CN106744849A - Polybenzimidazoles（PBI）The method that family macromolecule prepares three-dimensional grapheme - Google Patents

Polybenzimidazoles（PBI）The method that family macromolecule prepares three-dimensional grapheme Download PDF

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CN106744849A
CN106744849A CN201611236542.4A CN201611236542A CN106744849A CN 106744849 A CN106744849 A CN 106744849A CN 201611236542 A CN201611236542 A CN 201611236542A CN 106744849 A CN106744849 A CN 106744849A
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nitrogen
pbi
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CN106744849B (en
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李忠芳
战明明
王素文
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Shandong University of Technology
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Abstract

The present invention is a kind of method for preparing three-dimensional grapheme, uses polybenzimidazoles（PBI）In mPBI be carbon source and nitrogen source, it is template with nano silicon, iron oxide, iron hydroxide and magnesium oxide particle, uneven finish is in nano grain surface after PBI dissolvings, benzimidazole ring in its macromolecule is regularly arranged in template surface, pyrolysis, goes template to obtain three-dimensional nitrogen-doped graphene.It is required that：MPB viscosity average molecular weighs 3 ~ 50,000；Template particle diameter is 3 for the mass ratio of both 5 ~ 50nm:1~1:3；Pyrolysis temperature is 700 ~ 1100 DEG C, is pyrolyzed 2 ~ 3h, uses watery hydrochloric acid（Or hydrofluoric acid）Washing 3 times, deionized water is washed 3 times.The three-dimensional nitrogen-doped graphene of preparation is used for oxygen reduction catalyst, oxygen and separates out catalyst, for fields such as fuel cell, metal-air battery, electrolysis, it can also be used to ultracapacitor, lithium ion battery and sensor field.

Description

Polybenzimidazoles（PBI）The method that family macromolecule prepares three-dimensional grapheme
Technical field
Belong to field of nano material preparation, the negative electrode of fuel cell, metal-air battery for clean energy resource field is urged Agent, electrolysis water catalyst, the field such as electrode material for super capacitor and electrochemical sensor.
Background technology
Graphene is a kind of new carbon two-dimension nano materials, by the tightly packed bi-dimensional cellular shape of single layer of carbon atom Structure.With unique optics, calorifics, electronics and mechanical performance（Allen M J, et al. Chem Rev (chemistry comment), 2010, 110: 132）.But Graphene is often reunited because being interacted by π-π, is piled into graphite-structure, causes to compare table Area reduces, and the performance of each side is greatly reduced, so as to lose the good and bad performance of Graphene.And three-dimensional grapheme can not only keep The characteristic of Graphene, and the porous mass-transfer efficiency for improving reactant and product for being formed.Therefore three-dimensional grapheme catalysis, The fields such as sensor, environmental protection and energy storage have important application value, and cause the extensive concern of people（DongX et al. ACS Applied material Interface (American Chemical Society-interface application material), 2012,4:3129）.By right The research of grapheme material is it is found that the Graphene of nitrogen-doping, the cloud density generation on the adjacent carbon of its nitrogen Change so that the carbon atom around nitrogen-atoms carries part positive charge, is conducive to the adsorption activation of oxygen, so as to improve catalysis oxygen The activity and durability of gas reduction.
The method for preparing three-dimensional nitrogen-doped graphene is a lot：Can be by using the nitrogenous macromolecule such as melmac Materials pyrolysis；Graphene oxide is reduced in the small-molecule substance of ammonia or nitrogen atom；Or using nitrogenous macromolecular material, Such as polyaniline（PANI）(Wu G, et al. Science (science), 2011,332:443), polypyrrole（PPy）（Li H, Yang F. J Mater Chem A (materials chemistry magazine), 2013,1: 3446）N doping is prepared as forerunner's body method Carbon material or nitrogen-doped graphene material.People are often prepared with the pyrolysis such as phenolic resin, pollopas and melmac Carbon material.
