CN106744846B - 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- benzimidazole) (ABPBI) be carbon source and nitrogen source, it is template with the hydrophobic stratified material of cationic surfactant modified montmorillonoid, it is filled into stratiform template interlayer after ABPBI dissolution with vacuum aided method, and it is regularly arranged, pyrolysis, removes template agent removing, obtains the two-dimentional nitrogen-doped graphene of high nitrogen-containing.ABPBI, which is selected, can dissolve oligomer；Distance between stratiform template interlayer can be adjusted by changing the molecular structure for the ion ionic surface active agent that it is adsorbed, and interlamellar spacing is between 0.2~0.6 nm；ABPBI and stratiform template mass ratio are 2:1~1:3；Pyrolysis temperature is 700 ~ 1000 DEG C；Hydrofluoric acid removes template agent removing.Catalyst, the fields such as electrode material for super capacitor are precipitated for fuel cell or the oxygen reduction catalyst of metal air battery cathodes, the oxygen of anode of electrolytic water in the high nitrogen-containing two dimension nitrogen-doped graphene of preparation.
Description
Technical field
Belong to field of nano material preparation, is urged for the fuel cell in clean energy resource field, the cathode of metal-air battery
Agent, electrolysis water catalyst, the fields such as electrode material for super capacitor and electrochemical sensor.
Background technique
Graphene be by carbon atom it is tightly packed at single layer two dimension carbonaceous material.Due to fabulous electricity, optics,
The performances such as machinery, developmental research and application by people concern.Graphene is due to its ultralight quality and two-dimensional structure, tool
There are many special performances (Bacsa R R, et al. Carbon (carbon), 2015,89:350).Graphene after doping
Performance is more prominent, 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 shares 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 are planar structures, and they have been proved to possess oxygen reduction activity, on the contrary, three-dimensional structure
Nitrogen-atoms is without activity.With graphene oxide in the N doping stone that silica etc. is template ethylenediamine reduction preparation three-dimensional structure
Black alkene is it has been reported that still its oxygen reduction activity (Yang S B, et al. Angew Chem Int still lower than Pt/C
Ed (German applied chemistry), 2011,123:5451).The preparation method of nitrogen-doped graphene has very much: such as, graphite oxide
Reduction method；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, et the al. J Am Chem Soc(american chemical under ammonia atmosphere
Meeting will) 2009,131:15939)；Directly it is pyrolyzed the 2,6- diamino-pyridine of nitrogen atom Fe, Co coordination polymerization abundant
(Zhao Y, et al. J Am Chem Soc (American Chemical Society), 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 prepare two-dimentional nitrogen-doped graphene and have 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
Therefore meeting planar alignment, the two-dimentional nitrogen-doped graphene for being pyrolyzed preparation can be shown containing more pyridine nitrogens and pyrroles's nitrogen
Excellent catalytic oxidation-reduction performance.The method of document is template montmorillonite using the modified preparation H of acid+The montmorillonite of type, obtains
The interlayer of hydrophilic；It is the anilinechloride that small molecule aniline generates hydrophilic in acid condition, is conducive to be inserted into hydrophilic
Interlayer in, small molecule is also easy to enter in interlayer, does not need to carry out complicated operation；It is anti-that polymerization occurs in interlayer for aniline
It answers, obtains polyaniline, the process of polymerization is just controlled by vertical direction area size.Point of obtained polyaniline plane
Son is pyrolyzed under inert gas protection, obtains the graphene of two-dimentional N doping.
