CN106744846A - A kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing - Google Patents
A kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing Download PDFInfo
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Abstract
The present invention is a kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing.With poly-（2,5 benzimidazoles）（ABPBI）It is carbon source and nitrogen source, is template with the hydrophobic stratified material of cationic surfactant modified montmorillonoid, is filled into stratiform template interlayer with vacuum aided method after ABPBI dissolvings, and it is regularly arranged, pyrolysis, removes template agent removing, obtains the two-dimentional nitrogen-doped graphene of high nitrogen-containing.ABPBI is from dissolvable oligomer；Distance between stratiform template interlayer can be adjusted by changing the molecular structure of its ion surfactant for adsorbing, and interlamellar spacing is between 0.2~0.6 nm；ABPBI is 2 with stratiform template mass ratio:1~1:3；Pyrolysis temperature is 700 ~ 1000 DEG C；Hydrofluoric acid removes template agent removing.The high nitrogen-containing two dimension nitrogen-doped graphene of preparation is used for the oxygen reduction catalyst of fuel cell or metal air battery cathodes, and the oxygen of anode of electrolytic water separates out the fields such as catalyst, electrode material for super capacitor.
Description
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 be by carbon atom it is tightly packed into individual layer two dimension carbonaceous material.Due to fabulous electricity, optics,
The performances such as machinery, its developmental research and application are extensively paid close attention to by people.Graphene is due to its ultralight quality and two-dimensional structure, tool
There are many special performance (Bacsa R R, et al. Carbon (carbon), 2015,89: 350).Graphene after doping
Performance is more protruded, and mainly includes boron doping, N doping, phosphorus doping, sulfur doping and polyatomic codope or three doping etc..
In all kinds of Heteroatom doping Graphenes, nitrogen-doped graphene（NG）Most study, nitrogen has 5 kinds of bonding structures, respectively stone
Black nitrogen, pyridine nitrogen, pyrroles's nitrogen, ammonia nitrogen and nitrogen oxide（Nie Yao etc., Journal of Chemical Industry and Engineering）, 2015, 66: 3305）, wherein,
Only pyridine nitrogen and pyrroles's nitrogen is planar structure, and they have been proved to oxygen reduction activity, conversely, three-dimensional structure
Nitrogen-atoms is without activity.With graphene oxide in silica etc. for template ethylenediamine reduces the N doping stone for preparing three-dimensional structure
Black alkene is it has been reported that still its oxygen reduction activity is still lower than Pt/C（Yang S B, et al. Angew Chem Int
Ed (German applied chemistry), 2011,123: 5451）.The preparation method of nitrogen-doped graphene has a lot：Such as, graphite oxide
Reducing process；Micromechanics stripping method (Zhao W F, et al. J. Mater. Chem. (materials chemistry magazine), 2010;
20, 5817)；Chemical vapour deposition technique（CVD）(Jin Z, et al. ACS Nano (American Chemical Society-nanometer), 2011,
5(5): 4112)；Heat-treatment oxidation Graphene (Li X, the et al. J Am Chem Soc under ammonia atmosphere（American chemical
Can will） 2009, 131: 15939)；Directly it is pyrolyzed the 2,6- diamino-pyridines of abundant Fe, Co coordination polymerization of nitrogen atom
(Zhao Y, et al. J Am Chem Soc (JACS), 2012,134 (48):19528) etc..
Template is done with stratified material, the method limited with vertical direction size, aniline is in stratiform template internal-response system
Standby polyaniline, pyrolysis prepares two-dimentional nitrogen-doped graphene and has had been reported that (Ding W, et al. Angew Chem Int Ed
(German applied chemistry-world version), 2013,52: 1175）, due to its special sandwiched area limitation, the polyaniline of synthesis
Meeting planar alignment, being pyrolyzed the two-dimentional nitrogen-doped graphene for preparing can contain more pyridine nitrogens and pyrroles's nitrogen, therefore, it shows
Excellent catalytic oxidation-reduction performance.The method of document is that template montmorillonite prepares H using acid is modified+The montmorillonite of type, obtains
The interlayer of hydrophilic；It is anilinechloride that small molecule aniline generates hydrophilic in acid condition, is conducive to inserting hydrophilic
Interlayer in, small molecule be also easy to enter interlayer in, it is not necessary to carry out complexity operation；To there is polymerization in aniline anti-in interlayer
Should, polyaniline is obtained, the process of its polymerization is just controlled by vertical direction area size.The polyaniline plane for obtaining point
Son, is pyrolyzed under inert gas shielding, obtains the Graphene of two-dimentional N doping.