As nitrogen containing polymer material, polybenzimidazoles（PBI）With nitrogen content imidazole ring structure high.Benzimidazole ring It is the stiffening ring of armaticity, easily occurs the phenomenon for piling up aggregation in polymer molecule, in order to prevent its from piling up aggregation, can be with Some groups are added in PBI molecules, it is improved its molecular flexibility.Research finds, contains on imidazole ring in PBI molecules If imidazoles nitrogen and metal ion（Such as Cu, Mn, Fe, Ru, Ti, Mo and Os）Carrying out coordination can prepare catalyst, and catalyst is urged Change the redox reaction of organic compound, its catalysis activity and stability preferably (Cameron C G, et al. J Phys Chem B,（（The U.S.）Acta PhySico-Chimica Sinica B）2001, 105:8838).D Archivio are to porous PBI resin materials The redox reaction that metallic ion coordination prepares catalyst organic compound is studied（D Archivio, et Al. Chem-A Eur J, (European The Chemicals) 2000,6 (5): 794）Its catalytic performance is excellent.The synthetic method of PBI 5 kinds can be divided into：Tetramine and dintrile, tetramine and diester, tetramine and diacid, tetramine and diamides, tetramine and dialdehyde, wherein, virtue Fragrant tetramine is the most frequently used with the reaction of aromatic diacid.The structural formula of mPBI is:
The invention is using the polybenzimidazoles of armaticity（PBI）It is die with nano particle as the raw material for providing carbon and nitrogen Plate agent, soluble PBI is covered with paint, lacquer, colour wash, etc. to template surface, and rigid benzimidazole ring is regularly arranged in template surface, in inertia The lower pyrolysis of gases argon protection prepares nitrogenous carbon material.Template agent removing is removed with diluted acid, nano-pore is produced.By feed change with The ratio of hard template, the size of Control architecture particle control the aperture of nitrogenous carbon material, porosity and the Graphene of synthesis The parameters such as the number of plies, finally give preferable multi-layer three-dimension nitrogen-doped graphene.
Compared with phenolic resin, pollopas, melmac Polymer material, the difference of PBI is it Rigid benzimidazole ring containing armaticity, and nitrogen content on imidazole ring more enriches.Therefore high temperature pyrolysis PBI can be obtained The carbon material of the N doping of high nitrogen-containing, and by introducing the regularly arranged side of the aromatic rings of suitable template or control molecule To the grapheme material of multilayer N doping can be obtained respectively after pyrolysis.Nitrogen is prepared with the material such as polyaniline and polypyrrole to mix Miscellaneous Graphene is compared, and PBI can dissolve, it is easy to covered with paint, lacquer, colour wash, etc. on template surface, and polyaniline, polypyrrole etc. are insoluble, it is impossible to mould Plate agent mixes.
The content of the invention
The present invention, has invented a kind of use mPBI and has prepared three-dimensional nitrogen-doped graphene as nitrogen source and utilization of carbon source template Method.MPBI is better than ABPBI due to solubility, so the two can be with the slightly larger polymer of selective polymerization degree, its advantage Its caking property can be more preferable, is covered with paint, lacquer, colour wash, etc. more fully, because the rigid benzimidazole molecule of the Solarium lycopersicoide can in nano grain surface To be regularly arranged in template nano-material surface, it is pyrolyzed by under inert gas shielding, nitrogen is obtained after removing template agent removing Doping carbon material.It is required that PBI is soluble, and imidazole ring and end ammonia in its molecule rich in nitrogen, benzimidazole ring is firm Property armaticity ring, pyrolysis when easily formed nitrogen-doped graphene structure.Its aperture, porosity, specific surface area and N doping stone Number of plies of black alkene etc. has the factors such as PBI and nano template consumption, the particle diameter of template to determine.Mix according to different quality ratio, 2 ~ 3h of pyrolysis in the lower high temperature furnace of argon gas protection, uses watery hydrochloric acid（Or hydrofluoric acid）Three-dimensional nitrogen-doped graphene is obtained by going template. The materials application separates out catalyst and load in fuel cell and the oxygen reduction catalyst of metal air battery cathodes, electrolysis water oxygen The fields such as body, ultracapacitor, electrolysis, sensor material.
PBI is with above phenolic resin, pollopas and melmac Polymer material difference：PBI molecules Middle benzimidazole ring belongs to the stiffening ring of armaticity, contains imidazoles nitrogen in molecule on imidazole ring, belongs to the aroma type high score of rich nitrogen Sub- polymer.Therefore, its pyrolysis can obtain the carbon material of N doping, if the plane of the aromatic rings of control molecule is according to one Direction arranges, and its pyrolysis can obtain the graphene-structured of N doping.With polyaniline, poly-（O-phenylenediamine）, the high score such as polypyrrole Unlike sub- material：PBI family macromolecules are soluble in the organic solvents such as DMAc, DMSO, are easily sufficiently mixed with template, Cover with paint, lacquer, colour wash, etc. on template surface, not split-phase, because it is soluble, it has fine when 3D nitrogen-doped graphene nano materials are prepared Operability.However, polyaniline compound, polypyrrole Polymer material are insoluble, it is impossible to cover with paint, lacquer, colour wash, etc. to template surface, it is impossible to mould Plate agent is blended.