The present invention is the high molecular material for utilizing the benzimidazole unit of armaticity, poly- (2,5- benzimidazole) (ABPBI)
For carbon source and nitrogen source, pyrolysis prepares the carbon material of N doping under inert gas protection.It is covered with cationic surfactant is modified
De- soil stratified material, obtains hydrophobic interlayer and does template, keep rigid ABPBI molecule regularly arranged in interlayer, does not occur a large amount of
Stacking, curling etc. are unfavorable for the case where generating graphene, to prepare the material of multilayer two-dimension nitrogen-doped graphene structure.The present invention
It is with document difference: firstly, will be to the sour modification of stratiform mould material, to increase interlamellar spacing.Cationic surface is used again
Activating agent is modified processing, so that its interlayer is become hydrophobic, and interlamellar spacing becomes larger, it is made to be conducive to hydrophobic macromolecule material
Material is inserted into interlayer；Secondly, entering macromolecule ABPBI molecule in interlayer using the method for vacuum aided；Third, just
Property ABPBI molecule in interlayer drying can achieve the regularly arranged of molecule, it is unfavorable to be beneficial to prevent a large amount of stackings, curling etc.
In generate graphene the case where.It is pyrolyzed under inert gas protection after insertion ABPBI, goes template agent removing that two-dimentional nitrogen can be obtained and mix
Miscellaneous graphene.
And the method for document is template montmorillonite using the modified preparation H of acid+The montmorillonite of type obtains the folder of hydrophilic
Layer；Small molecule aniline generates water-soluble anilinechloride in acid condition, is conducive to be inserted into the interlayer of hydrophilic；Again
Person, small molecule are also easy to enter in interlayer, do not need the operation replicated；Polymerization reaction occurs in interlayer for aniline, obtains
The process of polyaniline, polymerization is just controlled by area size.The molecule of obtained polyaniline plane, 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 molecule and rule
The factors such as the proportion of arrangement and ABPBI and template.Hydrophobic treatment is the basis of macromolecule insertion, interlamellar spacing control and template
Agent and ABPBI proportion decide the regular degree of macromolecule arrangement and obtain the number of plies of graphene.
Poly- 2,5- benzimidazole (ABPBI) is simplest one kind in PBI family, is using 3,4- diaminobenzoic acid
Raw material, under inert gas argon gas shielded, condensation polymerization is made under the conditions of 200 DEG C in polyphosphoric acids (PPA).It prepares reaction
Equation is as follows:
Polybenzimidazoles (PBI) is a kind of high molecular polymer containing benzimidazole group, benzimidazole ring in molecule
The stiffening ring for belonging to armaticity, easily accumulation is assembled in PBI molecule, contains imidazoles nitrogen in molecule on imidazole ring, so, PBI
It can be used for the oxidation of organic compound with the complex formed after metal ion (such as Cu, Mn, Fe, Ru, Ti, Mo and Os) coordination
Reduction catalyst (Olason G, et al. React Funct Polmer (reaction and functional polymer) 1999,
42: 163;Cameron C G, et al. J Phys Chem B, ((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 has studied the preparation method and performance of porous PBI resin material, and has studied it and prepare with metallic ion coordination
Catalyst (D Archivio, et al. Chem-A Eur J, (European The Chemicals) 2000,6 (5): 794).
The invention is using the benzimidazole of armaticity as the raw material of offer carbon and 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,
Solvent is removed in vacuo, keeps 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 limit its reaction, can form two-dimensional plane N doping 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 template interlamellar spacing
Come control preparation nitrogen-doped graphene the number of plies and performance, finally obtain ideal multilayer two-dimension nitrogen-doped graphene.
Material, catalyst or catalyst carrier used in the fields such as energy conversion and storage, sensor, electrolysis, need
Certain electronic conductivity.Therefore, it is common method that high molecular material method for pyrolysis, which prepares carbon material, such as with phenolic aldehyde tree
The pyrolysis such as rouge, pollopas and melamine resin prepare carbon material.
Compared with the high molecular materials such as phenolic resin, pollopas and melamine resin, ABPBI the difference is that
It contains the stiffening ring benzimidazole ring of armaticity, and the imidazoles nitrogen on imidazole ring keeps its nitrogen content more abundant.Therefore high temperature
It is pyrolyzed the carbon material of the N doping of the available high-content of ABPBI, and by introducing suitable template or controlling the virtue of molecule
The orientation of fragrant plane of a loop, the after pyrolysis grapheme material of available multilayer N doping respectively.
