CN105731447B - A kind of preparation method and product of the classifying porous nitrogen-doped graphene of three-dimensional - Google Patents

A kind of preparation method and product of the classifying porous nitrogen-doped graphene of three-dimensional Download PDF

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CN105731447B
CN105731447B CN201610269986.1A CN201610269986A CN105731447B CN 105731447 B CN105731447 B CN 105731447B CN 201610269986 A CN201610269986 A CN 201610269986A CN 105731447 B CN105731447 B CN 105731447B
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CN105731447A (en
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黄云辉
张建
胡培
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Hubei Hongrun High Tech New Materials Co., Ltd.
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Huazhong University of Science and Technology
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Abstract

The invention discloses a kind of preparation method and product of the classifying porous nitrogen-doped graphene of three-dimensional, belong to field of preparation of graphene, it is raw material that it, which selects most common biological material in nature, using it simultaneously as solid carbon source and nitrogen source and synthesis template, first pass around serial dehydration processing, again by carbonization and preexpanding process, with K2CO3Solution mixes, and is freeze-dried after high-temperature activation processing and obtains three-dimensional classifying porous nitrogen-doped graphene.The graphene of gained has macropore, mesoporous and micropore hierarchical porous structure, and N doping content is 2.5~7.5at.%, and specific surface area is up to 1300m2/ more than g, there is the advantages that preparation technology is simple, the graphene function admirable of preparation, and good oxygen reduction activity has been shown in electro-catalysis field.

Description

A kind of preparation method and product of the classifying porous nitrogen-doped graphene of three-dimensional
Technical field
The invention belongs to field of preparation of graphene, more particularly, to a kind of classifying porous nitrogen-doped graphene of three-dimensional Preparation method and product.
Background technology
Graphene is the two-dimentional allotrope of carbon, its collect high carrier mobility, good translucency, high heat conductance, Numerous good characteristics such as high mechanical properties and high electrochemical stability, by people's extensive concern.Wherein, it is most important The electric property that the electronic structure that it is unique that part is graphene is shown, electron-trajectory transport such as at room temperature, unusual amount Sub- Hall effect and quantum tunneling effect etc..However, the band gap of intrinsic graphene is zero, Half-metallic is shown as, causes stone Device made of black alkene does not have switching behaviour, and this greatly limits its application in terms of electronics and opto-electronic device.
To solve this problem, the application of graphene is expanded, Heteroatom doping graphene is widely studied, and reason is miscellaneous The chemical doping of atom can not only adjust the position of fermi level, can also change the electronic structure of graphene, so as to effectively Regulate and control the electrical properties of grapheme material.Wherein, nitrogen atom doping graphene is studied earliest, and the most frequently used prepares N doping stone The method of black alkene mainly has three kinds：First, chemical vapour deposition technique (CVD), this method is straight to be deposited on the templates such as metal or catalyst Connect to obtain nitrogen-doped graphene；Handle to obtain nitrogen-doped graphene second, carrying out nitrating again after chemical treatment graphite；Third, high temperature Handle macromolecule or polymer precursor the synthesis nitrogen-doped graphene such as nitrogenous.But all there is open defect, CVD in above method Metallic catalyst and Si pieces etc. is not only needed to be used as template, it is also necessary to complicated organic gas environment, preparation procedure requirement is strict, Complex process；Chemical treatment graphite again nitrating the methods of also want later stage nitrating technique, and gained nitrogen-doped graphene specific surface area Generally not high (<1000m2/g)；High-temperature process nitrogen containing polymer etc. synthesizes, and technique is relatively simple, but how poisonous presoma used is, It is detrimental to health, is unfavorable for industrializing.
In addition to doping, some defects are introduced to graphenic surface, its electronic structure and band gap can also be adjusted. For example, some researchs recently show, by the porous graphene for punching to obtain in graphenic surface, show more preferable than graphene Machinery, electronics, optics and heat-conductive characteristic.Template is to prepare a kind of the most frequently used method of porous graphene, but the party For the loose structure that method is formed to sacrifice hard template as cost, the template of residual largely have impact on the property of porous graphene Energy.Therefore, a kind of method of the simple and easy high specific surface area porous graphene of nitrogen auto-dope for carrying template is invented for simplification Graphene preparation technology, lifts graphene performance, and the promotion and application for accelerating graphene are all significant.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of three-dimensional classifying porous N doping stone The preparation method and product of black alkene, its using the especially edible vegetables of biomass as raw material, while as solid carbon source and Nitrogen source, and using biomass as foraminous die plate, it is prepared for that there is macropore, mesoporous and micropore three-dimensional graded porous structure, with tradition Prepare porous graphene to compare, pore size distributions at different levels are more uniformly distributed, and gained graphene specific surface area is up to 1300m2/ more than g, tool There is the advantages that preparation technology is simple, the graphene function admirable of preparation.
