CN105731447A - Preparation method of three-dimensional hierarchical porous nitrogen-doped graphene and product - Google Patents

Preparation method of three-dimensional hierarchical porous nitrogen-doped graphene and product Download PDF

Info

Publication number
CN105731447A
CN105731447A CN201610269986.1A CN201610269986A CN105731447A CN 105731447 A CN105731447 A CN 105731447A CN 201610269986 A CN201610269986 A CN 201610269986A CN 105731447 A CN105731447 A CN 105731447A
Authority
CN
China
Prior art keywords
doped graphene
nitrogen
graphene
preparation
dimensional
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610269986.1A
Other languages
Chinese (zh)
Other versions
CN105731447B (en
Inventor
黄云辉
张建
胡培
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hubei Hongrun High Tech New Materials Co., Ltd.
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN201610269986.1A priority Critical patent/CN105731447B/en
Publication of CN105731447A publication Critical patent/CN105731447A/en
Application granted granted Critical
Publication of CN105731447B publication Critical patent/CN105731447B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • 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
    • C01P2002/82—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Abstract

The invention discloses a preparation method of three-dimensional hierarchical porous nitrogen-doped graphene and the product, and belongs to the field of graphene preparation.The preparation method comprises the steps that a biomass material which is most common in the natural world is selected as a raw material and taken as a solid carbon source, a nitrogen source and a synthesizing template simultaneously, gradient dewatering processing is firstly performed, then carbonization and pre-expansion processing is performed, the processed biomass material is mixed with a K2CO3 solution, high-temperature activation is performed, freeze-drying is performed, and then the three-dimensional hierarchical porous nitrogen-doped graphene is obtained.The obtained graphene has a hierarchical pore structure comprising macropores, mesopores and micropores, the nitrogen-doped content is 2.5 at.%-7.5 at.%, and the specific surface area reaches up to 1300 m<2>/g or above.The preparation method has the advantages that the preparation technology is simple and the prepared graphene is excellent in performance and shows the very good oxygen reduction activity in the electro-catalysis field.