Compared with the materials such as polyaniline and polypyrrole prepare nitrogen-doped graphene, ABPBI be can dissolve, and be inserted easily into template
In agent interlayer, and polyaniline, polypyrrole etc. are insoluble, can not mix with template.It can only be operated before the polymerization.Acid changes
Property montmorillonite interlayer in aniline in-situ polymerization preparation polyaniline, due to its special sandwiched area limitation, synthesis it is poly-
Aniline meeting planar alignment, the two-dimentional nitrogen-doped graphene for being pyrolyzed preparation can be containing more pyridine nitrogens and pyrroles's nitrogen, therefore, table
Reveal excellent catalytic oxidation-reduction performance.The method of document is template montmorillonite using the modified preparation H of acid+The montmorillonite of type,
Obtain the interlayer of hydrophilic；It is the 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, does not need to carry out complicated operation；Aniline polymerize in interlayer
Reaction, obtains polyaniline, and the process of polymerization is just controlled by vertical direction area size.Point of obtained polyaniline plane
Son is pyrolyzed under inert gas protection, obtains the graphene of two-dimentional N doping.It is acid modification that the present invention, which is different from place,
Montmorillonite is modified with cationic surfactant again, prepares hydrophobic interlayer, 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.
Summary 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 high molecular material for utilizing the benzimidazole unit of armaticity, poly- (2,5- benzimidazole) (ABPBI)
It is obtained hydrophobic interlayer with cationic surfactant modified montmorillonoid stratified material for carbon source and nitrogen source and does template, made rigid
Hydrophobic ABPBI molecule is inserted into hydrophobic interlayer, and regularly arranged in interlayer, prevents a large amount of stackings, curling etc. no
The case where conducive to graphene is generated, to prepare the material of multilayer two-dimension nitrogen-doped graphene structure.By selecting cationic surface
The molecular structure of activating agent regulates and controls hydrophobic interlayer interlamellar spacing, further the number of plies of the nitrogen-doped graphene of regulation preparation.Control is former
The mass ratio and raw material of material and template are inserted into the method for interlayer to control arrangement mode of the ABPBI molecule in interlayer, in turn
Control generates the quality and performance of nitrogen-doped graphene.
The present invention is with document difference: firstly, will be to the sour modification of stratiform mould material, to increase interlamellar spacing.
It is modified processing with cationic surfactant again, so that its interlayer is become hydrophobic, and interlamellar spacing becomes larger, passes through adjusting
The alkyl chain of cationic surfactant adjusts the interlamellar spacing of interlayer, so that it is conducive to hydrophobic high molecular material and is 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
Enter macromolecule ABPBI molecule in interlayer；Third, the drying in interlayer of the ABPBI molecule of rigidity can achieve molecule
It is regularly arranged, be beneficial to prevent a large amount of stackings, curling etc. and be unfavorable for the case where generating graphene.It is inserted into after ABPBI in inertia
It is pyrolyzed under gas shield, goes template agent removing that the graphene of two-dimentional N doping can be obtained.
And the method for document is template montmorillonite using the modified preparation H of acid+The montmorillonite of type obtains the folder of hydrophilic
Layer；Small molecule aniline generates water-soluble anilinechloride in acid condition, is conducive to be inserted into the interlayer of hydrophilic；Again
Person, small molecule are also easy to enter in interlayer, do not need the operation replicated；Polymerization reaction occurs in interlayer for aniline, obtains
The process of polyaniline, polymerization is just controlled by area size.The molecule of obtained polyaniline plane, 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 molecule and rule
The factors such as the proportion of arrangement and ABPBI and template.Hydrophobic treatment is the basis of macromolecule molecule insertion, and cationic surface is living
Property agent structure can regulate and control the interlamellar spacing of interlayer, template and ABPBI match and assist the side of ABPBI rigid macromolecule insertion
Formula decides the regular degree of arrangement of the macromolecule in interlayer and obtains the number of plies and performance of graphene.