The present invention is the macromolecular material using the benzimidazole unit of armaticity, is gathered（2,5- benzimidazoles）（ABPBI）
It is carbon source and nitrogen source, pyrolysis prepares the carbon material of N doping under inert gas shielding.Covered with cationic surfactant is modified
De- soil stratified material, obtains hydrophobic interlayer and does template, makes rigid ABPBI molecules regularly arranged in interlayer, occurs without a large amount of
Stacking, curling etc. are unfavorable for generating the situation of Graphene to prepare the material of multilayer two-dimension nitrogen-doped graphene structure.The present invention
It is with document difference：First, be to stratiform mould material acid modification, to increase interlamellar spacing.Cationic surface is used again
Activating agent is modified treatment, its interlayer is become hydrophobic, and interlamellar spacing becomes big, it is conducive to hydrophobic macromolecule material
Material is inserted into interlayer；Secondly, macromolecule ABPBI molecules are allow to enter in interlayer using the method for vacuum aided；Third, just
Property ABPBI molecules in interlayer drying can reach the regularly arranged of molecule, be conducive to preventing a large amount of stackings, curling etc. unfavorable
In the situation of generation Graphene.It is pyrolyzed under inert gas shielding after insertion ABPBI, two-dimentional nitrogen is obtained by removing template agent removing and is mixed
Miscellaneous Graphene.
And the method for document is the modified preparation H of template montmorillonite use acid+The montmorillonite of type, obtains the folder of hydrophilic
Layer；Small molecule aniline generates water-soluble anilinechloride in acid condition, be conducive to insert hydrophilic interlayer in；Again
Person, small molecule is also easy to enter in interlayer, it is not necessary to the operation for being replicated；There is polymerisation in aniline, obtain in interlayer
Polyaniline, the process of its polymerization is just controlled by area size.The molecule of the polyaniline plane for obtaining, in inert gas shielding
Lower pyrolysis, obtains the Graphene of two-dimentional N doping.
Key technology of the invention is the silicic acid anhydride of interlayer, the control of interlamellar spacing, the insertion of ABPBI molecules and regularly arranged
And the factor such as the proportioning of ABPBI and template.Hydrophobic treatment be macromolecule insertion basis, interlamellar spacing control and template and
ABPBI proportionings decide the regular degree of macromolecule arrangement and obtain the number of plies of Graphene.
Poly- 2,5- benzimidazoles (ABPBI）It is simplest one kind in PBI families, is using 3,4- diaminobenzoic acids
Raw material, under inert gas argon gas shielded, condensation polymerization is obtained under the conditions of 200 DEG C in the polyphosphoric acids (PPA).It prepares reaction
Equation is as follows：
Polybenzimidazoles（PBI）It is high molecular polymer that a class contains benzimidazole group, benzimidazole ring belongs in molecule
The stiffening ring of armaticity, in PBI molecules easily pile up aggregation, in molecule on imidazole ring contain imidazoles nitrogen, so, PBI with gold
Category ion（Such as Cu, Mn, Fe, Ru, Ti, Mo and Os）The complex formed after coordination can be used for the redox of organic compound
Catalysts（Olason G, et al. React Funct Polmer (reaction and functional polymer) 1999,42:
163; Cameron C G, et al. J Phys Chem B,（（The U.S.）Acta PhySico-Chimica Sinica B）2001, 105: 8838
；Mbelck R, et al. React Funct Polmer, (reaction and functional polymer) 2007,67:1448）, D
Archivio have studied the preparation method and performance of porous PBI resin materials, and have studied it with metallic ion coordination preparation
Catalyst（D Archivio, et al. Chem-A Eur J, (European The Chemicals) 2000,6 (5): 794）.
The invention is by the use of the benzimidazole of armaticity as offer carbon and the raw material of nitrogen, under inert gas argon gas shielded
Pyrolysis prepares nitrogenous carbon material.PBI solution is pressed between the interlayer of hydrophobic stratified material by the method for vacuum aided,
Vacuum removes solvent, makes the benzimidazole ring in interlayer in PBI regularly arranged, plane flush system structure is formed, in indifferent gas
The lower pyrolysis of body protection, PBI vertical direction in interlayer limits its reaction, the plane N doping of two dimension can be formed in the horizontal direction
Graphene-structured, goes template agent removing to obtain two-dimentional nitrogen-doped graphene.The ratio of feed change and hard template, Control architecture interlamellar spacing
To control the number of plies and performance of the nitrogen-doped graphene for preparing, preferable multilayer two-dimension nitrogen-doped graphene is finally given.
Material, catalyst or catalyst carrier used by the field such as energy conversion and storage, sensor, electrolysis, it is desirable to have
Certain electronic conductivity.Therefore, it is conventional method that macromolecular material method for pyrolysis prepares carbon material, such as with phenolic aldehyde tree
The pyrolysis such as fat, pollopas and melmac prepare carbon material.
Compared with phenolic resin, pollopas and melmac Polymer material, the difference of ABPBI is
It contains the stiffening ring benzimidazole ring of armaticity, and imidazoles nitrogen on imidazole ring makes its nitrogen content more enrich.Therefore high temperature
Pyrolysis ABPBI can obtain the carbon material of the N doping of high content, and by introducing the virtue of suitable template or control molecule
The orientation of fragrant plane of a loop, can obtain the grapheme material of multilayer N doping respectively after pyrolysis.