Description

The preparation method of the classifying porous nitrogen-doped graphene of a kind of three-dimensional and product
Technical field
The invention belongs to field of preparation of graphene, more particularly, to preparation method and the product of the classifying porous nitrogen-doped graphene of a kind of three-dimensional.
Background technology
Graphene is the two-dimentional allotrope of carbon, and it integrates numerous good characteristics such as high carrier mobility, good light transmission, high heat conductance, high mechanical properties and high electrochemical stability, is subject to people's extensive concern.Wherein, most important part is in that the electric property that the electronic structure of Graphene uniqueness shows, such as the electron-trajectory transport under room temperature, unusual quantum hall effect and quantum tunneling effect etc..But, the band gap of intrinsic Graphene is zero, shows as Half-metallic, causes that the device that Graphene is made does not have switching behaviour, this greatly limits its application in electronics and opto-electronic device.
For solving this problem, expanding the application of Graphene, Heteroatom doping Graphene is widely studied, and reason is in that heteroatomic chemical doping is possible not only to adjust the position of fermi level, the electronic structure of Graphene can also be changed, thus the electrical properties of Effective Regulation grapheme material.Wherein, nitrogen atom doping Graphene is studied the earliest, and the most frequently used method preparing nitrogen-doped graphene mainly has three kinds: one to be chemical vapour deposition technique (CVD), and this method directly obtains nitrogen-doped graphene with deposition on the templates such as metal or catalyst；Two is carry out nitrating process after chemical treatment graphite again to obtain nitrogen-doped graphene；Three is that high-temperature process is nitrogenous waits macromolecule or polymer precursor synthetic nitrogen doped graphene.But above method all exists open defect, CVD not only needs metallic catalyst and Si sheet etc. as template, in addition it is also necessary to complicated organic gas environment, and preparation procedure requires strict, complex process；The methods such as chemical treatment graphite nitrating more also want later stage nitrating technique and the general not high (< 1000m of gained nitrogen-doped graphene specific surface area2/g)；High-temperature process nitrogen containing polymers etc. synthesize, and technique is relatively simple, but how poisonous presoma used is, is detrimental to health, and is unfavorable for industrialization.
Except doping, graphenic surface is introduced some defects, it is also possible to its electronic structure and band gap are adjusted.Such as, some research recently shows, by the porous graphene obtained in graphenic surface punching, shows more better machinery than Graphene, electronics, optics and heat-conductive characteristic.Template is to prepare a kind of method that porous graphene is the most frequently used, but the loose structure that the method is formed is with sacrificial hard template for cost, and the template of residual largely have impact on the performance of porous graphene.Therefore, inventing a kind of method of simple high specific surface area porous Graphene of nitrogen auto-dope carrying template for simplifying Graphene preparation technology, promote Graphene performance, the promotion and application accelerating Graphene are all significant.
Summary of the invention
Disadvantages described above or Improvement requirement for prior art, the invention provides the preparation method of the classifying porous nitrogen-doped graphene of a kind of three-dimensional and product, it is with the especially edible vegetable of biomass for raw material, simultaneously as solid carbon source and nitrogenous source, and with biomass for foraminous die plate, it is prepared for having the three-dimensional graded porous structure of macropore, mesoporous and micropore, compared with preparing porous graphene with tradition, pore size distributions at different levels are more uniformly distributed, and gained Graphene specific surface area is up to 1300m2The advantages such as/more than g, has preparation technology simple, the Graphene function admirable of preparation.
For achieving the above object, according to one aspect of the present invention, it is proposed that the preparation method of the classifying porous nitrogen-doped graphene of a kind of three-dimensional, this Graphene is with multiporous biological material for self-template, and it comprises the steps:
1) multiporous biological material is cleaned, and be soaked in alcoholic solution；Then, it is drawn off being placed in tube furnace and performs carbonization under an inert atmosphere, be then incubated 1h-2h, be derived from required sample；
2) by step 1) sample that obtains weighs suitable weight and is placed in concentrated sulphuric acid, then be added to into NaNO3Solid and KMnO4Solid, stirring more than the 30min that is then collectively disposed in water-bath constant temperature again, in the process, the mass ratio of sample and concentrated sulphuric acid is set to 1:2～1:5, sample and NaNO3Mass ratio be set to 1:0.5～1:3, sample and KMnO4Mass ratio be set to 1:4～1:8；Then, it is further continued for adding excessive K2CO3Solid continues stirring more than 30min, finally dries, and is derived from consolidation block；
3) by step 2) in the consolidation block of gained be placed in tube furnace, heat up activation under inert gas shielding atmosphere, and activation temperature is 600 DEG C～900 DEG C, and activation temperature retention time is 1～3h, and heating rate is 5～10 DEG C of min-1；
4) by step 3) product of gained grind after as 0.5mol/LH2SO4Room temperature pickling 4-8h, sucking filtration, and add and be washed to neutrality, it is thus achieved that required sample；
5) by step 4) gained sample lyophilization obtains three-dimensional classifying porous nitrogen-doped graphene.
As it is further preferred that described step 1) in be soaked in the time in alcoholic solution be 48h～72h.
As it is further preferred that described step 1) in inert atmosphere be argon or nitrogen atmosphere, the temperature range of carbonization is 900～1400 DEG C, and heating rate is 1～2 DEG C of min-1。
As it is further preferred that described step 2) in concentrated sulphuric acid and K2CO3Mass ratio is 1:3～1:6.