The interlamellar spacing of interlayer is adjusted by adjusting the alkyl chain of cationic surfactant, controls ABPBI and template
Mass percent, the injection mode of ABPBI solution and template and the methods of ABPBI solution blending methods and pyrolytic process are adjusted
Control the number of plies of standby nitrogen-doped graphene.The material is applied to redox reaction catalyst, oxygen reduction catalyst, electrolysis water
Catalyst and carrier, supercapacitor, the fields such as electrolysis, sensor material are precipitated in oxygen.
The high molecular materials such as ABPBI and the above phenolic resin, pollopas and melamine resin difference is: 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, it is pyrolyzed the carbon material of available N doping, if can obtain under suitable template action
To the grapheme material of multilayer N doping.If the plane for controlling the aromatic rings of molecule is arranged according to a direction, pyrolysis can
To obtain the graphene-structured of N doping.If being pyrolyzed the graphene-structured of available three-dimensional N doping with shuttering supporting.With
Unlike the high molecular materials such as polyaniline, poly- (o-phenylenediamine), polypyrrole: ABPBI class macromolecule be soluble in DMAc,
It in the organic solvents such as DMSO, is easily sufficiently mixed with template, due to its solubility, is preparing nitrogen-doped graphene nano material
When have well operability.However, the high molecular materials such as polyaniline compound, polypyrrole are insoluble, can not 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 N-Methyl pyrrolidone equal solvent.Molecular weight is too big, and the solubility property of ABPBI is deteriorated；Its too small heat of molecular weight
The graphene performance for solving preparation is not good enough.
The method of the preparation of the graphene of N doping are as follows: montmorillonite carries out acidification first, 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 dissolution form solution, template to be filled in a solvent
After the container vacuum-pumping 30min of agent, valve is closed, injects the solution of appropriate ABPBI into container with syringe, submerged to solution
It after template, begins to warm up, vacuumize, steam solvent at leisure and done to close, it is repeated multiple times in this way until the solution of ABPBI is used
It is complete.It takes out, is dried at 60 ~ 120 DEG C in drying box.It is finely ground in mortar, it is laid in porcelain boat bottom, is put into electric tube furnace,
Under protection of argon gas, at 600~1200 DEG C, it is pyrolyzed 2 ~ 3h.It is cooled to room temperature to furnace temperature, takes out, repeatedly washed with hydrofluoric acid
It to go removing template montmorillonite, filters, is washed with deionized water, dry, obtain 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 it can control the hydrophobicity of interlayer, and the interlamellar spacing of adjustable interlayer.Alkyl carbon chain is longer, 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 insertion
In the case where, interlamellar spacing is wider, and ABPBI is inserted into more, and the number of plies of obtained graphene is also more.Therefore cationic surface is living
The modification of property agent is extremely important, preferably comprises C6-C12Alkyl cationic surfactant.Another key technology of the invention
It is filling and arranging situation of the ABPBI in interlayer: ABPBI is required to fill full interlayer first；Secondly, it is desirable that ABPBI is in interlayer
It is interior regularly arranged.It only in this way can just obtain complete two-dimentional nitrogen-doped carbon material.Repeatedly suck this requires ABPBI solution and
It is multiple slowly to drain rear repetitive operation.
ABPBI macromolecular chain is made of the rigid benzimidazole of armaticity, and contains the miaow rich in nitrogen in molecule
Azoles ring and Amino End Group；Polymer viscosity average molecular weigh is soluble in dimethyl acetamide (DMAC), dimethyl between 1~30,000
The organic solvents such as formamide (DMF), dimethyl sulfoxide (DMSO) and N-Methyl pyrrolidone.
The mass ratio of ABPBI and template modified montmorillonoid is 2:1~1:3；Hybrid mode are as follows: weigh a certain amount of template
Agent modified montmorillonoid 160~220 DEG C of heating 2h in high temperature furnace adsorb water, gas or impurity to remove in multilayer material interlayer.