Compared with the material such as polyaniline and polypyrrole prepares nitrogen-doped graphene, ABPBI can dissolve, it is easy to be inserted into template
In agent interlayer, and polyaniline, polypyrrole etc. are insoluble, it is impossible to mix with template.Can only be operated before the polymerization.Acid changes
Property montmorillonite interlayer in aniline the polyaniline for preparing of in-situ polymerization, due to its special sandwiched area limitation, synthesis it is poly-
Aniline meeting planar alignment, being pyrolyzed the two-dimentional nitrogen-doped graphene for preparing can contain more pyridine nitrogens and pyrroles's nitrogen, therefore, its table
Reveal excellent catalytic oxidation-reduction performance.The method of document is that template montmorillonite prepares H using acid is modified+The montmorillonite of type,
Obtain the interlayer of hydrophilic；It is anilinechloride that small molecule aniline generates hydrophilic in acid condition, is conducive to insertion parent
In the interlayer of water type, small molecule is also easy to enter in interlayer, it is not necessary to carry out the operation of complexity；Aniline is polymerized in interlayer
Reaction, obtains polyaniline, and the process of its polymerization is just controlled by vertical direction area size.The polyaniline plane for obtaining point
Son, is pyrolyzed under inert gas shielding, obtains the Graphene of two-dimentional N doping.It is acid modification that the present invention is different from part
Montmorillonite is modified with cationic surfactant again, hydrophobic interlayer is prepared, by the alkane for adjusting cationic surfactant
Base chain adjusts the interlamellar spacing of interlayer, with the method for vacuum aided hydrophobic Polymer Solution regular array in interlayer, it is lazy
Pyrolysis prepares the nitrogen-doped graphene of high nitrogen-containing under property gas shield.
The content of the invention
The content of the invention
The present invention, has invented a kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing.
The present invention is the macromolecular material using the benzimidazole unit of armaticity, is gathered（2,5- benzimidazoles）（ABPBI）
It is carbon source and nitrogen source, with cationic surfactant modified montmorillonoid stratified material, obtains hydrophobic interlayer and do template, makes rigid
Hydrophobic ABPBI molecules insert hydrophobic interlayer, and regularly arranged in interlayer, prevent a large amount of stackings, curling etc. no
The material of multilayer two-dimension nitrogen-doped graphene structure is prepared beneficial to the situation of generation Graphene.By selecting cationic surface
The molecular structure of activating agent, regulates and controls hydrophobic interlayer interlamellar spacing, further the number of plies of nitrogen-doped graphene prepared by regulation and control.Control is former
Material controls arrangement mode of the ABPBI molecules in interlayer with the method for mass ratio and raw material the insertion interlayer of template, and then
The quality and performance of control generation nitrogen-doped graphene.
The present invention is with document difference：First, be to stratiform mould material acid modification, to increase interlamellar spacing.
Treatment is modified with cationic surfactant again, its interlayer is become hydrophobic, and interlamellar spacing becomes big, by regulation
The alkyl chain of cationic surfactant adjusts the interlamellar spacing of interlayer, makes it be conducive to hydrophobic macromolecular material to be inserted into folder
In layer, the optional quaternary ammonium type of cationic surfactant and salt form ionic surface active agent：Such as,（C6~C18Alkyl trimethyl bromination
Ammonium；C4~C16Alkyl dimethyl benzyl ammonium bromide）, C4~C16Cetylpyridinium bromide salt etc.；Secondly, using the method for vacuum aided
Macromolecule ABPBI molecules are allow to enter in interlayer；Third, the drying in interlayer of rigid ABPBI molecules can reach molecule
It is regularly arranged, be conducive to preventing a large amount of stackings, curling etc. to be unfavorable for generating the situation of Graphene.In inertia after insertion ABPBI
It is pyrolyzed under gas shield, the Graphene of two-dimentional N doping is obtained by removing template agent removing.
And the method for document is the modified preparation H of template montmorillonite use acid+The montmorillonite of type, obtains the folder of hydrophilic
Layer；Small molecule aniline generates water-soluble anilinechloride in acid condition, be conducive to insert hydrophilic interlayer in；Again
Person, small molecule is also easy to enter in interlayer, it is not necessary to the operation for being replicated；There is polymerisation in aniline, obtain in interlayer
Polyaniline, the process of its polymerization is just controlled by area size.The molecule of the polyaniline plane for obtaining, in inert gas shielding
Lower pyrolysis, obtains the Graphene of two-dimentional N doping.
Key technology of the invention is the silicic acid anhydride of interlayer, the control of interlamellar spacing, the insertion of ABPBI molecules and regularly arranged
And the factor such as the proportioning of ABPBI and template.Hydrophobic treatment is the basis of macromolecule molecule insertion, cationic surfactant
Structure can regulate and control the interlamellar spacing of interlayer, template matched with ABPBI and auxiliary ABPBI rigid macromolecule insertions mode,
The regular degree that decide arrangement of the macromolecule in interlayer and the number of plies and performance that obtain Graphene.