To achieve the above object, according to one aspect of the present invention, it is proposed that a kind of three-dimensional classifying porous N doping graphite The preparation method of alkene, using multiporous biological material as self-template, it comprises the following steps the graphene：
1) multiporous biological material is cleaned, and be soaked in ethanol solution；Then, it is drawn off being placed in tubular type Carbonization is performed in stove under an inert atmosphere, is then incubated 1h-2h, is derived from required sample；
2) sample for being obtained step 1) weighs appropriate weight and is placed in the concentrated sulfuric acid, then is added into NaNO3Gu Body and KMnO4Solid, constant temperature in water-bath is then collectively disposed at again and stirs more than 30min, in the process, sample and the concentrated sulfuric acid Mass ratio be set to 1：2~1:5, sample and NaNO3Mass ratio be set to 1：0.5~1：3, sample and KMnO4Matter Amount ratio is set to 1：4~1：8；Then, it is further continued for adding excessive K2CO3Solid continues to stir more than 30min, is finally dried It is dry, it is derived from consolidating block；
3) the consolidation block of gained in step 2) is placed in tube furnace, heats up and live under inert gas shielding atmosphere Change, activation temperature is 600 DEG C~900 DEG C, and activation soaking time is 1~3h, and heating rate is 5~10 DEG C of min-1；
4) as 0.5mol/L H after the product obtained by step 3) is ground2SO4Normal temperature pickling 4-8h, filter, and add washing To neutrality, sample needed for acquisition；
5) sample obtained by step 4) is freeze-dried to obtain three-dimensional classifying porous nitrogen-doped graphene.
As it is further preferred that the time being soaked in the step 1) in ethanol solution is 48h~72h.
As it is further preferred that inert atmosphere is argon gas or nitrogen atmosphere in the step 1), the temperature range of carbonization For 900~1400 DEG C, heating rate is 1~2 DEG C of min-1。
As it is further preferred that the concentrated sulfuric acid and K in the step 2)2CO3Mass ratio is 1：3~1：6.
As it is further preferred that the temperature control of constant temperature stirring is at 20~80 DEG C in the step 2).
As it is further preferred that protective atmosphere is argon gas or nitrogen in the step 3).
Carried out as it is further preferred that being freeze-dried in the step 5) under the conditions of -60~-30 DEG C, 10~50Pa, Drying time is 20h~60h.
As it is further preferred that the multiporous biological is of fine quality to elect water hyacinth, cucumber, eggplant, mushroom or lotus rhizome as.
It is another aspect of this invention to provide that provide the three-dimensional classifying porous nitrogen-doped graphene prepared by methods described.
As it is further preferred that the specific surface area of the classifying porous nitrogen-doped graphene of the three-dimensional reaches 1300m2/ g, nitrogen are mixed Miscellaneous content is up to 2.5~7.5at.%.
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 uses the especially edible vegetables of biomass as raw material, the cellulose and egg enriched with its inside White matter, solid carbon source and nitrogen source can be used as simultaneously, compared with tradition prepares nitrogen-doped graphene, raw material sources are more wide General, price is lower, and renewable, and without the processing of later stage nitrating, the practicable auto-dope of material itself, N doping content is up to 2.5 ~7.5at.%, processing step is greatly simplified, save process costs.
2. water process is gone for biomass in the present invention,, can be more preferable compared with traditional drying using Gradient elution using ethanol Holding biomass internal morphology, be unlikely to because of moisture evaporation and hole is shunk；Porous carbon materials are converted into by high temperature cabonization, then Pass through NaNO3And KMnO4Etc. mixed processing, further increase carbon material internal holes, with synthesising biological matter foraminous die plate, prepare stone Without any other template in black alkene technique, biological material is using itself as the synthesizing porous stone of template combination potassium carbonate high-temperature activation Black alkene, compared with tradition prepares porous graphene or CVD prepares graphene, biological material is while sacrificial using itself as template Domestic animal self form, is converted into graphene, has saved the template cost and processing step of extra configuration, while it is stagnant also to solve template Take a photograph and ring graphene performance issue.
