poisonous and harmfuls of organic gas, serious threat health.Separately, CN201510201085.4 discloses a kind of animal bone base class graphene lithium ion battery negative material and preparation method thereof, it adopts animal bone as raw material, by carbonization, activation and graphitization, prepares Graphene in conjunction with the heat treatment under uniform temperature, the method needs high-temperature activation, and needing pyrolytic conversion after activating is Graphene, complicated process of preparation, cost is high, the Graphene obtained is common undoped, and the Graphene in layer structure.Therefore, invent a kind of new mild condition and simply prepare high-specific surface area doped graphene MATERIALS METHODS, particularly prepare complex sulfur nitrogen diatomic doping, there is real value very much.
Summary of the invention
Disadvantages described above or Improvement requirement for prior art, the invention provides the preparation method of the sulfur and nitrogen co-doped porous graphene of a kind of superhigh specific surface area and product, wherein utilize keratic special chain and circulus, biomass keratin is converted into the sulfur and nitrogen co-doped porous graphene of 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 present the cystose graphene-structured of porous, the raw material sources of its use is extensive, cheap, it is prepared as Graphene, not only promote its using value, also efficiently solve these refuses and abandon the environmental problem brought, have and prepare simple and environmentally-friendly, low cost and other advantages.
For achieving the above object, according to one aspect of the present invention, it is proposed that the preparation method of the sulfur and nitrogen co-doped porous graphene of a kind of superhigh specific surface area, the method comprises the steps:
1) will dry containing keratic biological material is clean, required sample is obtained as carbonization in tube furnace inert atmosphere, this biological material is simultaneously as solid carbon source, nitrogenous source and sulfur source, wherein, the concrete technology of carbonization is set to temperature 200～300 DEG C, temperature retention time 1～5h, 1～2 DEG C of min of heating rate-1。
2) by step 1) in the sample for preparing be placed in vacuum glove box alkaline solution to carry out decompression absorption, then dry, it is thus achieved that required sample；
3) by step 2) in dry sample as, in the tube furnace of inert atmosphere, being tentatively warming up to 200～350 DEG C, and be incubated 0.5～3h, be then warming up to 600～900 DEG C again, be incubated 0.5～2h, to carry out activation processing, then natural cooling；
4) by step 3) sample of gained grinds rear pickling, sucking filtration, and add and be washed to neutrality；
5) by step 4) to be placed in vacuum drying oven dry for the sample of gained, obtains the porous graphene that superhigh specific surface area is sulfur and nitrogen co-doped.
As it is further preferred that described step 1) in the inert atmosphere that adopts be argon or nitrogen.
As it is further preferred that described step 2) in alkaline solution used be 0.5～1.0mol L-1KOH or NaOH solution.
As it is further preferred that described step 2) in the air pressure that keeps of vacuum glove box be 0～50pa, decompression adsorption time is 1～6h.
As it is further preferred that described step 2) in the temperature dried be 80 DEG C～100 DEG C, the time of drying is 10h～12h.
As it is further preferred that described step 3) in inert atmosphere be argon or nitrogen, step 3) in omnidistance heating rate be 3～7 DEG C of min-1。
As it is further preferred that described step 4) in pickling be impregnated in pickling 4～10h in the acid solution of 60～90 DEG C, acid solution is specially 0.2～0.6mol L-1H2SO4, HCl or HNO3。
As it is further preferred that described step 5) in vacuum drying carry out when 5Pa～50Pa, baking temperature is 60 DEG C～90 DEG C, and drying time is 10h～12h.
As it is further preferred that described is animal hair, Bauhinia variegata Linn or angle containing abundant keratic biological material, it is preferred to Pilus Sus domestica, ox hair, Pilus Caprae seu Ovis, chicken feather, drake feather, Pluma Anseris domestica, Unguis Sus domestica, Unguis Bovis seu Bubali, Bauhinia purpurea, Cornu Bovis seu Bubali or Cornu Caprae seu Ovis.
It is another aspect of this invention to provide that provide a kind of sulfur and nitrogen co-doped porous graphene of the superhigh specific surface area prepared by described method, this sulfur and nitrogen co-doped porous graphene is porous foam shape structure, and 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.%.