By the interlamellar spacing for adjusting the alkyl chain of cationic surfactant to adjust interlayer, ABPBI is controlled with template
Mass percent, the injection mode of ABPBI solution and the method such as template and ABPBI solution blending methods and pyrolytic process are adjusted
The number of plies of the standby nitrogen-doped graphene of control.The materials application is in redox reaction catalyst, oxygen reduction catalyst, electrolysis water
Oxygen separates out the fields such as catalyst and carrier, ultracapacitor, electrolysis, sensor material.
ABPBI is with above phenolic resin, pollopas and melmac Polymer material difference：ABPBI
Benzimidazole ring belongs to the stiffening ring of armaticity in molecule, contains imidazoles nitrogen in molecule on imidazole ring, belongs to the aroma type of rich nitrogen
High molecular polymer.Therefore, its pyrolysis can obtain the carbon material of N doping, if under suitable template action, can obtain
To the grapheme material of multilayer N doping.If controlling the plane of the aromatic rings of molecule to be arranged according to a direction, its pyrolysis can
To obtain the graphene-structured of N doping.If be pyrolyzed the graphene-structured of three-dimensional N doping can be obtained with shuttering supporting.With
It is polyaniline, poly-（O-phenylenediamine）, unlike polypyrrole Polymer material：ABPBI family macromolecules be soluble in DMAc,
In the organic solvents such as DMSO, easily it is sufficiently mixed with template, because it is soluble, it is preparing nitrogen-doped graphene nano material
When have well operability.However, polyaniline compound, polypyrrole Polymer material are insoluble, it is impossible to be blended with template.
ABPBI is that viscosity average molecular weigh prepared by solid phase method or liquid phase method is soluble in DMAC between 10,000~30,000,
DMF, DMSO, in 1-METHYLPYRROLIDONE equal solvent.Molecular weight is too big, and the solubility property of ABPBI is deteriorated；Too small its heat of molecular weight
Solve the Graphene performance for preparing not good enough.
The method of the preparation of the Graphene of N doping is：Montmorillonite first carries out acidification, cleans drying, is separately added into
The cationic surfactant of different alkyl chains is modified, and prepares the montmorillonite of hydrophobic interlayer as template.A certain amount of
Template be put into the container that can be vacuumized, a certain amount of ABPBI dissolving form solution, template to be filled in a solvent
After the container vacuum-pumping 30min of agent, valve is closed, with syringe to the solution that appropriate ABPBI is injected in container, treat that solution is submerged
After template, begin to warm up, vacuumize, solvent is steamed at leisure near dry, it is so repeated multiple times until the solution of ABPBI is used
It is complete.Take out, dried at 60 ~ 120 DEG C in the drying box.It is finely ground in mortar, porcelain boat bottom is laid in, it is put into electric tube furnace,
Under argon gas protection, at 600~1200 DEG C, 2 ~ 3h is pyrolyzed.Treat that furnace temperature is cooled to room temperature, take out, repeatedly washed with hydrofluoric acid
To go removing template montmorillonite, suction filtration is washed with deionized water net, drying, obtains two-dimentional nitrogen-doped graphene product.
In the present invention：The optional quaternary ammonium type of cationic surfactant and salt form ionic surface active agent：Such as,（C6~C18
Alkyl trimethyl ammonium bromide；C4~C16Alkyl dimethyl benzyl ammonium bromide）, cetylpyridinium bromide salt etc..The length of its alkyl is not
But the hydrophobicity of interlayer can be controlled, and the interlamellar spacing of interlayer can be adjusted.Alkyl carbon chain is more long, and the hydrophobicity of interlayer is got over
By force, interlamellar spacing is wider.The interbedded distance of template determines the number of plies of prepared Graphene, abundant in ABPBI insertions
In the case of, interlamellar spacing is wider, and it is more that ABPBI is inserted, and the number of plies of the Graphene for obtaining is also more.Therefore cationic surface is lived
The modification of property agent is extremely important, preferably comprises C6-C12Alkyl cationic surfactant.Another key technology of the invention
It is fillings and arranging situation of the ABPBI in interlayer：The full interlayer of ABPBI fillings is required first；Secondly, it is desirable to which ABPBI is in interlayer
It is interior regularly arranged.Only in this way can just obtain complete two-dimentional nitrogen-doped carbon material.This require ABPBI solution repeatedly suction and
Repeated after slowly draining repeatedly.
ABPBI macromolecular chains are made up of the rigid benzimidazole of armaticity, and contain the miaow rich in nitrogen in molecule
Azoles ring and Amino End Group；Polymer viscosity average molecular weigh is soluble in dimethylacetylamide between 1~30,000（DMAC）, dimethyl
Formamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）With the organic solvent such as 1-METHYLPYRROLIDONE.
ABPBI is 2 with the mass ratio of template modified montmorillonoid:1~1:3；Hybrid mode is：Weigh a certain amount of template
Agent modified montmorillonoid 160~220 DEG C of heating 2h in high temperature furnace, water, gas or impurity are adsorbed in multilayer material interlayer to remove.