Viscosity average molecular weigh being soluble between 30,000~50,000 that PBI can be prepared with solid phase method or liquid phase method DMAc, DMF, DMSO, in 1-METHYLPYRROLIDONE equal solvent.Molecular weight is too big, and the solubility property of PBI is deteriorated；Molecular weight is too small Its viscosity is too small, it is impossible to coated die plate agent well.
The method of the preparation of the Graphene of three-dimensional N doping is：The appropriate PBI of the degree of polymerization is prepared first, and PBI is dissolved in Solution is formed in solvent, appropriate to being added in solution, particle diameter does template for the nanoparticle template agent of 5 ~ 50 nm, and stirring makes It is sufficiently mixed uniformly.Under agitation, heat, solvent is steamed at leisure near dry, be transferred in vacuum drying chamber at 60 ~ 120 DEG C Drying.It is finely ground in mortar, porcelain boat bottom is laid in, it is put into electric tube furnace, under argon gas protection, at 700~1100 DEG C, 2 ~ 3h of pyrolysis.Treat that furnace temperature is cooled to room temperature, take out, use watery hydrochloric acid（Or hydrofluoric acid）Repeatedly wash to go template agent removing, suction filtration to use Deionized water is cleaned, and dries to obtain product.
In the present invention, template can be various nano-scale oxides or hydroxide particles.Three-dimensional can be prepared Nitrogen-doped graphene, the particle diameter and addition of template are crucial：The particle diameter of template determines the aperture of the carbon material of preparation； The addition of template determines the number of plies and performance of the Graphene of preparation, and addition very little, can only obtain porous carbon materials, plus Enter excessively, the three-dimensional grapheme number of plies for obtaining very little, after removing template agent removing, is easily collapsed, and can only obtain broken Graphene broken Piece.The granularity of template has a certain impact to the amount for adding template, and granularity is small, its surface area it is big, it is necessary to template The amount of agent is just few；, whereas if granularity it is big, it is necessary to template amount it is just many.The consumption of template is：PBI and template Mass ratio be 3:1~1:3；Ratio change is relevant with the granularity of template.Granularity is from 5 ~ 50 nm.In inert gas shielding Lower pyrolysis, pyrolysis temperature is：700~1100 DEG C；Washing watery hydrochloric acid（Or hydrofluoric acid）, after repeatedly template agent removing is removed in washing, use Deionized water is washed to neutrality and dried.
The Graphene characterizing method of three-dimensional N doping is：Aperture, porosity, pore volume and specific surface area nitrogen adsorption instrument （BET）, the Morphology analysis SEM of product（SEM）And projection electron microscope（TEM）, the Graphene number of plies Can be by high power transmission electron microscope（HRTEM）Characterized with Raman spectrum.The degree of graphitization of product, graphene-structured X-ray powder diffraction can be used with the number of plies（XRD）, Raman spectrum characterizes.The element composition of product, valence state can be penetrated with X- Photoelectron spectra（XPS）Characterized, used rotating disk electrode (r.d.e)（RDE）Carry out the catalytic oxidation-reduction reaction of test product （ORR）Performance, water electrolysis oxygen evolution reaction（EOR）, evolving hydrogen reaction（EHR）Capacitive property test with product can be lied prostrate with circulation Peace（CV）, linear volt-ampere（LSV）, Tafel curve and charge-discharge performance test.Product as catalyst durability test CV, LSV and chronoa mperometric plot can be used（i-t）.The catalytic performance of product finally needs assembling metal-air battery, hydrogen-oxygen Fuel cell, the electrolytic cell of electrolysis water, ultracapacitor and sensor test its performance.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 700~1100 DEG C.The too low PBI of temperature can not be pyrolyzed completely, obtain The electric conductivity of product is poor；After pyrolysis temperature reaches optimum temperature, then to raise pyrolysis temperature its performance constant, but, indifferent gas Body protection can occur oxidation reaction when insufficient, so pyrolysis temperature is unsuitable too high.