3. the present invention also enters to the proportional quantity of some key process parameters such as sample and solid, the specific process parameter of activation Row research and setting, presentation can be produced with macropore, the graphene of mesoporous and micropore three-dimensional graded porous structure, made with tradition Standby porous graphene is compared, and pore size distributions at different levels are more uniformly distributed, and gained graphene specific surface area is up to 1300m2/ more than g is remote high In prepared with conventional method porous graphene material specific surface area (<900m2/ g), graphene layer spacing is also larger, reaches 0.39nm, it can effectively suppress carbon material π-pi-conjugated structure, prevent material from stacking.Gained graphene is in electro-catalysis field In application for, its oxygen reduction activity is also above the grapheme material prepared with conventional method.
Brief description of the drawings
Fig. 1 is metallographic electron microscope (MLM) figure of biomass raw material duckweed in the embodiment of the present invention 1；
Fig. 2 (a) is the transmission electron microscope of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1 (TEM) figure；
Fig. 2 (b) is the high power transmission electron microscopy of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1 Mirror (HR-TEM) figure；
Fig. 3 (a) is the nitrogen desorption accompanying drawing of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1；
Fig. 3 (b) is the graph of pore diameter distribution of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1；
Fig. 4 is Raman (Raman) figure of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1；
Fig. 5 is the x-ray photoelectron power spectrum of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1 (XPS) figure；
Fig. 6 is the polarization curves of oxygen reduction (LSV) of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1 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 Conflict can is not formed each other to be mutually combined.
The general principle of the present invention is to prepare three-dimensional classifying porous nitrogen-doped graphene, biomass by self-template of biomass Material source is extensive, renewable, and carbon nitrogen element content enriches, and has substantial amounts of protein, amino acid etc., and with naturally more Pore structure, its own feature can be made full use of, using it simultaneously as carbon source, nitrogen source and template, by experiment process by its turn Three-dimensional classifying porous nitrogen-doped graphene is turned to, lifts the industrial application value of biological material, while reduces graphene preparation Cost.It is raw material that the present invention, which selects ten several biological materials that source is most wide in nature, is taken off first with ethanol Water, its internal structure pattern is kept, prevents hole from shrinking；It is more by this multiporous biological matter thaumatropy again by high temperature cabonization Hole carbon and NaNO3And KMnO4Deng mixing, further expansion processing is carried out to carbon material internal holes；Again during high-temperature activation, Using its own as template, carbon atom is reset by synergies such as K, Mn, Na, forms graphene-structured, but because of metal potassium ion and Caused H2O、H2、CO、CO2Deng gas, non-directional shuttles in the material, and forms porous graphene structure.Meanwhile biological material Material contains substantial amounts of protein and amino acid in itself, can function simultaneously as solid carbon source and nitrogen source, therefore, using biomass as forerunner Body, more biomass can be converted into by three-dimensional classifying porous nitrogen-doped graphene by the experimental program of setting.
The method of the present invention that three-dimensional classifying porous nitrogen-doped graphene is prepared using multiporous biological matter as template, its with Multiporous biological material such as duckweed, stalk, peanut shell, banana skin, water hyacinth, cucumber, eggplant, lotus leaf, mushroom, beans shell, lotus Lotus root etc. is used as solid carbon source and nitrogen source simultaneously, first passes around serial dehydration processing, then by carbonization and expansion process, with K2CO3It is molten Liquid mixes, and is freeze-dried and obtains after high-temperature activation processing, specifically includes following steps：
1) multiporous biological material is cleaned, is soaked in ethanol solution and is taken out after certain time, be placed in tube furnace It is carbonized under inert atmosphere, is heated up with heating rate at a slow speed, and is incubated 1-2h, sample needed for acquisition.Temperature increasing schedule at a slow speed has Beneficial to the further crystallization water removed in material, and keep the loose structure of raw material in itself；Insulation a period of time has at high temperature Beneficial to the degree of graphitization of lifting material.