In general, by the contemplated above technical scheme of the present invention compared with prior art, mainly possess following technological merit:
1. the present invention selects containing abundant keratic biomass such as animal hair, Bauhinia variegata Linn etc. as raw material, it can be used as unique presoma, simultaneously as solid carbon source, nitrogenous source and sulfur source, directly preparation has the sulfur and nitrogen co-doped porous graphene of high-specific surface area, this raw material sources is extensive, environmental protection is friendly, cost is low, achieve the recycling of animal hair, Bauhinia variegata Linn, decrease environmental pollution, it is not only and prepares Heteroatom doping porous graphene and provide a kind of new way, improve the using value of biological material, also necessarily promote meaning to having optimized the environment.Comparing the presoma that traditional method is selected, the presoma that the present invention selects is single, it is not necessary to tradition multiple material mixing, is greatly saved raw material, reduces Graphene preparation cost, and raw material is nontoxic, is of value to large-scale production.
2. technique and the parameter of each step have all been studied and have set by the present invention, best technological parameter is obtained by continuous development test, cooperating by each technique, obtained sulfur and nitrogen co-doped porous graphene has superhigh specific surface area, up to 1500m2/ more than g, is the twice even several times of the Graphene specific surface area that traditional method is prepared；And Heteroatom doping is very efficient in Graphene, wherein nitrogen element content reaches more than 5.0at.%, reach as high as more than 8.0at.%, sulfur content reaches more than 1.0at.%, much higher than with traditional method doping gained, additionally, the Graphene prepared has the Graphene blister pattern that traditional preparation methods is difficult to obtain, the Graphene with this pattern has the meso-hole structure of excellence, it is possible to be effectively promoted the transmission of three phase boundary reacting substance.
3. the present invention selects decompression absorption hybrid technique in preparation, compares the mixed methods such as tradition stirring, and highly efficient, mixing is more uniformly distributed；In high-temperature process, it is not necessary to special vacuum environment and complicated organic gas environment, technique is simple, and running cost is low.
4. biomass hair selected by the present invention etc. prepare Graphene, only needing low-temperature carbonization and 900 DEG C and temperature below activation can be converted into Graphene, and directly can be converted into Graphene in activation step, preparation technology is more simple, more, save energy, reduce preparation cost.
Accompanying drawing explanation
Fig. 1 (a) is transmission electron microscope (TEM) figure of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the embodiment of the present invention 1 gained；
Fig. 1 (b) is high power transmission electron microscope (HR-TEM) figure of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the embodiment of the present invention 1 gained；
Fig. 2 is the nitrogen adsorption desorption figure of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the embodiment of the present invention 1 gained；
Fig. 3 is Raman (Raman) figure of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the embodiment of the present invention 1 gained；
Fig. 4 is x-ray photoelectron power spectrum (XPS) figure of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the embodiment of the present invention 1 gained.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.As long as just can be mutually combined additionally, technical characteristic involved in each embodiment of invention described below does not constitute conflict each other.
The invention provides a kind of method that biomass keratin is converted into the sulfur and nitrogen co-doped Graphene of superhigh specific surface area.Animal hair in biology, Bauhinia variegata Linn, angle etc. are containing abundant keratin, and keratin contains the elements such as abundant sulfur, nitrogen and carbon.The present invention utilizes the feature of biomass, selecting common animal nails, angle, hair etc. is raw material, with it simultaneously as solid carbon, nitrogen, sulfur raw material, first preliminary carbonization treatment, again through decompression absorption mixing KOH or NaOH alkaline solution, in tube furnace, low temperature anhydrates further and processes and high-temperature activation process, and then pickling vacuum drying obtains Graphene.Utilize keratic special chain and circulus, this natural biomass keratin is converted into sulfur and nitrogen co-doped Graphene.Due in high-temperature activation process, this special chain of keratin and ring molecule thereof, it is easy to reset by synergism such as K, Na, reconnect and form graphene-structured, again because of the H of metallic potassium ion and generation2O、H2、CO、CO2Deng gas in high-temperature activation process in the material non-directional shuttle back and forth, substantial amounts of hole can be formed, greatly increase the surface area of Graphene.Therefore, with biomass keratin for presoma, can be translated into, by the experimental program set, the porous graphene that high-specific surface area is sulfur and nitrogen co-doped.
A kind of method preparing the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area of the present invention, specifically includes following steps:
1) will containing abundant keratic biological material such as animal hair, Bauhinia variegata Linn or angle, it is preferably Pilus Sus domestica, ox hair, Pilus Caprae seu Ovis, chicken feather, drake feather, Pluma Anseris domestica, Unguis Sus domestica, Unguis Bovis seu Bubali, Bauhinia purpurea, Cornu Bovis seu Bubali or Cornu Caprae seu Ovis, clean and dry, then obtaining required sample as preliminary carbonization in tube furnace inert atmosphere, this biological material is simultaneously as solid carbon source, nitrogenous source and sulfur source.