As it is further preferred that described step 2) in the temperature of constant temperature stirring control at 20～80 DEG C.
As it is further preferred that described step 3) in protective atmosphere be argon or nitrogen.
As it is further preferred that described step 5) in lyophilization-60～-30 DEG C, 10～50Pa when carry out, drying time is 20h～60h.
As it is further preferred that described multiporous biological is of fine quality elects Herba Eichhorniae, Fructus Cucumidis sativi, Fructus Solani melongenae, Lentinus Edodes or Rhizoma Nelumbinis as.
It is another aspect of this invention to provide that provide the classifying porous nitrogen-doped graphene of the three-dimensional prepared by described method.
As it is further preferred that the specific surface area of this three-dimensional classifying porous nitrogen-doped graphene reaches 1300m2/ g, N doping content reaches 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 adopts the especially edible vegetable of biomass to be raw material, the cellulose abundant with its inside and protein, it is possible to simultaneously as solid carbon source and nitrogenous source, compared with preparing nitrogen-doped graphene with tradition, raw material sources is more extensive, price is lower, and renewable, it is not necessary to later stage nitrating processes, the practicable auto-dope of material itself, N doping content, up to 2.5～7.5at.%, is greatly simplified processing step, saves process costs.
2. for the process of anhydrating of biomass in the present invention, adopt Gradient elution using ethanol, compared with traditional drying, can better keep biomass internal morphology, be unlikely to the hole contraction because of moisture evaporation；It is converted into porous carbon materials, again through NaNO through high temperature cabonization3And KMnO4Etc. mixed processing, increase material with carbon element internal holes further, with synthesising biological matter foraminous die plate, prepare in Graphene technique without any other template, biological material with from as template in conjunction with the synthesizing porous Graphene of potassium carbonate high-temperature activation, porous graphene is prepared or compared with CVD prepares Graphene with tradition, biological material is with from as template, sacrifice self form simultaneously, it is converted into Graphene, save template cost and the processing step of additional configuration, also can solve template retention effects Graphene performance issue simultaneously.
3. the present invention also proportional quantity to some key process parameters such as sample Yu solid, the concrete technology parameter of activation carries out studying and sets, the Graphene presenting the three-dimensional graded porous structure with macropore, mesoporous and micropore can be produced, compared with preparing porous graphene with tradition, pore size distributions at different levels are more uniformly distributed, and gained Graphene specific surface area is up to 1300m2/ more than g, much higher than with porous graphene material specific surface area (< 900m prepared by traditional method2/ g), graphene layer spacing is also relatively big, reaches 0.39nm, it is possible to effective suppression material with carbon element π-pi-conjugated structure, it is prevented that material is stacking.The application in electro-catalysis field of the gained Graphene, its oxygen reduction activity is also above the grapheme material prepared by traditional method.
Accompanying drawing explanation
Fig. 1 is metallographic ultramicroscope (MLM) figure of biomass raw material Herba Spirodelae in the embodiment of the present invention 1；
Fig. 2 (a) is transmission electron microscope (TEM) figure of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1；
Fig. 2 (b) is high power transmission electron microscope (HR-TEM) figure of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1；
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 x-ray photoelectron power spectrum (XPS) figure of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1；
Fig. 6 is polarization curves of oxygen reduction (LSV) figure of the three-dimensional classifying porous nitrogen-doped graphene of gained in the embodiment of the present invention 1.
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 ultimate principle of the present invention is to prepare three-dimensional classifying porous nitrogen-doped graphene with biomass for self-template, biological material wide material sources, renewable, carbon nitrogen element content enriches, there are substantial amounts of protein, aminoacid etc., and there is natural loose structure, himself feature can be made full use of, with it simultaneously as carbon source, nitrogenous source and template, process by experiment and be translated into three-dimensional classifying porous nitrogen-doped graphene, promote the industrial application value of biological material, reduce Graphene preparation cost simultaneously.The present invention selects the widest tens kind biological material of originating in nature to be raw material, first with dewatering of ethanol, keeps its internal structure pattern, it is prevented that hole is shunk；Again through high temperature cabonization, it is porous carbon and NaNO by this multiporous biological matter thaumatropy3And KMnO4Deng mixing, material with carbon element internal holes is carried out further expansion process；Again in high-temperature activation process, with himself for template, carbon atom is reset by synergism such as K, Mn, Na, forms graphene-structured, again because of the H of metallic potassium ion and generation2O、H2、CO、CO2Shuttle back and forth Deng gas non-directional in the material, and form porous graphene structure.Meanwhile, biological material itself contains substantial amounts of protein and aminoacid, can function simultaneously as solid carbon source and nitrogenous source, and therefore, with biomass for presoma, many biomass are converted into three-dimensional classifying porous nitrogen-doped graphene by the experimental program that can pass through setting.
The method preparing three-dimensional classifying porous nitrogen-doped graphene for template with multiporous biological matter of the present invention, its with multiporous biological material such as Herba Spirodelae, straw, Pericarppium arachidis hypogaeae, Pericarpium Musae, Herba Eichhorniae, Fructus Cucumidis sativi, Fructus Solani melongenae, Folium Nelumbinis, Lentinus Edodes, bean shell, Rhizoma Nelumbinis etc. simultaneously as solid carbon source and nitrogenous source, first pass around serial dehydration to process, then through carbonization and expansion process, with K2CO3Solution mixes, and high-temperature activation processes postlyophilization and obtains, and specifically includes following steps:
1) multiporous biological material is cleaned, be soaked in alcoholic solution after certain time and take out, be placed in tube furnace carbonization under inert atmosphere, heat up with heating rate at a slow speed, and be incubated 1-2h, it is thus achieved that required sample.Temperature increasing schedule at a slow speed is conducive to the water of crystallization removing in material further, and keeps the loose structure of raw material itself；At high temperature insulation a period of time is conducive to promoting the degree of graphitization of material.
Wherein, the time being soaked in alcoholic solution is specially 48h～72h, thoroughly removes the moisture in raw material, and described inert atmosphere is argon or nitrogen atmosphere, and carburizing temperature scope is 900～1400 DEG C, and heating rate is 1～2 DEG C of min-1。
2) by step 1) in sample weigh certain weight, as, in concentrated sulphuric acid, adding NaNO3Solid and KMnO4Solid is placed in water-bath constant temperature stirring 20-40min, to carry out expansion process, is subsequently adding excessive K2CO3Solid continues stirring 20-40min, then is placed in common drying baker and fully dries, it is thus achieved that consolidation block.
Concrete, material addition is respectively as follows: sample and concentrated sulphuric acid mass ratio: 1:2～1:5, and concentrated sulphuric acid, as strong protonic acid, enters the interlayer of sample；Sample and NaNO3Mass ratio: 1:0.5～1:3, NaNO3Play Catalytic Proton at this and enter the effect of interlayer；Sample and KMnO4Mass ratio: 1:4～1:8, KMnO4As strong oxidizer oxidation sample；With K2CO3Mass ratio: 1:3～1:6, K2CO3As activator activated sample in next step high-temperature process, and K2CO3Material can be carried out pore-creating by the carbon dioxide decomposed；The temperature of constant temperature stirring controls at 20～80 DEG C, and drying baker temperature controls at 80～100 DEG C.
3) by step 2) in the consolidation block of gained be placed in tube furnace, heat up activation under inert gas shielding atmosphere, concrete:
Described protective atmosphere is argon or nitrogen, and activation temperature is 600 DEG C～900 DEG C, and activation temperature retention time is 1～3h, and heating rate is 5～10 DEG C of min-1, under this technique, the potassium ion under high temperature can effectively be free between the layer of sample, while activated sample, struts the interlamellar spacing of sample further, it is thus achieved that the graphene-structured of porous
4) by step 3) products therefrom grind after as 0.5M (mol/L) H2SO4Room temperature pickling 4-8h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample is placed in freezer dryer freezing, and make the moisture in sample freeze completely, obtain three-dimensional classifying porous nitrogen-doped graphene by lyophilization afterwards, wherein:
Described lyophilization-60～-30 DEG C, under 10Pa～50Pa condition carries out, drying time is 20h～60h.This process can make the ice in freezing sample without dissolving, overflows with the form of distillation, is conducive to keeping the complete pattern of sample, it is prevented that sample is stacking, caking.
It is below specific embodiments of the invention.
Embodiment 1
1) for raw material, Herba Spirodelae is cleaned with Herba Spirodelae (its microstructure is as it is shown in figure 1, Herba Spirodelae itself is containing three-dimensional porous shape structure as we can see from the figure), be soaked in alcoholic solution after 48h and take out；It is subsequently placed in tube furnace the lower 1000 DEG C of carbonizations of argon gas atmosphere, is incubated 2h, with 2 DEG C of min-1Heating rate heats up；
2) by step 3) in sample weigh 5g, as in 10g concentrated sulphuric acid, add 5gNaNO3Solid and 20gKMnO4Solid adds excessive 30gK after being placed in water-bath 30 DEG C of constant temperature stirring 30min2CO3Solid continues stirring 30min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 700 DEG C of activation, activation temperature retention time is 1h, and heating rate is 5 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 6h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-60 DEG C, under 5Pa condition carries out, dry 30h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein, the microstructure of the classifying porous nitrogen-doped graphene of three-dimensional of gained is such as shown in Fig. 2 (a), 2 (b), it can be seen that the stacking lamellar structure of Graphene and hole at different levels from Fig. 2 (a), from Fig. 2 (b) it can be seen that the Graphene number of plies < 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, nitrogen adsorption desorption isothermal curve the specific surface area (BET) obtaining this Graphene is 1309m2g-1.Fig. 3 (b) is the three-dimensional classifying porous nitrogen-doped graphene graph of pore diameter distribution of gained, and this Graphene contains substantial amounts of micropore, mesoporous and macropore simultaneously as seen from the figure.Fig. 4 is Raman spectrum (Raman) figure of the three-dimensional classifying porous nitrogen-doped graphene of gained, at 2683cm-1There is sharp-pointed Graphene 2D peak in place, it was shown that have the existence of graphene-structured.Fig. 5 is x-ray photoelectron power spectrum (XPS) figure of three-dimensional classifying porous nitrogen-doped graphene, and as can be seen from the figure this product mainly contains tri-kinds of elements of C, N, O, and wherein the content of N element is 3.08at.%.The classifying porous nitrogen-doped graphene of the three-dimensional embodiment of the present invention prepared is used in electro-catalysis field and has shown good oxygen reduction activity, result is as shown in Figure 6, as can be seen from the figure, under the alkali condition that oxygen is saturated, this Graphene onset potential is 0.98V (Vvs.RHE), and half way up the mountain electromotive force is 0.82V.
Embodiment 2