Room temperature to be cooled to, is transferred in the pressure vessel for being connected with vavuum pump, vacuumizes 30~40min, with syringe in pressure vessel
A certain amount of ABPBI solution is injected, ABPBI solution is soaked template, continue to vacuumize, after after no liquid in container, continued
Aforesaid operations run out up to ABPBI solution, drain.The template of suction ABPBI solution, take out in vacuum drying chamber
Interior 60~120 DEG C of ageings, the sample for being cooled to room temperature takes out, finely ground, is put into porcelain boat, 700 under argon gas protection in high temperature furnace ~
2~3h is pyrolyzed at 1000 DEG C, after after furnace temperature cooling, sample is taken out, template is washed away with hydrofluoric acid, acid is washed with deionized water,
Dried at 80~120 DEG C in the vacuum drying chamber, that is, obtain the two-dimentional nitrogen-doped graphene product of black.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 600~1200 DEG C, preferably 700~1000 DEG C.Temperature is too low
ABPBI can not be pyrolyzed, and the electric conductivity for obtaining product is poor；After pyrolysis temperature reaches optimum temperature, then raise pyrolysis temperature its property
Can be constant, so pyrolysis temperature is unsuitable too high.
The Graphene characterizing method of two-dimentional 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）To characterize.The degree of graphitization of product, graphene-structured and the number of plies can be with
Use X-ray powder diffraction（XRD）, Raman spectrum characterizes.The element composition of product, valence state can use X-ray photoelectron energy
Spectrum（XPS）Characterized, used rotating disk electrode (r.d.e)（RDE）Carry out the catalytic oxidation-reduction reaction of test product（ORR）Performance, water power
Solution oxygen evolution reaction（EOR）, evolving hydrogen reaction（EHR）Capacitive property test with product can use cyclic voltammetric（CV）, linear volt
Peace（LSV）, Tafel curve and charge-discharge performance test.Product can use CV, LSV as the durability test of catalyst
And chronoa mperometric plot（i-t）.The catalytic performance of product finally needs assembling metal-air battery, hydrogen-oxygen fuel cell, electrolysis
The electrolytic cell of water, ultracapacitor and sensor test its performance.
The present invention is with document difference：First, be to stratiform mould material acid modification, to increase interlamellar spacing.
Treatment is modified with cationic surfactant again, its interlayer is become hydrophobic, and interlamellar spacing becomes big, is conducive to it
Hydrophobic macromolecular material is inserted into interlayer；Secondly, enter macromolecule ABPBI molecules using the method for vacuum aided
In interlayer；Third, the drying in interlayer of rigid ABPBI molecules can reach the regularly arranged of molecule, be conducive to preventing a large amount of
Stacking, curling etc. are unfavorable for generating the situation of Graphene.It is pyrolyzed under inert gas shielding after insertion ABPBI, removes template agent removing
Can obtain the Graphene of two-dimentional N doping.
Specific embodiment
The preparation of [embodiment 1] ABPBI（Method one, solid phase method）：Take appropriate 3,4- diaminobenzoic acids（DABA）
It is transferred to after in mortar, being fully ground equipped with electric stirring, inert gas shielding there-necked flask, leads to N2, 15min is arranging
Air to the greatest extent in flask.N2Protection, under stirring, 225 DEG C of heating of oil bath keep 3h.Taken out after cooling, finely ground, N2Under protection, electricity
Heating in stove, is warmed up to 270-275 DEG C, keeps 3h.Be cooled to room temperature, by product take out, it is finely ground, that is, obtain ABPBI, use Ubbelohde
Viscosimeter determines the molecular weight of ABPBI.
The preparation of [embodiment 2] ABPBI（Method two, liquid phase method）：Polyphosphoric acids (PPA) (50g) is added to three mouthfuls
In flask, under nitrogen protection, 160 DEG C are stirred 1 h to remove moisture and air.Add 3,4- diaminobenzoic acids (6 g, 39.5
Mmol 190 DEG C) and by temperature are increased to, N is controlled2Flow velocity, prevents DABA to be oxidized, and stirring reaction 3h, reacted at 200 DEG C
About 5g P are dividedly in some parts in journey2O5With the water generated during absorbing reaction.With the increase in reaction time, polymerization system is gradually
Become sticky.Reaction mixture is slowly transferred in deionized water, is reeled off raw silk from cocoons, and forms fibrous black solid, takes out drying, powder
It is broken, wash to remove the polyphosphoric acids in reactant mixture and unreacted raw material.Obtain ABPBI products.Use Ubbelohde viscometer
Determine the molecular weight of ABPBI.
Sour modification and the cationic surfactant modification of [embodiment 3] montmorillonite.
The acid of montmorillonite is modified：
Take 10g montmorillonites（Na-MMT）It is put into 1000mL beakers, adds the HCl of the mol L-1 of 600mL 0.1, under stirring, soaks
Bubble 2 days, suction filtration is repeatedly washed, suction filtration with substantial amounts of deionized water, 60 °C of dry sour modified montmorillonites（H-MMT）.Survey
Fixed its ion exchange capacity is 0.25meq/g.