Wherein, the inert atmosphere of employing is argon or nitrogen, and preliminary carburizing temperature is 200 DEG C～300 DEG C, and temperature retention time is 1h～5h, and heating rate is 1 DEG C of min-1～2 DEG C of min-1.In the process, adopt temperature increasing schedule at a slow speed, be conducive to raw material is carried out preexpanding, remove the water of crystallization in raw material, enough ducts and gap are provided for follow-up mixed active material.
2) by step 1) in prepare sample be placed in vacuum glove box alkaline solution, decompression absorption some hours, then as in common drying baker dry.Decompression is adsorbed with the deep layer duct being beneficial to solution entrance material, is beneficial to activation；And remove solvent at drying baker.
Wherein, alkaline solution used is 0.5mol L-1～1.0mol L-1KOH or NaOH solution；The air pressure that vacuum glove box keeps is 0～50pa, and decompression adsorption time is 1h～6h；The drying temperature of drying baker is 80 DEG C～100 DEG C, and drying time is 10h～12h.
3) by step 2) in the sample dried as, in the tube furnace of inert atmosphere, being tentatively warming up to uniform temperature and be incubated, then be warming up to activation temperature and be incubated a period of time, to carry out activation processing, then natural cooling.The front section processed at inert atmosphere (argon or nitrogen) is primarily to the water of crystallization removing in material further, and sample is mainly effectively activated by follow-up process.
Wherein, inert atmosphere is argon or nitrogen, tentatively heats up and the temperature that keeps is 200 DEG C～350 DEG C, and temperature retention time is 0.5h～3h；The activation temperature of activation processing is 600 DEG C～900 DEG C, and temperature retention time is 0.5h～2h；Omnidistance heating rate is 3 DEG C of min-1～7 DEG C of min-1。
4) by step 3) sample of gained grinds rear pickling, sucking filtration, and add and be washed to neutrality.
Wherein, pickling is specially in the acid solution that impregnated in 60 DEG C～90 DEG C pickling 4h～10h, and acid solution is specially 0.2mol L-1～0.6mol L-1H2SO4, HCl or HNO3.Sucking filtration instrument adopts water circulating pump, and pressure is about 10Pa.And repeatedly use deionized water rinsing 3-5 time, remove impurity and the soluble substance of the inside.Can effectively be removed alkali metal (K and the Na) compound in sample and soluble impurity by said process, obtain the sample of higher degree.
5) by step 4) to be placed in vacuum drying oven dry for the sample of gained, obtains the porous graphene that superhigh specific surface area is sulfur and nitrogen co-doped.
Wherein, vacuum drying carries out when 5Pa～50Pa, and baking temperature is 60 DEG C～90 DEG C, and drying time is 10h～12h.
Certainly, the preparation method of the sulfur and nitrogen co-doped high specific surface area porous Graphene of the present invention, it is not only applicable to above listed animal hair and Bauhinia variegata Linn etc., and applies to all containing keratic material.
It is below specific embodiments of the invention.
Embodiment 1
1) drying clean for Pilus Sus domestica, as, in tube furnace argon gas atmosphere, being warming up to 300 DEG C of preliminary carbonizations, temperature retention time is 2h, and heating rate is 1 DEG C of min-1；
2) by step 1) in prepare sample be placed in vacuum glove box 0.5mol L-1In KOH, decompression absorption 2h, air pressure is set to 10pa, and dries 12h as in common drying baker 80 DEG C；
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 be warming up to 800 DEG C, be incubated 1h, heating rate is 5 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom impregnated in 0.5mol L after grinding-1H2SO4In solution after 80 DEG C of constant temperature pickling 8h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in vacuum drying oven (pressure is 5pa, and temperature is 60 DEG C) dry 12h and obtains the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area.