Room temperature to be cooled to, is transferred in the pressure vessel for being connected with vacuum pump, vacuumizes 30~40min, with syringe into pressure vessel
A certain amount of ABPBI solution is injected, so that ABPBI solution is impregnated template, continues to vacuumize, after no liquid in container, is continued
Aforesaid operations run out up to ABPBI solution, drain.The template of sucking ABPBI solution, take out in vacuum oven
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 is protected in high temperature furnace ~
It is pyrolyzed 2~3h at 1000 DEG C, after furnace temperature is cooling, takes out sample, washes away template with hydrofluoric acid, acid is washed with deionized water,
It is dried at 80~120 DEG C in vacuum oven to get the two-dimentional nitrogen-doped graphene product of black is arrived.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 600~1200 DEG C, preferably 700~1000 DEG C.Temperature is too low
ABPBI cannot be pyrolyzed, and the electric conductivity for obtaining product is poor；After pyrolysis temperature reaches optimum temperature, then increase its property of pyrolysis temperature
Can be constant, so pyrolysis temperature is unsuitable excessively high.
The graphene characterizing method of two-dimentional N doping are as follows: aperture, porosity, Kong Rong and specific surface area nitrogen adsorption instrument
(BET), the Morphology analysis of product scanning electron microscope (SEM) and projection electron microscope (TEM), graphene number of plies
It can be characterized by high power transmission electron microscope (HRTEM).Degree of graphitization, graphene-structured and the number of plies of product can be with
It is characterized with X-ray powder diffraction (XRD), Raman spectrum.The element of product forms, and valence state can use X-ray photoelectron energy
Spectrum (XPS) is characterized, and reacts (ORR) performance, water power with rotating disk electrode (r.d.e) (RDE) come the catalytic oxidation-reduction of test product
It solves oxygen evolution reaction (EOR), the capacitive property test of evolving hydrogen reaction (EHR) and product can use cyclic voltammetric (CV), linear volt
Peace (LSV), Tafel curve and charge-discharge performance are tested.CV, LSV can be used as the durability test of catalyst in product
With chronoa mperometric plot (i-t).The catalytic performance of product finally needs to assemble metal-air battery, hydrogen-oxygen fuel cell, electrolysis
Electrolytic cell, supercapacitor and the sensor of water tests its performance.
The present invention is with document difference: firstly, will be to the sour modification of stratiform mould material, to increase interlamellar spacing.
It is modified processing with cationic surfactant again, so that its interlayer is become hydrophobic, and interlamellar spacing becomes larger, is conducive to it
Hydrophobic high molecular material is inserted into interlayer；Secondly, entering macromolecule ABPBI molecule using the method for vacuum aided
In interlayer；Third, the drying in interlayer of the ABPBI molecule of rigidity can achieve the regularly arranged of molecule, it is beneficial to prevent a large amount of
Stacking, curling etc. are unfavorable for the case where generating graphene.It is pyrolyzed under inert gas protection after insertion ABPBI, removes template agent removing
The graphene of two-dimentional N doping can be obtained.
Specific embodiment
The preparation (method one, solid phase method) of [embodiment 1] ABPBI: suitable 3,4- diaminobenzoic acid (DABA) is taken
It is transferred to after being fully ground in mortar equipped in electric stirring, inert gas shielding three-necked flask, leads to N2, 15min is to arrange
Air to the greatest extent in flask.N2Protection, under stirring, 225 DEG C of oil bath heating keep 3h.It is taken out after cooling, finely ground, N2Under protection, electricity
Heating in furnace, is warming up to 270-275 DEG C, keeps 3h.It is cooled to room temperature, product is taken out, is finely ground to get ABPBI is arrived, uses Ubbelohde
The molecular weight of viscosimeter measurement ABPBI.
The preparation (method two, liquid phase method) of [embodiment 2] ABPBI: polyphosphoric acids (PPA) (50g) is added to three mouthfuls
In flask, under nitrogen protection, 160 DEG C of 1 h of stirring are to remove moisture and air.Addition 3,4- diaminobenzoic acid (6 g, 39.5
Mmol 190 DEG C) and by temperature are increased to, controls N2Flow velocity prevents DABA to be oxidized, and is stirred to react 3h at 200 DEG C, reacted
About 5g P is added portionwise 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 is formed fibrous black solid, is taken out drying, powder
It is broken, it washs to remove the polyphosphoric acids and unreacted raw material in reaction mixture.Obtain ABPBI product.Use Ubbelohde viscometer
Measure the molecular weight of ABPBI.