Specific embodiment
The preparation of [embodiment 1] mPBI：Polyphosphoric acids is added in the there-necked flask protected equipped with electric stirring and nitrogen (PPA) (100g), lower 160 DEG C of nitrogen protection stirs 1h to remove unnecessary moisture and air.By DABz (4g, 18.7 Mmol) and M-phthalic acid (3.1g, 18.7 mmol) is well mixed, it is slowly added in there-necked flask.Control nitrogen Flow velocity, prevents DABz to be oxidized, while reaction temperature being lifted to 200 DEG C and continuing insulation, stirring reaction 5-8h.With reaction The increase of time, polymerization system gradually becomes sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred to largely Reeled off raw silk from cocoons in deionized water, clean, dry, crushed, deionized water is repeatedly washed to remove polyphosphoric acids and unreacted reactant, i.e., MPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
[embodiment 2] Solid phase synthesis mPBI：By DABz (4g, 18.7 mmol) and 4,4 '-diphenyl ether diformazan Sour (4.83g, 18.7 mmol) are well mixed in mortar, being fully ground, be transferred to nitrogen protection, agitator three In mouth flask.Lead to nitrogen 15min to drain the air in flask.N2Protection, under stirring, 225 DEG C of heating of oil bath keep 3h.It is cold But take out afterwards, finely ground, N2Under protection, heating in electric furnace is warmed up to 270-275 DEG C, keeps 3h.Room temperature is cooled to, product is taken Go out, it is finely ground, that is, mPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
[embodiment 3] uses the SiO of particle diameter 30nm2For template mixes with mPBI, with mPBI and SiO2Template mass ratio is 1:As a example by 1：In the beaker of 250mL, the mPBI of 1g is added（Viscosity average molecular weigh 3 ~ 50,000）With 20mL DMAc, heating, stirring make Its dissolving, is slowly added into 1g SiO under agitation2Particle diameter makes it be uniformly dispersed for the nano particle of 30nm.The thick liquid for obtaining Body heats and is concentrated near dry under agitation, is dried at 100 DEG C in the vacuum drying chamber, and solid is finely ground in mortar, is transferred to porcelain In boat, under argon gas protection, 900 DEG C of pyrolysis 2-3h, treat that furnace temperature is down to room temperature in high-temperature electric resistance furnace, take out, finely ground, obtain black Pulverulent solids, are transferred in 250mL conical flasks, add the hydrofluoric acid of 70mL, heating, stirring 24h, suction filtration so to use hydrogen fluorine Acid elution three times, neutrality is washed to, is dried to obtain black powder solid product 0.71g.BET is tested and shown, its pore-size distribution It is 30nm, specific surface area is 948.6 m2 g-1, SEM tests show that the product for obtaining is porous carbon materials, TEM and HRTEM point Analysis shows that product is three-dimensional grapheme structure carbon material, and aperture is 30nm, and Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD Show with Raman spectrum test, product is 2 ~ 4 layers of graphene-structured；XPS analysis show that product nitrogen content is 6.4%, and nitrogen It is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping.Under its 0.1mol/LKOH Catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.96V vs RHE, and electron transfer number is 3.97, and durability is good；Magnesium Air cell performance is up to 98 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 580.2 mW/cm2, the sulfuric acid of 0.5mol/L It is 1.55V vs RHE that oxygen separates out take-off potential in solution, and limiting current density reaches 110mA/cm2.Ultracapacitor is than electricity It is 338F g to hold-1, be recycled 10000 times still holding capacitor value 97%.