1) straw is cleaned, be soaked in alcoholic solution after 52h and take out, be subsequently placed in tube furnace the lower 900 DEG C of carbonizations of argon gas atmosphere, be incubated 1h, with 1.4 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 15g concentrated sulphuric acid, add 7.5gNaNO3Solid and 25gKMnO4Solid adds excessive 55gK after being placed in water-bath 20 DEG C of constant temperature stirring 20min2CO3Solid continues stirring 40min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 800 DEG C of activation, activation temperature retention time is 1.5h, and heating rate is 7 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 4h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-50 DEG C, under 10Pa condition carries out, dry 36h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 that oxygen is saturated, its polarization curves of oxygen reduction shows that its onset potential is 0.97V (Vvs.RHE), and half way up the mountain electromotive force is 0.83V.
Embodiment 3
1) Pericarppium arachidis hypogaeae is cleaned, be soaked in alcoholic solution after 56h and take out, be subsequently placed in tube furnace the lower 1100 DEG C of carbonizations of nitrogen atmosphere, be incubated 1.5h, with 2 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 10g concentrated sulphuric acid, add 10gNaNO3Solid and 28gKMnO4Solid adds excessive 40gK after being placed in water-bath 40 DEG C of constant temperature stirring 40min2CO3Solid continues stirring 20min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 900 DEG C of activation, activation temperature retention time is 2h, and heating rate is 6 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 8h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-40 DEG C, under 15Pa condition carries out, dry 30h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 that oxygen is saturated, its polarization curves of oxygen reduction shows that its onset potential is 0.97V (Vvs.RHE), and half way up the mountain electromotive force is 0.83V.
Embodiment 4
1) Pericarpium Musae is cleaned, be soaked in alcoholic solution after 62h and take out, be subsequently placed in tube furnace the lower 1200 DEG C of carbonizations of argon gas atmosphere, be incubated 2h, with 1.2 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 20g concentrated sulphuric acid, add 2.5gNaNO3Solid and 30gKMnO4Solid adds excessive 85gK after being placed in water-bath 30 DEG C of constant temperature stirring 25min2CO3Solid continues stirring 35min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 850 DEG C of activation, activation temperature retention time is 3h, and heating rate is 8 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 7h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-30 DEG C, under 30Pa condition carries out, dry 48h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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, its polarization curves of oxygen reduction shows that its onset potential is 0.99V (Vvs.RHE), and half way up the mountain electromotive force is 0.84V.
Embodiment 5
1) Herba Eichhorniae is cleaned, be soaked in alcoholic solution after 56h and take out, be placed in tube furnace the lower 1250 DEG C of carbonizations of argon gas atmosphere, be incubated 1.7h, with 1.8 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 25g concentrated sulphuric acid, add 15gNaNO3Solid and 35gKMnO4Solid adds excessive 80gK after being placed in water-bath 50 DEG C of constant temperature stirring 35min2CO3Solid continues stirring 30min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 800 DEG C of activation, activation temperature retention time is 1h, and heating rate is 10 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 5h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-30 DEG C, under 18Pa condition carries out, dry 60h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 (Vvs.RHE), and half way up the mountain electromotive force is 0.83V.
Embodiment 6
1) Fructus Cucumidis sativi is cleaned, be soaked in alcoholic solution after 72h and take out, be placed in tube furnace the lower 950 DEG C of carbonizations of argon gas atmosphere, be incubated 1h, with 2 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 15g concentrated sulphuric acid, add 5gNaNO3Solid and 20gKMnO4Solid adds excessive 40gK after being placed in water-bath 65 DEG C of constant temperature stirring 30min2CO3Solid continues stirring 30min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 700 DEG C of activation, activation temperature retention time is 1.5h, and heating rate is 5 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 6h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-35 DEG C, under 24Pa condition carries out, dry 40h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 (Vvs.RHE), and half way up the mountain electromotive force is 0.81V.
Embodiment 7
1) Fructus Solani melongenae is cleaned, be soaked in alcoholic solution after 60h and take out；It is placed in tube furnace the lower 900 DEG C of carbonizations of argon gas atmosphere, is incubated 2h, with 1.8 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 10g concentrated sulphuric acid, add 10gNaNO3Solid and 35gKMnO4Solid adds excessive 50gK after being placed in water-bath 50 DEG C of constant temperature stirring 30min2CO3Solid continues stirring 30min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 900 DEG C of activation, activation temperature retention time is 1.5h, and heating rate is 9 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 5h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-50 DEG C, under 5Pa condition carries out, dry 36h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 (Vvs.RHE), and half way up the mountain electromotive force is 0.82V.
Embodiment 8
1) Folium Nelumbinis is cleaned, be soaked in alcoholic solution after 48h and take out；It is placed in tube furnace the lower 1300 DEG C of carbonizations of argon gas atmosphere, is incubated 2h, with 1.2 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 20g concentrated sulphuric acid, add 7.5gNaNO3Solid and 25gKMnO4Solid adds excessive 65gK after being placed in water-bath 70 DEG C of constant temperature stirring 30min2CO3Solid continues stirring 30min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 600 DEG C of activation, activation temperature retention time is 3h, and heating rate is 7 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 6h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-60 DEG C, under 10Pa condition carries out, dry 50h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 (Vvs.RHE), and half way up the mountain electromotive force is 0.80V.
Embodiment 9