The modified montmorillonite of cationic surfactant（MMTCX）,
Weigh 5g H-MMT（0.25meq/g）, dried at 120 DEG C, to remove the impurity such as its water for adsorbing, under agitation slowly
The cetyl trimethylammonium bromide cationic surfactant of 0.456g is added to be dissolved in 300mL deionized water solutions,
4h is sufficiently stirred in 60 °C of water-baths, it is uniformly dispersed, stood overnight, centrifugation, cleaned with deionized water to without Br-,
Dried under 120 °C, grinding obtains surfactant-modified MMT and is abbreviated as MMTC16。
The illiteracy of the acid modification that [embodiment 4] is modified with cetyl trimethylammonium bromide cationic surfactant takes off
Soil（MMTC16, the montmorillonite of other alkyl modifieds is labeled as MMTCX, wherein X is the carbon number of alkyl）, with ABPBI and template
Agent mass ratio is 1:As a example by 1：
In the beaker of 250mL, the ABPBI of 1g is added（Viscosity average molecular weigh 2 ~ 30,000）With 20mL DMAc, heating, stirring make its molten
Solution, solution suction filtration is standby to remove insoluble matter.In the bottle,suction of 250mL, 1g MMT are addedC16It is laid in bottom of bottle, take out
After filter flask vacuumizes 30min, valve is closed, stop vacuumizing, the DMAc solution of ABPBI is added with syringe, it is fully moistened
Wet template, continues to vacuumize to remove solvent, it is to be dried it is rear it is repeated multiple times all added until the DMAc solution of ABPBI,
After draining, the MMT of suction ABPBIC16Template takes out 60~120 DEG C of ageings in vacuum drying chamber, is cooled to room temperature and takes
Go out, it is finely ground, porcelain boat is put into, 2~3h is pyrolyzed at 800 DEG C under argon gas protection in the high temperature furnace, after after furnace temperature cooling, sample is taken out,
Template is washed away with hydrofluoric acid, is washed with deionized water to neutrality, dried at 80~120 DEG C in the vacuum drying chamber.Obtain black
Pulverulent solids 0.68g.BET tests show that its surface area is 15 ~ 22nm, 562 m2 g-1, SEM test show, the product for obtaining
Product are porous carbon materials, TEM and HRTEM analysis shows, product is multi-layer graphene structure carbon material, and Graphene is drawn a bow to the full back and is shown to be
3 ~ 4 layer graphenes.XRD and Raman spectrum test show that product is 3 ~ 4 layers of graphene-structured；XPS analysis show, product nitrogen
Content is 7.8%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the two-dimensional graphene structure of N doping.
In its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, initial hydrogen reduction current potential is 0.987V vs RHE, and electron transfer number is
3.98, durability is good；Magnesium air cell performance reaches 120mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 458.6mW/
cm2, it is 1.43 vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches 72mA/cm2。
Ultracapacitor specific capacitance is 756F g-1, be recycled 10000 times still holding capacitor value 97%.
[embodiment 5] as described in Example 4, other conditions are identical, and simply pyrolysis temperature is changed to 700 DEG C.The product for obtaining
Product are 0.72g black powders, and test result shows that its product remains as the material of 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure,
Only because its degree of graphitization is relatively low, its electronic conductivity is slightly worse, so its chemical property is slightly worse：Its 0.1mol/
In LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.82V vs RHE, and electron transfer number is 3.58, resistance to
Long property is good；Magnesium air cell performance reaches 79mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 325mW/cm2, 0.5mol/L
Sulfuric acid solution in oxygen to separate out take-off potential be 1.51 vs RHE, limiting current density reaches 65mA/cm2.Ultracapacitor
Specific capacitance is 542F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 6] as described in Example 4, other conditions are identical, simply change pyrolysis temperature and are changed to 900 DEG C.Obtain
Product be 0.66g black powders, test result shows that its product remains as 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.985V vs RHE, electronics
Transfer number is 3.98, and durability is good；Magnesium air cell performance reaches, 127mW/cm2.For hydrogen-oxygen fuel cell, its peak power is
526mW/cm2, it is 1.45 vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches
79mA/cm2.Ultracapacitor specific capacitance is 687F g-1, be recycled 10000 times still holding capacitor value 97%.
[embodiment 7] as described in Example 4, other conditions are identical, and simply pyrolysis temperature is changed to 1000 DEG C.Obtain
Product is 0.65g black powders, and test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.967V vs RHE, and electronics turns
It is 3.97 to move number, and durability is good；Magnesium air cell performance reaches 121mW/cm2.For hydrogen-oxygen fuel cell, its peak power is
452mW/cm2, it is 1.48 vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches
85mA/cm2.Ultracapacitor specific capacitance is 621F g-1, be recycled 10000 times still holding capacitor value 97%.