Wherein, the time being soaked in ethanol solution is specially 48h~72h, thoroughly removes the moisture in raw material, described lazy Property atmosphere is argon gas or nitrogen atmosphere, and carburizing temperature scope is 900~1400 DEG C, and heating rate is 1~2 DEG C of min-1。
2) sample in step 1) is weighed to certain weight, as in the concentrated sulfuric acid, adds NaNO3Solid and KMnO4Solid It is placed in constant temperature in water-bath and stirs 20-40min, to carry out expansion process, then adds excessive K2CO3Solid continues to stir 20- 40min, then be placed in common drying box and fully dry, obtain consolidation block.
Specifically, material addition is respectively：Sample and concentrated sulfuric acid mass ratio：1：2~1:5, the concentrated sulfuric acid is as strong proton Acid, into the interlayer of sample；Sample and NaNO3Mass ratio：1：0.5~1：3, NaNO3Catalytic Proton is played herein into interlayer Effect；Sample and KMnO4Mass ratio：1：4~1：8, KMnO4As strong oxidizer oxidation sample；With K2CO3Mass ratio：1：3~ 1：6, K2CO3As activator in next step high-temperature process activated sample, and K2CO3The carbon dioxide of decomposition can Pore-creating is carried out to material；The temperature control of constant temperature stirring is at 20~80 DEG C, and drying box temperature control is at 80~100 DEG C.
3) the consolidation block of gained in step 2) is placed in tube furnace, heats up and live under inert gas shielding atmosphere Change, specifically：
The protective atmosphere is argon gas or nitrogen, and activation temperature is 600 DEG C~900 DEG C, and activation soaking time is 1~3h, Heating rate is 5~10 DEG C of min-1, between the potassium ion under the technique under high temperature effectively can be free on the layer of sample, While activated sample, the interlamellar spacing of sample is further strutted, obtains porous graphene-structured
4) as 0.5M (mol/L) H after step 3) products therefrom is ground2SO4Normal temperature pickling 4-8h, filter, and add washing To neutrality；
5) sample obtained by step 4) is placed in freeze drier and freezed, the moisture in sample is frozen completely, Zhi Houtong Cross freeze-drying and obtain three-dimensional classifying porous nitrogen-doped graphene, wherein：
In the case where -60~-30 DEG C, 10Pa~50Pa conditions are carried out, drying time is 20h~60h for the freeze-drying.This mistake Journey can make the ice in frozen samples be overflowed in the form of distillation without dissolving, be advantageous to keep the complete pattern of sample, prevent Sample stacks, caking.
It is below the specific embodiment of the present invention.
Embodiment 1
1) with duckweed, (its microstructure is as shown in figure 1, duckweed contains three-dimensional porous shape knot in itself as we can see from the figure Structure) it is raw material, duckweed is cleaned, is soaked in ethanol solution and is taken out after 48h；It is subsequently placed in tube furnace 1000 under argon gas atmosphere DEG C carbonization, be incubated 2h, with 2 DEG C of min-1Heating rate heats up；
2) sample in step 3) is weighed into 5g, as in the 10g concentrated sulfuric acids, adds 5g NaNO3Solid and 20g KMnO4Gu Body is placed in water-bath and adds excessive 30g K after 30 DEG C of constant temperature stirring 30min2CO3Solid continues to stir 30min, then is placed in common Fully dried in drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 700 DEG C of activation, activation soaking time is 1h, and heating rate is 5 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 6h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -60 DEG C, 5Pa conditions carry out down, dry 30h, obtain three Tie up classifying porous nitrogen-doped graphene.