1) Lentinus Edodes is cleaned, be soaked in alcoholic solution after 72h and take out；It is placed in tube furnace the lower 1100 DEG C of carbonizations of argon gas atmosphere, is incubated 1h, with 1.5 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 15g concentrated sulphuric acid, add 15gNaNO3Solid and 40gKMnO4Solid adds excessive 50gK after being placed in water-bath 80 DEG C of constant temperature stirring 30min2CO3Solid continues stirring 30min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 800 DEG C of activation, activation temperature retention time is 2h, and heating rate is 7 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 4h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-30 DEG C, under 30Pa condition carries out, dry 56h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 (Vvs.RHE), and half way up the mountain electromotive force is 0.81V.
Embodiment 10
1) bean shell is cleaned, be soaked in alcoholic solution after 66h and take out；It is placed in tube furnace the lower 1400 DEG C of carbonizations of argon gas atmosphere, is incubated 2h, with 2 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 15g concentrated sulphuric acid, add 10gNaNO3Solid and 36gKMnO4Solid adds excessive 60gK after being placed in water-bath 60 DEG C of constant temperature stirring 40min2CO3Solid continues stirring 30min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 800 DEG C of activation, activation temperature retention time is 2.5h, and heating rate is 6 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 6h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-50 DEG C, under 10Pa condition carries out, dry 20h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 (Vvs.RHE), and half way up the mountain electromotive force is 0.80V.
Embodiment 11
1) Rhizoma Nelumbinis skin is cleaned, be soaked in alcoholic solution after 72h and take out；It is placed in tube furnace the lower 1200 DEG C of carbonizations of argon gas atmosphere, is incubated 1.5h, with 1.5 DEG C of min-1Heating rate heats up；
2) by step 1) in sample weigh 5g, as in 20g concentrated sulphuric acid, add 7.5gNaNO3Solid and 25gKMnO4Solid adds excessive 70gK after being placed in water-bath 30 DEG C of constant temperature stirring 30min2CO3Solid continues stirring 40min, then is placed in common drying baker and fully dries；
3) by step 2) in the consolidation block of gained be placed in tube furnace, under inert gas shielding atmosphere, be warming up to 800 DEG C of activation, activation temperature retention time is 1.5h, and heating rate is 7 DEG C of min-1；
4) by step 3) products therefrom grind after as 0.5MH2SO4Room temperature pickling 8h, sucking filtration, and add and be washed to neutrality；
5) by step 4) gained sample be placed in freeze-drying machine-45 DEG C, under 10Pa condition carries out, dry 45h, obtain three-dimensional classifying porous nitrogen-doped graphene.
Wherein the nitrogen element content of the 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 (Vvs.RHE), and half way up the mountain electromotive force is 0.84V.
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 classifying porous nitrogen-doped graphene of three-dimensional, it is characterised in that this Graphene prepares with multiporous biological material for template, and it comprises the steps:
1) multiporous biological material is cleaned, and be soaked in alcoholic solution；Then, it is drawn off being placed in tube furnace and performs carbonization under an inert atmosphere, be then incubated 1h-2h, be derived from required sample；
2) by step 1) sample that obtains weighs suitable weight and is placed in concentrated sulphuric acid, then be added to into NaNO3Solid and KMnO4Solid, the stirring 20-40min that is then collectively disposed in water-bath constant temperature again, in the process, the mass ratio of sample and concentrated sulphuric acid is set to 1:2～1:5, sample and NaNO3Mass ratio be set to 1:0.5～1:3, sample and KMnO4Mass ratio be set to 1:4～1:8；Then, it is further continued for adding excessive K2CO3Solid continues stirring 20-40min, finally dries, and is derived from consolidation block；
3) by step 2) in the consolidation block of gained be placed in tube furnace, heat up activation under inert gas shielding atmosphere, and activation temperature is 600 DEG C～900 DEG C, and activation temperature retention time is 1～3h, and heating rate is 5～10 DEG C of min-1；
4) by step 3) in the product of gained grind after as 0.5mol/LH2SO4Room temperature pickling 4-8h, sucking filtration, and add and be washed to neutrality, it is thus achieved that required sample；
5) by step 4) gained sample lyophilization obtains 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 described step 1) in be soaked in alcoholic solution time be 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 described step 1) in inert atmosphere be argon or nitrogen atmosphere, the temperature range of carbonization is 900～1400 DEG C, and heating rate is 1～2 DEG C of min-1。
4. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that described step 2) in concentrated sulphuric acid and K2CO3Mass ratio is 1:3～1:6.
5. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that described step 2) in constant temperature stirring temperature control at 20～80 DEG C.
6. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that described step 3) in protective atmosphere be argon or nitrogen.
7. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that described step 5) in lyophilization-60～-30 DEG C, 10～50Pa when carry out, drying time is 20h～60h.
8. the preparation method of three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 1, it is characterised in that described multiporous biological is of fine quality elects Herba Eichhorniae, Fructus Cucumidis sativi, Fructus Solani melongenae, Lentinus Edodes or Rhizoma Nelumbinis as.
9. the classifying porous nitrogen-doped graphene of three-dimensional that prepared by the method described in any one of claim 1-8.
10. three-dimensional classifying porous nitrogen-doped graphene as claimed in claim 9, it is characterised in that the specific surface area of this three-dimensional classifying porous nitrogen-doped graphene reaches 1300m2/ g, N doping content reaches 2.5～7.5at.%.
CN201610269986.1A 2016-04-27 2016-04-27 A kind of preparation method and product of the classifying porous nitrogen-doped graphene of three-dimensional Active CN105731447B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610269986.1A CN105731447B (en) 2016-04-27 2016-04-27 A kind of preparation method and product of the classifying porous nitrogen-doped graphene of three-dimensional