The sour modification of [embodiment 3] montmorillonite and cationic surfactant modification.
The acid of montmorillonite is modified:
It takes 10g montmorillonite (Na-MMT) to be put into 1000mL beaker, the HCl of 0.1 mol L-1 of 600mL, stirring is added
Under, impregnate 2 days, filter, repeatedly washed, filtered with a large amount of deionized water, the montmorillonite (H- of 60 °C of dry sour modifications
MMT).Measuring its ion exchange capacity is 0.25meq/g.
Modified montmorillonite (the MMT of cationic surfactantCX),
Weigh 5g H-MMT(0.25meq/g), it is dry at 120 DEG C, with impurity such as the water that removes its absorption, under stiring
The cetyl trimethylammonium bromide cationic surfactant for being slowly added into 0.456g is dissolved in 300mL deionized water solution
In, 4h is sufficiently stirred in 60 °C of water-baths, so that it is uniformly dispersed, stands overnight, is centrifugated, is cleaned with deionized water to nothing
Br- is dried under 120 °C, is ground, is obtained surfactant-modified MMT and be abbreviated as MMTC16。
The illiteracy for the acid modification that [embodiment 4] is modified with cetyl trimethylammonium bromide cationic surfactant is de-
Soil (MMTC16, the montmorillonite of other alkyl modifieds is labeled as MMTCX, wherein X is the carbon atom number of alkyl), with ABPBI and template
For agent mass ratio is 1:1:
In the beaker of 250mL, ten thousand) the ABPBI(viscosity average molecular weigh 2 ~ 3 of 1g is added to be made with 20mL DMAc, heating, stirring
It is dissolved, and solution filters, spare to remove insoluble matter.In the bottle,suction of 250mL, 1g MMT is addedC16It is set to be laid in bottle
Bottom after bottle,suction vacuumizes 30min, closes valve, stops vacuumizing, the DMAc solution of ABPBI is added with syringe, fills it
Share in the benefit wet template, continue to vacuumize to remove solvent, after to be dried it is repeated multiple times until the DMAc solution of ABPBI all plus
Enter, after draining, the MMT of sucking ABPBIC16Template takes out 60~120 DEG C of ageings in vacuum oven, is cooled to room
Temperature is taken out, finely ground, is put into porcelain boat, is pyrolyzed 2~3h at 800 DEG C under argon gas protection in high temperature furnace, after furnace temperature is cooling, takes out sample
Product wash away template with hydrofluoric acid, are washed with deionized water to neutrality, dry at 80~120 DEG C in vacuum oven.It obtains black
Color pulverulent solids 0.68g.BET test shows that its surface area is 15 ~ 22nm, 562 m2 g-1, SEM test shows
Product be porous carbon materials, TEM and HRTEM analysis shows, product is multi-layer graphene structure carbon material, and graphene, which is drawn a bow to the full back, to be shown
For 3 ~ 4 layers of graphene.XRD and Raman spectrum test show that product is 3 ~ 4 layers of graphene-structured；XPS analysis shows 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
Material.In its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, starting hydrogen reduction current potential is 0.987V vs RHE, electronics transfer
Number is 3.98, and durability is good；Magnesium air battery performance reaches 120mW/cm2.For hydrogen-oxygen fuel cell, its peak power is
458.6mW/cm2, it is 1.43 vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches
72mA/cm2.Supercapacitor 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 only pyrolysis temperature is changed to 700 DEG C.Obtained production
Product are 0.72g black powder, 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 lower, 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 3.58 is resistance to
Long property is good；Magnesium air battery performance reaches 79mW/cm2.It is 325mW/cm for its peak power of hydrogen-oxygen fuel cell2, 0.5mol/L
Sulfuric acid solution in oxygen take-off potential is precipitated is 1.51 vs RHE, limiting current density reaches 65mA/cm2.Supercapacitor
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, only change pyrolysis temperature and are changed to 900 DEG C.It obtains
Product be 0.66g black powder, test result shows that its product remains as 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.985V vs RHE, electronics
Shifting number is 3.98, and durability is good；Magnesium air battery performance reaches, 127mW/cm2.For hydrogen-oxygen fuel cell, its peak power is
526mW/cm2, it is 1.45 vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches
79mA/cm2.Supercapacitor 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 only pyrolysis temperature is changed to 1000 DEG C.It obtains
Product is 0.65g black powder, and test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Expect, in 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.967V vs RHE, and electronics turns
Moving number is 3.97, and durability is good；Magnesium air battery performance reaches 121mW/cm2.For hydrogen-oxygen fuel cell, its peak power is