Wherein, shown in microstructure such as Fig. 2 (a), 2 (b) of the three-dimensional classifying porous nitrogen-doped graphene of gained, from Fig. 2 (a) in the it can be seen that lamellar structure of graphene stacking and hole at different levels, it can be seen that the graphene number of plies from Fig. 2 (b)<8 layers, and Its interlamellar spacing is about 0.39nm.Fig. 3 (a) is the three-dimensional classifying porous nitrogen-doped graphene nitrogen adsorption desorption isothermal curve of gained, by The specific surface area (BET) that nitrogen adsorption desorption isothermal curve obtains this graphene is 1309m2g-1.Fig. 3 (b) is the three-dimensional classification of gained Porous nitrogen-doped graphene graph of pore diameter distribution, the graphene is simultaneously containing substantial amounts of micropore, mesoporous and macropore as seen from the figure.Fig. 4 For Raman spectrum (Raman) figure of the three-dimensional classifying porous nitrogen-doped graphene of gained, in 2683cm-1There is sharp graphene in place 2D peaks, show the presence for having graphene-structured.Fig. 5 is the x-ray photoelectron power spectrum of three-dimensional classifying porous nitrogen-doped graphene (XPS) figure, as can be seen from the figure the product mainly contain tri- kinds of elements of C, N, O, the wherein content of N element is 3.08at.%. Three-dimensional classifying porous nitrogen-doped graphene prepared by the embodiment of the present invention good oxygen has been shown into also used in electro-catalysis field Former activity, as a result as shown in fig. 6, it can be seen that under the alkalescence condition of oxygen saturation, the graphene onset potential is 0.98V (V vs.RHE), half way up the mountain potential are 0.82V.
Embodiment 2
1) stalk is cleaned, is soaked in ethanol solution and is taken out after 52h, be subsequently placed in tube furnace 900 under argon gas atmosphere DEG C carbonization, be incubated 1h, with 1.4 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 15g concentrated sulfuric acids, adds 7.5g NaNO3Solid and 25g KMnO4 Solid is placed in water-bath and adds excessive 55g K after 20 DEG C of constant temperature stirring 20min2CO3Solid continues to stir 40min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 800 DEG C of activation, activation soaking time is 1.5h, and heating rate is 7 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 4h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -50 DEG C, 10Pa conditions carry out down, dry 36h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 4.02at.%, and specific surface area is 1400m2/g.Electro-chemical test shows, in the alkaline solution of oxygen saturation, its polarization curves of oxygen reduction shows its onset potential For 0.97V (V vs.RHE), half way up the mountain potential is 0.83V.
Embodiment 3
1) peanut shell is cleaned, is soaked in ethanol solution and is taken out after 56h, be subsequently placed in tube furnace under nitrogen atmosphere 1100 DEG C of carbonizations, are incubated 1.5h, with 2 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 10g concentrated sulfuric acids, adds 10g NaNO3Solid and 28g KMnO4 Solid is placed in water-bath and adds excessive 40g K after 40 DEG C of constant temperature stirring 40min2CO3Solid continues to stir 20min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 900 DEG C of activation, activation soaking time is 2h, and heating rate is 6 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 8h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -40 DEG C, 15Pa conditions carry out down, dry 30h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 4.08at.%, and specific surface area is 1400m2/g.Electro-chemical test shows, in the alkaline solution of oxygen saturation, its polarization curves of oxygen reduction shows its onset potential For 0.97V (V vs.RHE), half way up the mountain potential is 0.83V.
Embodiment 4
1) banana skin is cleaned, is soaked in ethanol solution and is taken out after 62h, be subsequently placed in tube furnace under argon gas atmosphere 1200 DEG C of carbonizations, are incubated 2h, with 1.2 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 20g concentrated sulfuric acids, adds 2.5g NaNO3Solid and 30g KMnO4 Solid is placed in water-bath and adds excessive 85g K after 30 DEG C of constant temperature stirring 25min2CO3Solid continues to stir 35min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 850 DEG C of activation, activation soaking time is 3h, and heating rate is 8 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 7h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -30 DEG C, 30Pa conditions carry out down, dry 48h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 3.59at.%, and specific surface area is 1360m2/g., the electro-chemical test in alkaline solution shows that its polarization curves of oxygen reduction shows that its onset potential is 0.99V (V vs.RHE), half way up the mountain potential are 0.84V.
Embodiment 5
1) water hyacinth is cleaned, is soaked in ethanol solution and is taken out after 56h, be placed in lower 1250 DEG C of argon gas atmosphere in tube furnace Carbonization, 1.7h is incubated, with 1.8 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 25g concentrated sulfuric acids, adds 15g NaNO3Solid and 35g KMnO4 Solid is placed in water-bath and adds excessive 80g K after 50 DEG C of constant temperature stirring 35min2CO3Solid continues to stir 30min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 800 DEG C of activation, activation soaking time is 1h, and heating rate is 10 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 5h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -30 DEG C, 18Pa conditions carry out down, dry 60h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 5.27at.%, and specific surface area is 1538m2/g.Electro-chemical test shows, its polarization curves of oxygen reduction shows that its onset potential is 0.99V (V vs.RHE), half way up the mountain Potential is 0.83V.