[embodiment 4] as described in Example 3, other conditions are identical, and simply mPBI is changed into 2 with the quality of silica： 1, it is similarly obtained the solid powder of black.BET tests show that its pore-size distribution is still 30nm, but its specific surface area is then reduced to 703 m2 g-1, its SEM and TEM tests show, are the carbon material of loose structure inside it, and surface is multi-layer graphene structure, XRD and Raman data show, 7 ~ 8 layers of the number of plies of its Graphene.XPS data are similar with the product of embodiment 3.Its 0.1mol/ Catalytic oxidation-reduction performance under LKOH, oxygen initial reduction current potential is 0.87V vs RHE, and electron transfer number is 3.63, and durability is good It is good；Magnesium air cell performance reaches 77mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 279mW/cm2, the sulfuric acid of 0.5mol/L It is 1.58V vs RHE that oxygen separates out take-off potential in solution, and limiting current density reaches 40mA/cm2.Ultracapacitor specific capacitance It is 227F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 5] as described in Example 3, other conditions are identical, and simply mPBI is changed into 1 with the quality of silica： 2, it is similarly obtained the solid powder of black.BET is tested and shown, 10 ~ 30nm of its pore size distribution range, but its specific surface area then drops It is 847 m2 g-1, its SEM and TEM tests show, are the carbon material of loose structure inside it, and surface is multi-layer graphene structure, XRD and Raman data show, 7 ~ 8 layers of the number of plies of its Graphene.XPS data are similar with the product of embodiment 3.Its 0.1mol/ Catalytic oxidation-reduction performance under LKOH, oxygen initial reduction current potential is 0.87V vs RHE, and electron transfer number is 3.63, and durability is good It is good；Magnesium air cell performance reaches 77mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 279mW/cm2, the sulfuric acid of 0.5mol/L It is 1.58V vs RHE that oxygen separates out take-off potential in solution, and limiting current density reaches 40mA/cm2.Ultracapacitor specific capacitance It is 247 F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 6] as described in Example 3, other conditions are identical, and simply pyrolysis temperature is 700 DEG C, the product of preparation Similar with embodiment 3, simply electric conductivity is poor, and catalytic performance is also poorer.Other conditions are identical, and pyrolysis temperature is 1100 DEG C, Product various aspects of performance is similar than embodiment 3.
[embodiment 7] as described in Example 3, other conditions are identical, are simply 5nm SiO with particle diameter2Particle does template Agent, at this moment, because the particle diameter of template diminishes, its surface area increase, the consumption of mPBI increases, then the quality of mPBI and template Than being changed to be 3:1, the product for obtaining is similar to Example 3, and simply in 5 ~ 10nm, specific surface area is 1698 m to its pore-size distribution2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.93V vs under its 0.1mol/LKOH RHE, electron transfer number is 3.95, and durability is good；Magnesium air cell performance reaches 95mW/cm2.For its peak of hydrogen-oxygen fuel cell Power is 571.6mW/cm2, it is 1.54V vs RHE, carrying current that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L Density reaches 120 mA/cm2.Ultracapacitor specific capacitance is 445F g-1, it is recycled 10000 still holding capacitor values 96%。
[embodiment 8] as described in Example 3, other conditions are identical, are simply 50nm SiO with particle diameter2Particle does mould Plate agent, at this moment because the particle diameter of template increases, its surface area reduces, and the consumption of mPBI is reduced, then the matter of mPBI and template Amount ratio is changed to be 1:3, the product for obtaining is similar to Example 3, and simply in 50nm, specific surface area is 765 m to its pore-size distribution2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.89V vs under its 0.1mol/LKOH RHE, electron transfer number is 3.96, and durability is good；Magnesium air cell performance reaches 89mW/cm2.For its peak of hydrogen-oxygen fuel cell Power is 468mW/cm2, it is 1.54V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L, and carrying current is close Degree reaches 80 mA/cm2.Ultracapacitor specific capacitance is 248F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 9] uses Fe2O3Or iron hydroxide nano particle is template, particle diameter is 30 nanometers.Other experiment conditions are same Embodiment 3.MPBI is 1 with the mass ratio of template:1.Its result is similar to Example 3.Product is three-dimensional grapheme structural carbon Material, aperture is 30nm, 1088.3 m2 g-1, it is 2 ~ 4 layer graphenes.Nitrogen content is 7.7%, and nitrogen is pyridine type nitrogen and pyrroles Type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping.Catalytic oxidation-reduction performance, oxygen under its 0.1mol/LKOH Gas initial reduction current potential is 0.95V vs RHE, and electron transfer number is 3.96, and durability is good；Magnesium air cell performance reaches 106mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 573.5mW/cm2, oxygen separates out starting in the sulfuric acid solution of 0.5mol/L Current potential is 1.56V vs RHE, and limiting current density reaches 120mA/cm2.Ultracapacitor specific capacitance is 468F g-1, can follow The 96% of the still holding capacitor value of ring 10000 times.Iron oxide and iron hydroxide template remove template with watery hydrochloric acid, due to receiving The iron ion on rice grain surface can generate coordinate bond with the nitrogen-atoms in mPBI molecules, can play a part of fixed nitrogen, make three The nitrogen content for tieing up nitrogen-doped graphene is higher.The template of other particle diameters is similar with above example as the situation of template.