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610269986.1A CN105731447B (en) 2016-04-27 2016-04-27 A kind of preparation method and product of the classifying porous nitrogen-doped graphene of three-dimensional

Publications (2)

Publication Number Publication Date
CN105731447A true CN105731447A (en) 2016-07-06
CN105731447B CN105731447B (en) 2017-12-12

Family

ID=56287537

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610269986.1A Active CN105731447B (en) 2016-04-27 2016-04-27 A kind of preparation method and product of the classifying porous nitrogen-doped graphene of three-dimensional

Country Status (1)

Country Link
CN (1) CN105731447B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106365144A (en) * 2016-08-31 2017-02-01 青岛大学 Method for preparing lotus leaf carbon nanometer material
CN107068410A (en) * 2017-02-27 2017-08-18 安徽桑瑞斯环保新材料有限公司 A kind of graphene that there is high conductivity and ion is can pass through available for electrical storage device and electric device
CN107188156A (en) * 2017-06-27 2017-09-22 上海应用技术大学 A kind of preparation method of lotus flower stem nitrogen-doped carbon nano material
WO2018120067A1 (en) * 2016-12-30 2018-07-05 The University Of Hong Kong Waste biomass-derived metal-free catalysts for oxygen reduction reaction
CN108793155A (en) * 2018-07-03 2018-11-13 济南大学 A kind of preparation method of high-specific surface area lotus root shape porous carbon materials
CN109004199A (en) * 2018-08-01 2018-12-14 北京理工大学 A kind of preparation method of sodium-ion battery cathode biomass hard carbon material
CN112299389A (en) * 2020-09-23 2021-02-02 鸡西市唯大新材料科技有限公司 Method for preparing sodium ion carbon negative electrode material by using nitrogen-doped porous biomass carbon
CN113443626A (en) * 2020-03-26 2021-09-28 华东理工大学 Preparation method of mixed biomass activated carbon and application of mixed biomass activated carbon in super capacitor
CN114471659A (en) * 2022-02-07 2022-05-13 吉林大学 Preparation method and application of superfine gold-palladium nanoparticle/nitrogen-doped porous carbon composite material
CN115818628A (en) * 2022-09-30 2023-03-21 中国人民解放军陆军装甲兵学院 Three-dimensional graphene foam, preparation method and application thereof, and wave-absorbing material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108264037B (en) * 2018-02-06 2019-10-22 北京科技大学 Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103922328A (en) * 2014-04-18 2014-07-16 山东大学 Method for preparing nitrogenous hierarchical pore three-dimensional graphene by using chitosan
CN105314629A (en) * 2015-11-27 2016-02-10 燕山大学 Method for directly preparing co-doping three-dimensional graphene electrode material through biomass carbon sources

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103922328A (en) * 2014-04-18 2014-07-16 山东大学 Method for preparing nitrogenous hierarchical pore three-dimensional graphene by using chitosan
CN105314629A (en) * 2015-11-27 2016-02-10 燕山大学 Method for directly preparing co-doping three-dimensional graphene electrode material through biomass carbon sources