452mW/cm2, it is 1.48 vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches
85mA/cm2.Supercapacitor 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, only change ABPBI and MMTC16The ratio of template
Example is 1:2.Obtained product is 0.72g black powder, 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 filling is not enough, obtained two-dimentional N doping graphite
Alkene lamella becomes smaller, and electric conductivity is deteriorated, in 0.1mol/LKOH solution, catalytic oxidation-reduction performance, and oxygen initial reduction current potential
For 0.725V vs RHE, electron transfer number 3.58, durability is good；Magnesium air battery performance reaches 88mW/cm2.For hydrogen-oxygen
Its peak power of fuel cell is 410mW/cm2.It is 1.56 vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L,
Limiting current density reaches 55mA/cm2.Supercapacitor 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, only change ABPBI and MMTC16The ratio of template
Example is 1:3.Obtained product is 0.71g black powder, 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 filling is not enough, obtained two-dimentional N doping
Graphene sheet layer becomes smaller, and 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 3.51, durability is good；Magnesium air battery performance reaches 62mW/cm2.For
Its peak power of hydrogen-oxygen fuel cell is 312mW/cm2, it is 1.61 vs that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L
RHE, limiting current density reach 45mA/cm2.Supercapacitor 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, only change ABPBI and MMTC16Template
Ratio is 2:1.Obtained product is 0.67g black powder, and test result shows its product in addition to 2 ~ 4 layers of two-dimentional N doping
Except the material of graphene-structured, there are also the carbon materials of part N doping.This is because the increase of ABPBI amount, so that ABPBI is removed
Except filling interlayer gap, there are also some residual, remaining ABPBI coats the porous carbon to form N doping on template surface
Material, catalytic performance are deteriorated.In its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is
0.66V vs RHE, electron transfer number 3.52, durability is good；Magnesium air battery performance reaches 52mW/cm2.It is fired for hydrogen-oxygen
Material its peak power of battery is 310mW/cm2, it is 1.68 vs RHE, pole that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L
Current density of rationing the power supply reaches 42mA/cm2.Supercapacitor 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 only template uses MMT insteadC6.Obtained product
For 0.72g black powder, test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, only
It is since 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 battery performance reaches 102mW/cm2.It is 452mW/cm for its peak power of hydrogen-oxygen fuel cell2,
It is 1.51 vs RHE that take-off potential, which is precipitated, in oxygen 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, only MMTC8.Obtained product 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 cationic
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 3.95, durability is good
It is good；Magnesium air battery performance reaches 116mW/cm2.It is 476mW/cm for its peak power of hydrogen-oxygen fuel cell2.The sulphur of 0.5mol/L
It is 1.51 vs RHE that take-off potential, which is precipitated, in oxygen in acid solution, and limiting current density reaches 84mA/cm2.Supercapacitor specific capacitance
For 426F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 13] as described in Example 4, other conditions are identical, only MMTC14.Obtained product is that 0.76g is black
Color powder, test result show that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, 0.1mol/
In LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.88V vs RHE, and electron transfer number 3.83 is resistance to
Long property is good；Magnesium air battery performance reaches, 87mW/cm2.It is 780mW/cm for its peak power of hydrogen-oxygen fuel cell2, 0.5mol/
It is 1.47V vs RHE that take-off potential, which is precipitated, in the sulfuric acid solution oxygen of L, and limiting current density reaches 156mA/cm2.Supercapacitor
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, only MMTC18.Obtained product is that 0.75g is black
Color powder, test result show that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, 0.1mol/
In LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.78V vs RHE, and electron transfer number 3.81 is resistance to
Long property is good；Magnesium air battery performance reaches, 75mW/cm2.It is 687mW/cm for its peak power of hydrogen-oxygen fuel cell2, 0.5mol/
It is 1.49V vs RHE that take-off potential, which is precipitated, in the sulfuric acid solution oxygen of L, and limiting current density reaches 135mA/cm2.Supercapacitor
Specific capacitance is 654F g-1, be recycled 10000 times still holding capacitor value 96%.