[embodiment 10] uses MgO templates, and particle diameter is 30 nanometers.Other experiment conditions are with embodiment 3.MPBI and template The mass ratio of agent is 1:1.Its result is similar to Example 3.Aperture is 30nm, 1074.9 m2 g-1, it is 2 ~ 4 layer graphenes.Nitrogen Content is 6.6%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping. Catalytic oxidation-reduction performance under its 0.1mol/LKOH, oxygen initial reduction current potential is 0.94V vs RHE, and electron transfer number is 3.91, durability is good；Magnesium air cell performance reaches 92mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 465.7mW/ cm2, it is 1.53V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches 110mA/ cm2.Ultracapacitor specific capacitance is 337F g-1, be recycled 10000 times still holding capacitor value 96%.Magnesium oxide template can be with Removed with watery hydrochloric acid.
[embodiment 11] is also similar to the above embodiments with the structure of other templates.Prepared by template of different shapes The situation of three-dimensional nitrogen-doped graphene is similar with above example, and the pattern in the hole simply seen from pattern is different, but, Its performance is similar with above example.

Claims (6)

1. polybenzimidazoles is used（PBI）The method that family macromolecule prepares three-dimensional nitrogen-doped graphene, it is characterised in that:Such virtue The rigid polybenzimidazoles molecule of fragrance can be regularly arranged on the surface of template nano particle, under argon gas protection, Pyrolysis, goes the method for template agent removing to prepare three-dimensional nitrogen-doped graphene；PBI is soluble, and its macromolecular chain is by armaticity Rigid benzimidazole composition, and containing imidazole ring and Amino End Group rich in nitrogen in molecule, the lower pyrolysis of argon gas protection, easy shape Into nitrogen-doped graphene structure, pore-creating effect is played in depickling when the carboxyl in molecule is pyrolyzed；PBI solution and different-grain diameter template Using different quality than mixing, stirring, steaming solvent, vacuum drying, grinding, in high temperature furnace, argon gas protection is lower to be pyrolyzed 2- for agent 3h, after cooling, takes out, and is washed with diluted hydrofluoric acid or watery hydrochloric acid（Remove template agent removing）The three-dimensional nitrogen prepared with activating process Doped graphene.
2. PBI according to claim 1 is poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmale] (mPBI), and it is special Levy and be：Polymer viscosity average molecular weigh is soluble in dimethylacetylamide between 3~50,000（DMAc）, dimethyl formyl Amine（DMF）, dimethyl sulfoxide (DMSO)（DMSO）, 1-METHYLPYRROLIDONE, the PBI polymer in the organic solvent such as dimethylbenzene, due to The solubility property of mPBI is better than ABPBI, so their degree of polymerization is bigger than ABPBI.
3. nano template according to claim 1 is：SiO2, magnesia, iron oxide, iron hydroxide etc., its feature exists In, particle diameter in 5~50nm, grain shape can be a nanometer ball-type, cube, multiedge cylinder or cylindric etc..
4. mPBI according to claim 1 and the mass ratio of nano template are 3:1~1:3；Hybrid mode is：MPBI is molten Liquid mixes with nano particle, and after being uniformly mixed, the lower heating of stirring steams solvent near dry, is vacuum dried, finely ground, pyrolysis Afterwards, with watery hydrochloric acid or HF acid elutions removing template agent removing.
5. pyrolysis temperature according to claim 1 is 700 ~ 1100 DEG C.
6. the three-dimensional nitrogen-doped graphene for obtaining according to claim 1, is applied to the catalyst of catalytic oxidation-reduction reaction, Used in metal-air battery, fuel cell；Can also be used for the catalyst of catalytic electrolysis water oxygen evolution reaction；Can be additionally used in super electricity The electrode material of container.
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CN108630455A (en) * 2018-05-28 2018-10-09 青岛大学 A method of using tri- imidazole radicals benzene of 1,3,5- ultracapacitor is prepared for carbon source
CN108766787A (en) * 2018-05-28 2018-11-06 青岛大学 A method of using the bis- imidazole radicals biphenyl of 4,4`- ultracapacitor is prepared for carbon source

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CN105836738A (en) * 2016-05-06 2016-08-10 清华大学 Non-carbon heteroatom-modified porous graphene framework and preparation method thereof

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CN108630455A (en) * 2018-05-28 2018-10-09 青岛大学 A method of using tri- imidazole radicals benzene of 1,3,5- ultracapacitor is prepared for carbon source
CN108766787A (en) * 2018-05-28 2018-11-06 青岛大学 A method of using the bis- imidazole radicals biphenyl of 4,4`- ultracapacitor is prepared for carbon source

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