[embodiment 8] as described in Example 4, other conditions are identical, simply change ABPBI and MMTC16The ratio of template
Example is 1：2.The product for obtaining is 0.72g black powders, and test result shows that its product remains as 2 ~ 4 layers of two-dimentional N doping
The material of graphene-structured, due to MMTC16The increase of amount so that ABPBI fillings are not abundant enough, the two-dimentional N doping graphite for obtaining
Alkene lamella diminishes, and its electric conductivity is deteriorated, in its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential
It is 0.725V vs RHE, electron transfer number is 3.58, and durability is good；Magnesium air cell performance reaches 88mW/cm2.For hydrogen-oxygen
Its peak power of fuel cell is 410mW/cm2.It is 1.56 vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L,
Limiting current density reaches 55mA/cm2.Ultracapacitor specific capacitance is 426F g-1, it is recycled 10000 still holding capacitor values
94%.
[embodiment 9] as described in Example 4, other conditions are identical, simply change ABPBI and MMTC16The ratio of template
Example is 1：3.The product for obtaining is 0.71g black powders, and test result shows that its product remains as 2 ~ 4 layers of two-dimentional N doping
The material of graphene-structured, only because MMTC16The increase of amount so that ABPBI fillings are not abundant enough, the two-dimentional N doping for obtaining
Graphene sheet layer diminishes, and its electric conductivity is deteriorated.In its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction
Current potential is 0.71V vs RHE, and electron transfer number is 3.51, and durability is good；Magnesium air cell performance reaches 62mW/cm2.For
Its peak power of hydrogen-oxygen fuel cell is 312mW/cm2, it is 1.61 vs that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L
RHE, limiting current density reaches 45mA/cm2.Ultracapacitor specific capacitance is 321F g-1, it is recycled 10000 times and still keeps
The 93% of capacitance.
[embodiment 10] as described in Example 4, other conditions are identical, simply change ABPBI and MMTC16Template
Ratio is 2：1.The product for obtaining is 0.67g black powders, and test result shows, its product is except 2 ~ 4 layers of two-dimentional N doping
Outside the material of graphene-structured, the also carbon material of part N doping.This is due to the increase of ABPBI amounts so that ABPBI is removed
Outside filling interlayer space, also some residual, remaining ABPBI forms the porous carbon of N doping in template Surface coating
Material, its catalytic performance is deteriorated.In its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is
0.66V vs RHE, electron transfer number is 3.52, and durability is good；Magnesium air cell performance reaches 52mW/cm2.For hydrogen-oxygen combustion
Its peak power of material battery is 310mW/cm2, it is 1.68 vs RHE, pole that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L
Current density of rationing the power supply reaches 42mA/cm2.Ultracapacitor specific capacitance is 268F g-1, it is recycled 10000 still holding capacitor values
90%。
[embodiment 11] as described in Example 4, other conditions are identical, and simply template uses MMT insteadC6.The product for obtaining
It is 0.72g black powders, test result shows, its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, only
It is because the alkyl carbon chain of cationic surfactant is shorter so that MMTC6Interlamellar spacing reduces, and the amount for obtaining ABPBI is on the high side.Its
In 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.845V vs RHE, and electron transfer number is
3.94, durability is good；Magnesium air cell performance reaches 102mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 452mW/cm2,
It is 1.51 vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches 74mA/cm2.It is super
Capacitor specific capacitance is 421F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 12] as described in Example 4, other conditions are identical, simply MMTC8.The product for obtaining is that 0.71g is black
Color powder, test result shows that its product is the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, only because cation
The alkyl carbon chain of surfactant is shorter so that MMTC8Interlamellar spacing reduces, and the amount for obtaining ABPBI is on the high side.Its 0.1mol/LKOH is molten
In liquid, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.849V vs RHE, and electron transfer number is 3.95, and durability is good
It is good；Magnesium air cell performance reaches 116mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 476mW/cm2.The sulphur of 0.5mol/L
It is 1.51 vs RHE that oxygen separates out take-off potential in acid solution, and limiting current density reaches 84mA/cm2.Ultracapacitor specific capacitance
It is 426F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 13] as described in Example 4, other conditions are identical, simply MMTC14.The product for obtaining is that 0.76g is black
Color powder, test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, its 0.1mol/
In LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.88V vs RHE, and electron transfer number is 3.83, resistance to
Long property is good；Magnesium air cell performance reaches, 87mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 780mW/cm2, 0.5mol/
It is 1.47V vs RHE that the sulfuric acid solution oxygen of L separates out take-off potential, and limiting current density reaches 156mA/cm2.Ultracapacitor
Specific capacitance is 726F g-1, be recycled 10000 times still holding capacitor value 97%.
[embodiment 14] as described in Example 4, other conditions are identical, simply MMTC18.The product for obtaining is 0.75g black powder
End, test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, and its 0.1mol/LKOH is molten
In liquid, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.78V vs RHE, and electron transfer number is 3.81, and durability is good
It is good；Magnesium air cell performance reaches, 75mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 687mW/cm2, the sulphur of 0.5mol/L
It is 1.49V vs RHE that acid solution oxygen separates out take-off potential, and limiting current density reaches 135mA/cm2.Ultracapacitor specific capacitance
It is 654F g-1, be recycled 10000 times still holding capacitor value 96%.