Embodiment 6
1) cucumber is cleaned, is soaked in ethanol solution and is taken out after 72h, be placed in the lower 950 DEG C of carbon of argon gas atmosphere in tube furnace Change, 1h is incubated, with 2 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 15g concentrated sulfuric acids, adds 5g NaNO3Solid and 20g KMnO4Gu Body is placed in water-bath and adds excessive 40g K after 65 DEG C of constant temperature stirring 30min2CO3Solid continues to stir 30min, then is placed in common Fully dried in drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 700 DEG C of activation, activation soaking time is 1.5h, and heating rate is 5 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 6h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -35 DEG C, 24Pa conditions carry out down, dry 40h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 6.02at.%, and specific surface area is 1663m2/g.Electro-chemical test shows, its polarization curves of oxygen reduction shows that its onset potential is 0.98V (V vs.RHE), half way up the mountain Potential is 0.81V.
Embodiment 7
1) eggplant is cleaned, is soaked in ethanol solution and is taken out after 60h；It is placed in the lower 900 DEG C of carbon of argon gas atmosphere in tube furnace Change, 2h is incubated, with 1.8 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 10g concentrated sulfuric acids, adds 10g NaNO3Solid and 35g KMnO4 Solid is placed in water-bath and adds excessive 50g K after 50 DEG C of constant temperature stirring 30min2CO3Solid continues to stir 30min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 900 DEG C of activation, activation soaking time is 1.5h, and heating rate is 9 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 5h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -50 DEG C, 5Pa conditions carry out down, dry 36h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 2.98at.%, and specific surface area is 1956m2/g.Electro-chemical test shows, its polarization curves of oxygen reduction shows that its onset potential is 0.97V (V vs.RHE), half way up the mountain Potential is 0.82V.
Embodiment 8
1) lotus leaf is cleaned, is soaked in ethanol solution and is taken out after 48h；It is placed in the lower 1300 DEG C of carbon of argon gas atmosphere in tube furnace Change, 2h is incubated, with 1.2 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 20g concentrated sulfuric acids, adds 7.5g NaNO3Solid and 25g KMnO4 Solid is placed in water-bath and adds excessive 65g K after 70 DEG C of constant temperature stirring 30min2CO3Solid continues to stir 30min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 600 DEG C of activation, activation soaking time is 3h, and heating rate is 7 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 6h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -60 DEG C, 10Pa conditions carry out down, dry 50h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 7.50at.%, and specific surface area is 1670m2/g.Electro-chemical test shows, its polarization curves of oxygen reduction shows that its onset potential is 0.96V (V vs.RHE), half way up the mountain Potential is 0.80V.
Embodiment 9
1) mushroom is cleaned, is soaked in ethanol solution and is taken out after 72h；It is placed in the lower 1100 DEG C of carbon of argon gas atmosphere in tube furnace Change, 1h is incubated, with 1.5 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 15g concentrated sulfuric acids, adds 15g NaNO3Solid and 40g KMnO4 Solid is placed in water-bath and adds excessive 50g K after 80 DEG C of constant temperature stirring 30min2CO3Solid continues to stir 30min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 800 DEG C of activation, activation soaking time is 2h, and heating rate is 7 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 4h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -30 DEG C, 30Pa conditions carry out down, dry 56h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 2.53at.%, and specific surface area is 1460m2/g.Electro-chemical test shows, its polarization curves of oxygen reduction shows that its onset potential is 0.94V (V vs.RHE), half way up the mountain Potential is 0.81V.
Embodiment 10
1) beans shell is cleaned, is soaked in ethanol solution and is taken out after 66h；It is placed in the lower 1400 DEG C of carbon of argon gas atmosphere in tube furnace Change, 2h is incubated, with 2 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 15g concentrated sulfuric acids, adds 10g NaNO3Solid and 36g KMnO4 Solid is placed in water-bath and adds excessive 60g K after 60 DEG C of constant temperature stirring 40min2CO3Solid continues to stir 30min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 800 DEG C of activation, activation soaking time is 2.5h, and heating rate is 6 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 6h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -50 DEG C, 10Pa conditions carry out down, dry 20h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 6.36at.%, and specific surface area is 1590m2/g.Electro-chemical test shows, its polarization curves of oxygen reduction shows that its onset potential is 0.94V (V vs.RHE), half way up the mountain Potential is 0.80V.