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PIN HAO ET AL.: "Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high performance supercapacitors", 《NANO ENERGY》 *
ZHU-YIN SUI ET AL.: "A highly nitrogen-doped porous graphene–an anode material for lithium ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106365144A (en) * 2016-08-31 2017-02-01 青岛大学 Method for preparing lotus leaf carbon nanometer material
CN110248731A (en) * 2016-12-30 2019-09-17 香港大学 The non-metal catalyst for being originated from useless biomass for oxygen reduction reaction
WO2018120067A1 (en) * 2016-12-30 2018-07-05 The University Of Hong Kong Waste biomass-derived metal-free catalysts for oxygen reduction reaction
CN110248731B (en) * 2016-12-30 2022-11-29 香港大学 Metal-free catalysts derived from waste biomass for oxygen reduction reactions
CN107068410A (en) * 2017-02-27 2017-08-18 安徽桑瑞斯环保新材料有限公司 A kind of graphene that there is high conductivity and ion is can pass through available for electrical storage device and electric device
CN107188156A (en) * 2017-06-27 2017-09-22 上海应用技术大学 A kind of preparation method of lotus flower stem nitrogen-doped carbon nano material
CN108793155A (en) * 2018-07-03 2018-11-13 济南大学 A kind of preparation method of high-specific surface area lotus root shape porous carbon materials
CN109004199A (en) * 2018-08-01 2018-12-14 北京理工大学 A kind of preparation method of sodium-ion battery cathode biomass hard carbon material
CN113443626A (en) * 2020-03-26 2021-09-28 华东理工大学 Preparation method of mixed biomass activated carbon and application of mixed biomass activated carbon in super capacitor
CN112299389A (en) * 2020-09-23 2021-02-02 鸡西市唯大新材料科技有限公司 Method for preparing sodium ion carbon negative electrode material by using nitrogen-doped porous biomass carbon
CN114471659A (en) * 2022-02-07 2022-05-13 吉林大学 Preparation method and application of superfine gold-palladium nanoparticle/nitrogen-doped porous carbon composite material
CN115818628A (en) * 2022-09-30 2023-03-21 中国人民解放军陆军装甲兵学院 Three-dimensional graphene foam, preparation method and application thereof, and wave-absorbing material
CN115818628B (en) * 2022-09-30 2024-01-30 中国人民解放军陆军装甲兵学院 Three-dimensional graphene foam, preparation method and application thereof, and wave-absorbing material

Also Published As

Publication number Publication date
CN105731447B (en) 2017-12-12

Similar Documents

Publication Publication Date Title
CN105731447A (en) Preparation method of three-dimensional hierarchical porous nitrogen-doped graphene and product
Yang et al. Preparation and N2, CO2 and H2 adsorption of super activated carbon derived from biomass source hemp (Cannabis sativa L.) stem
CN104528720B (en) The preparation method of a kind of multi-stage porous Carbon Materials and product
Tan et al. Three-dimensional high graphitic porous biomass carbon from dandelion flower activated by K2FeO4 for supercapacitor electrode
CN107585758B (en) A kind of graphene aerogel and its preparation method and application
CN104045077B (en) The three-dimensional classifying porous Carbon Materials of a kind of Graphene and preparation method
Zhao et al. High performance N-doped porous activated carbon based on chicken feather for supercapacitors and CO 2 capture
Yan et al. Biomass‐derived activated carbon nanoarchitectonics with Hibiscus flowers for high‐performance supercapacitor electrode applications
Zhao et al. Pore structure control of mesoporous carbon as supercapacitor material
CN106783197B (en) A kind of ZIF-8 pyrolysis porous carbon-graphene composite material and its preparation method and application
CN106698409B (en) A kind of three-dimensional graphene foam and its preparation method and application
CN105480975A (en) Method for preparing high-specific-surface-area porous carbon with hemp stems as carbon source
CN107628597B (en) By using SiO2Method for preparing biomass carbon material with micropore and mesopore structure by coating method
CN105752969A (en) Method for preparing polyatomic self-doped graphene by using natural porous and laminated vegetables
Luo et al. Sustainable biomass-based hierarchical porous carbon for energy storage: A novel route to maintain electrochemically attractive natural structure of precursor
Wang et al. Activated pyrolysed bacterial cellulose as electrodes for supercapacitors
Quach et al. The influence of the activation temperature on the structural properties of the activated carbon xerogels and their electrochemical performance
CN111153403B (en) Alginate-based porous carbon and preparation method and application thereof
CN102701181A (en) Chiral mesoporous carbon nanometer fiber and preparation method of chiral mesoporous carbon nanometer fiber
Zheng et al. The simple preparation of a hierarchical porous carbon with high surface area for high performance supercapacitors
Ashok Kumar et al. A review on the recent progress of the plant-based porous carbon materials as electrodes for high-performance supercapacitors
Duan et al. Effects of heating method and activating agent on the porous structure of activated carbons from coconut shells
Morali et al. Preparation of new carbon molecular sieves for optimized carbon dioxide adsorption and product yield
CN109319762A (en) The preparation of biomass porous carbon material with superhigh specific surface area and application as electrode material
CN102923703A (en) Method for manufacturing longstalck peach nuclear shell activated carbon

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20190510

Address after: 436070 Hubei Gedian Development Zone, Ezhou, 1, industrial and Commercial Service Center

Patentee after: Hubei Hongrun High Tech New Materials Co., Ltd.

Address before: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 1037

Patentee before: Huazhong University of Science and Technology