Claims (7)
1. the preparation method of the two-dimentional nitrogen-doped graphene of a kind of high nitrogen-containing, it is characterised in that：It is by virtue from macromolecular chain
The rigid benzimidazole composition of fragrance, and gather containing the imidazole ring rich in nitrogen and the soluble of Amino End Group in molecule（2,
5- benzimidazoles）（ABPBI）It is carbon source and nitrogen source, the hydrophobic interlayer of montmorillonite being modified with cationic surfactant etc. is mould
Plate, the method for the solution vacuum aided of the ABPBI of solubility is filled into the interlayer of template, the fragrance in ABPBI molecules
Ring is regularly arranged in interlayer, imidazole ring and end ammonia in its molecule rich in nitrogen, under inert gas shielding, pyrolysis, use
Hydrofluoric acid wash removes template, prepares the two-dimentional nitrogen-doped graphene of high nitrogen-containing；ABPBI is soluble, its benzo miaow
Azoles ring is rigid armaticity ring, and nitrogen-doped graphene structure is easily formed in pyrolysis, and depickling rises when the carboxyl in molecule is pyrolyzed
To pore-creating effect；The stratiform template of ABPBI solution and different interlamellar spacings is high under being protected than mixing, argon gas according to different quality
2 ~ 3h of pyrolysis in warm stove, the two-dimentional nitrogen-doped graphene obtained by going template with hydrofluoric acid, the two dimension of described high nitrogen-containing
Nitrogen-doped graphene, 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 the electrode material of ultracapacitor.
2. ABPBI according to claim 1, it is characterised in that：Macromolecular chain is by the rigid benzimidazole group of armaticity
Into, and contain imidazole ring and Amino End Group rich in nitrogen in molecule；Polymer viscosity average molecular weigh, can be with molten between 1~30,000
Solution is in dimethylacetylamide（DMAc）, dimethylformamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）Have with 1-METHYLPYRROLIDONE etc.
Machine solvent.
3. template according to claim 1 is the montmorillonite being modified with cationic surfactant, different cation forms
Face activating agent can adjust the interlamellar spacing of stratified material, and cationic surfactant is changed into hydrophobic state between can making interlayer, easily
In the insertion of hydrophobic polymer ABPBI molecules, it is characterised in that the interlamellar spacing of its interlayer is in 0.2~0.6nm, interlayer anaplasia
For hydrophobic, cationic surfactant selects C6~C18Alkyl trimethyl ammonium bromide type cationic surfactant etc..
4. ABPBI according to claim 1 and the mass ratio of template modified montmorillonoid are 2:1~1:3；Hybrid mode
For：A certain amount of template modified montmorillonoid 160~220 DEG C of heating 2h in high temperature furnace are weighed, to remove multilayer material interlayer
Middle absorption water, gas or impurity.
5. room temperature to be cooled to, is transferred in the pressure vessel for being connected with vavuum pump, vacuumizes 30~40 min, with syringe to pressure
A certain amount of ABPBI solution of injection in container, makes ABPBI solution soak template, continues to vacuumize, and treats no liquid in container
Afterwards, continue aforesaid operations up to ABPBI solution runs out, drain.
6. the template of suction ABPBI solution, 60~120 DEG C of ageings in vacuum drying chamber are taken out, be cooled to room temperature
Sample is taken out, finely ground, is put into porcelain boat, and 2~3h is pyrolyzed under argon gas protection in high temperature furnace, after after furnace temperature cooling, takes out sample, is used
Hydrofluoric acid washes away template, and acid is washed with deionized water, and is dried at 80~120 DEG C in the vacuum drying chamber, that is, obtain black
Two-dimentional nitrogen-doped graphene product.
7. pyrolysis temperature according to claim 1 is 700 ~ 1000 DEG C.
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| CN108190865A (en) * | 2018-02-08 | 2018-06-22 | 东华大学 | A kind of method that graphene is prepared based on template-solid-phase carbon source thermal cracking |
| CN112591738A (en) * | 2020-12-15 | 2021-04-02 | 南京工业大学 | Metal-doped graphene-like carbon material and preparation method and application thereof |
| CN113422082A (en) * | 2021-07-06 | 2021-09-21 | 中国科学技术大学 | Nitrogen-doped carbon five-membered ring structure-containing graphene-like carbon material electrocatalyst and preparation method and application thereof |
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| CN108190865A (en) * | 2018-02-08 | 2018-06-22 | 东华大学 | A kind of method that graphene is prepared based on template-solid-phase carbon source thermal cracking |
| CN108190865B (en) * | 2018-02-08 | 2020-07-28 | 东华大学 | Method for preparing graphene based on template agent-solid carbon source thermal cracking |
| CN112591738A (en) * | 2020-12-15 | 2021-04-02 | 南京工业大学 | Metal-doped graphene-like carbon material and preparation method and application thereof |
| CN113422082A (en) * | 2021-07-06 | 2021-09-21 | 中国科学技术大学 | Nitrogen-doped carbon five-membered ring structure-containing graphene-like carbon material electrocatalyst and preparation method and application thereof |
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