The structure of the sulfur and nitrogen co-doped porous graphene of gained is such as shown in Fig. 1 (a), 1 (b), transmission electron microscope (TEM) figure that wherein Fig. 1 (a) is gained Graphene, it can be seen that Graphene balloon-shaped structure and microcellular structure.High power transmission electron microscope (HR-TEM) figure that Fig. 1 (b) is gained Graphene, Graphene stacked and balloon-shaped structure thereof are high-visible.The specific surface area of the sulfur and nitrogen co-doped porous graphene of gained is as in figure 2 it is shown, up to 1799m2/g.Fig. 3 is Raman spectrum (Raman) figure of gained Graphene, at 2655cm-1Place occurs in that Graphene 2D peak, it was shown that have the existence of graphene-structured.As shown in Figure 4, as can be seen from the figure this Graphene mainly contains tetra-kinds of elements of C, N, O, N to the component result of the sulfur and nitrogen co-doped porous graphene of gained, and wherein the content of N element is 8.25at.%, and the content of element sulphur is 1.29at.%.
Embodiment 2
1) drying clean for chicken feather, as, in tube furnace argon gas atmosphere, being warming up to 250 DEG C of preliminary carbonizations, temperature retention time is 3h, and heating rate is 2 DEG C of min-1；
2) by step 1) in prepare sample be placed in glove box 0.7mol L-1In NaOH, decompression absorption 1h, air pressure is set to 5pa, and dries 11h as in common drying baker 90 DEG C；
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, be incubated 1h, heating rate is 3 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom impregnated in 0.3mol L after grinding-1HCl solution in after 90 DEG C of constant temperature pickling 5h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in vacuum drying oven (pressure is 40pa, and temperature is 70 DEG C) dry 11h and obtains 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 element is 6.93at.%, and the content of element sulphur is 1.67at.%.
Embodiment 3
1) drying clean for drake feather, as, in tube furnace argon gas atmosphere, being warming up to 200 DEG C of preliminary carbonizations, temperature retention time is 4h, and heating rate is 1.5 DEG C of min-1；
2) by step 1) in prepare sample be placed in glove box 0.8mol L-1In KOH, decompression absorption 3h, air pressure is set to 20pa, and dries 10h as in common drying baker 100 DEG C；
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, be incubated 0.5h, heating rate is 4 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom impregnated in 0.6mol L after grinding-1Hydrochloric acid solution in after 90 DEG C of constant temperature pickling 10h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in vacuum drying oven (pressure is 25pa, and temperature is 90 DEG C) dry 10h and obtains 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 element is 6.65at.%, and the content of element sulphur is 1.42at.%.
Embodiment 4
1) drying clean for Pluma Anseris domestica, as, in tube furnace argon gas atmosphere, being warming up to 275 DEG C of preliminary carbonizations, temperature retention time is 3h, and heating rate is 1.7 DEG C of min-1；
2) by step 1) in prepare sample be placed in glove box 0.4mol L-1In KOH, decompression absorption 1h, air pressure is set to 10pa, and as 70 DEG C of common drying baker is dried 11.5h；
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 be warming up to 900 DEG C, be incubated 1h, heating rate is 6 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom impregnated in 0.5mol L after grinding-1HNO3In solution after 70 DEG C of constant temperature pickling 11h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in vacuum drying oven (pressure is 15pa, and temperature is 80 DEG C) dry 10.5h and obtains 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 element is 5.43at.%, and the content of element sulphur is 1.04at.%.
Embodiment 5
1) drying clean for ox hair, as, in tube furnace argon gas atmosphere, being warming up to 300 DEG C of preliminary carbonizations, temperature retention time is 3h, and heating rate is 1 DEG C of min-1；
2) by step 1) in prepare sample be placed in glove box 0.9mol L-1In NaOH, decompression absorption 4h, air pressure is set to 40pa, and dries 10h as in common drying baker 100 DEG C；
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 be warming up to 700 DEG C, be incubated 2h, heating rate is 5 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom impregnated in 0.6mol L after grinding-1H2SO4In solution after 60 DEG C of constant temperature pickling 8h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in vacuum drying oven (pressure is 5pa, and temperature is 90 DEG C) dry 10h and obtains 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 1709m2/ g, the content of nitrogen element is 6.65at.%, and the content of element sulphur is 1.09at.%.
Embodiment 6
1) drying clean for Pilus Caprae seu Ovis, as, in tube furnace argon gas atmosphere, being warming up to 300 DEG C of preliminary carbonizations, temperature retention time is 1h, and heating rate is 2 DEG C of min-1；
2) by step 1) in prepare sample be placed in glove box 0.6mol L-1In KOH, decompression absorption 4h, air pressure is set to 5pa, and dries 11h as in common drying baker 90 DEG C；
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, be incubated 1.2h, heating rate is 3 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom impregnated in 0.5mol L after grinding-1HCl solution in after 90 DEG C of constant temperature pickling 6h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in vacuum drying oven (pressure is 10pa, and temperature is 90 DEG C) dry 10h and obtains 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 element is 5.87at.%, and the content of element sulphur is 1.19at.%.