Embodiment 11
1) lotus rhizome skin is cleaned, is soaked in ethanol solution and is taken out after 72h；It is placed in lower 1200 DEG C of argon gas atmosphere in tube furnace Carbonization, 1.5h is incubated, with 1.5 DEG C of min-1Heating rate heats up；
2) sample in step 1) is weighed into 5g, as in the 20g concentrated sulfuric acids, adds 7.5g NaNO3Solid and 25g KMnO4 Solid is placed in water-bath and adds excessive 70g K after 30 DEG C of constant temperature stirring 30min2CO3Solid continues to stir 40min, then is placed in general Fully dried in logical drying box；
3) the consolidation block of gained in step 2) is placed in tube furnace, be warming up under inert gas shielding atmosphere 800 DEG C of activation, activation soaking time is 1.5h, and heating rate is 7 DEG C of min-1；
4) as 0.5M H after step 3) products therefrom is ground2SO4Normal temperature pickling 8h, filter, and add and be washed to neutrality；
5) by sample obtained by step 4) be placed in freeze-drying machine -45 DEG C, 10Pa conditions carry out down, dry 45h, obtain three Tie up classifying porous nitrogen-doped graphene.
The nitrogen element content of the wherein three-dimensional classifying porous nitrogen-doped graphene of gained is 3.99at.%, and specific surface area is 1625m2/g.Electro-chemical test shows, its polarization curves of oxygen reduction shows that its onset potential is 0.99V (V vs.RHE), half way up the mountain Potential is 0.84V.
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, not to The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included Within protection scope of the present invention.

Claims (8)

1. a kind of preparation method of the classifying porous nitrogen-doped graphene of three-dimensional, it is characterised in that the graphene is with multiporous biological matter Material prepares for template, and the multiporous biological material while solid carbon source and nitrogen source as graphene, it includes as follows Step：
1) multiporous biological material is cleaned, and be soaked in ethanol solution；Then, it is drawn off being placed in tube furnace Carbonization is performed under an inert atmosphere, is then incubated 1h-2h, is derived from required sample；
2) sample for being obtained step 1) weighs appropriate weight and is placed in the concentrated sulfuric acid, then is added into NaNO3Solid and KMnO4Solid, constant temperature in water-bath is then collectively disposed at again and stirs 20-40min, in the process, the matter of sample and the concentrated sulfuric acid Amount ratio is set to 1：2~1:5, sample and NaNO3Mass ratio be set to 1：0.5~1：3, sample and KMnO4Mass ratio It is set to 1：4~1：8；Then, it is further continued for adding excessive K2CO3Solid continues to stir 20-40min, is finally dried, by This obtains consolidation block, the concentrated sulfuric acid and K2CO3Mass ratio is 1：3~1：6；
3) the consolidation block of gained in step 2) is placed in tube furnace, heat up activation under inert gas shielding atmosphere, living It is 600 DEG C~900 DEG C to change temperature, and activation soaking time is 1~3h, and heating rate is 5~10 DEG C of min-1；
4) 0.5mol/L H are placed in after the product of gained in step 3) is ground2SO4Normal temperature pickling 4-8h, filter, and add and be washed to Neutrality, sample needed for acquisition；
5) sample obtained by step 4) is freeze-dried to obtain three-dimensional classifying porous nitrogen-doped graphene.
2. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that the step 1) time being soaked in in ethanol solution is preferably 48h~72h.
3. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that the step 1) inert atmosphere is argon gas or nitrogen atmosphere in, and the temperature range of carbonization is 900~1400 DEG C, and heating rate is 1~2 DEG C min-1。
4. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that the step 2) temperature control that constant temperature stirs in is at 20~80 DEG C.
5. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that the step 3) protective atmosphere is argon gas or nitrogen in.
6. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that the step 5) freeze-drying is carried out under the conditions of -60~-30 DEG C, 10~50Pa in, and drying time is 20h~60h.
7. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that described porous Biomass is preferably water hyacinth, cucumber, eggplant, mushroom or lotus rhizome.
8. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that the three-dimensional The specific surface area of classifying porous nitrogen-doped graphene reaches 1300m2/ g, N doping content is up to 2.5~7.5at.%.
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