Embodiment 7
1) drying clean for Unguis Bovis seu Bubali, as, in tube furnace argon gas atmosphere, being warming up to 300 DEG C of preliminary carbonizations, temperature retention time is 3h, and heating rate is 1.2 DEG C of min-1；
2) by step 1) in prepare sample be placed in glove box 1.0mol L-1In KOH, decompression absorption 4h, air pressure is set to 3pa, and dries 11.5h as in common drying baker 85 DEG C；
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, be incubated 2h, heating rate is 6 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom impregnated in 0.3mol L after grinding-1H2SO4In solution after 90 DEG C of constant temperature pickling 12h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in vacuum drying oven (pressure is 5pa, and temperature is 85 DEG C) dry 10.5h and obtains 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 element is 5.25at.%, and the content of element sulphur is 1.26at.%.
Embodiment 8
1) drying clean for Cornu Caprae seu Ovis, as, in tube furnace argon gas atmosphere, being warming up to 300 DEG C of preliminary carbonizations, temperature retention time is 3h, and heating rate is 1.8 DEG C of min-1；
2) by step 1) in prepare sample be placed in glove box 1.0mol L-1In NaOH, decompression absorption 3h, air pressure is set to 10pa, and dries 11.6h as in common drying baker 88 DEG C；
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, be incubated 2h, heating rate is 3 DEG C of min-1, then natural cooling；
4) by step 3) products therefrom impregnated in 0.5mol L after grinding-1HCl acid solution in after 80 DEG C of constant temperature pickling 4h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in vacuum drying oven (pressure is 5pa, and temperature is 90 DEG C) dry 10h and obtains 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 1656m2/ g, the content of nitrogen element is 6.30at.%, and the content of element sulphur is 1.06at.%.
Those skilled in the art will readily understand; the foregoing is only presently preferred embodiments of the present invention; not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area, it is characterised in that the method comprises the steps:
1) will dry containing keratic biological material is clean, required sample is obtained as carbonization in tube furnace inert atmosphere, this biological material is simultaneously as solid carbon source, nitrogenous source and sulfur source, wherein, the concrete technology of carbonization is set to temperature 200～300 DEG C, temperature retention time 1～5h, 1～2 DEG C of min of heating rate-1。
2) by step 1) in the sample for preparing be placed in vacuum glove box alkaline solution to carry out decompression absorption, then dry, it is thus achieved that required sample；
3) by step 2) in dry sample as, in the tube furnace of inert atmosphere, being tentatively warming up to 200～350 DEG C, and be incubated 0.5～3h, be then warming up to 600～900 DEG C again, be incubated 0.5～2h, to carry out activation processing, then natural cooling；
4) by step 3) sample of gained grinds rear pickling, sucking filtration, and add and be washed to neutrality；
5) by step 4) to be placed in vacuum drying oven dry for the sample of gained, obtains the porous graphene that superhigh specific surface area is sulfur and nitrogen co-doped.
2. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 1, it is characterised in that described step 1) in adopt inert atmosphere be argon or nitrogen.
3. the preparation method of the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area according to claim 2, it is characterised in that described step 2) in alkaline solution used be 0.5～1.0mol L-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, it is characterised in that described step 2) in the air pressure that keeps 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, it is characterised in that described step 2) in dry temperature be 80 DEG C～100 DEG C, the 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, it is characterised in that described step 3) in inert atmosphere be argon or nitrogen, step 3) in omnidistance 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, it is characterised in that described step 4) in pickling be impregnated in pickling 4～10h in the acid solution of 60～90 DEG C, 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, it is characterized in that, described step 5) in vacuum drying carry out when 5Pa～50Pa, baking 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, it is characterized in that, described is animal hair, Bauhinia variegata Linn or angle containing abundant keratic biological material, it is preferred to Pilus Sus domestica, ox hair, Pilus Caprae seu Ovis, chicken feather, drake feather, Pluma Anseris domestica, Unguis Sus domestica, Unguis Bovis seu Bubali, Bauhinia purpurea, Cornu Bovis seu Bubali or Cornu Caprae seu Ovis.
10. the sulfur and nitrogen co-doped porous graphene of superhigh specific surface area that prepared by the method described in any one of claim 1-9, it is characterised in that this sulfur and nitrogen co-doped porous graphene is porous foam shape structure, and 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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