Claims (3)
1. a kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing, it is characterised in that: selecting macromolecular chain is by virtue
The rigid benzimidazole of fragrance forms, and in molecule containing rich in nitrogen imidazole ring and Amino End Group it is soluble it is poly- (2,
5- benzimidazole) (ABPBI) be carbon source and nitrogen source, it is template with the modified montmorillonite of cationic surfactant, it is soluble
The method of the solution of ABPBI vacuum aided is filled into the interlayer of template, and the aromatic rings in ABPBI molecule is in interlayer
It is regularly arranged, the imidazole ring and Amino End Group of nitrogen are rich in molecule, under inert gas protection, pyrolysis is washed with hydrofluoric acid
Template is washed away, the two-dimentional nitrogen-doped graphene of high nitrogen-containing is prepared；ABPBI be it is soluble, benzimidazole ring is rigid
Property armaticity ring, nitrogen-doped graphene structure is easily formed in pyrolysis, pore-creating work is played in decarboxylation when carboxyl pyrolysis in molecule
With；Cationic surfactant C6~C18Alkyl trimethyl ammonium bromide type, the interlamellar spacing of the hydrophobicity interlayer of template are 0.2
~0.6 nm, ABPBI are mixed with template by the mass ratio of 2:1~1:3, argon gas is protected in lower high temperature furnace at 700~1000 DEG C
Under, it is pyrolyzed 2~3h, goes template that two-dimentional nitrogen-doped graphene can be obtained with hydrofluoric acid, the two-dimentional nitrogen of the high nitrogen-containing is mixed
Miscellaneous graphene is used in metal-air battery, fuel cell applied to the catalyst of catalytic oxidation-reduction reaction；It is also used for catalysis electricity
Solve the catalyst of water oxygen evolution reaction；It is also used to the electrode material of supercapacitor.
2. a kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing according to claim 1, it is characterised in that:
ABPBI macromolecular chain is made of the rigid benzimidazole of armaticity, and contains the imidazole ring and end for being rich in nitrogen in molecule
Amino；Polymer viscosity average molecular weigh can be dissolved in dimethyl acetamide (DMAc), dimethylformamide between 1~30,000
(DMF), in dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone any one organic solvent.
3. a kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing according to claim 1, ABPBI and mould
The mass ratio of plate agent is 2:1~1:3；Hybrid mode are as follows: weigh a certain amount of template, 160~220 DEG C of heating in high temperature furnace
2h, to remove the water adsorbed in multilayer material interlayer, gas or impurity；Room temperature to be cooled to is transferred to the pressure for being connected with vacuum pump
In container, 30~40 min are vacuumized, a certain amount of ABPBI solution is injected into pressure vessel with syringe, makes ABPBI solution
Template is impregnated, continues to vacuumize, after no liquid in container, continuation aforesaid operations run out up to ABPBI solution, drain i.e.
It can；The template of sucking ABPBI solution, 60~120 DEG C of ageings in vacuum oven are taken out, the sample of room temperature is cooled to
It takes out, it is finely ground, it is put into porcelain boat, in high temperature furnace under argon gas protection, at 700~1000 DEG C, is pyrolyzed 2~3h, after furnace temperature is cooling,
Sample is taken out, template is washed away with hydrofluoric acid, acid is washed with deionized water, it is dry at 80~120 DEG C in vacuum oven, i.e.,
Obtain the two-dimentional nitrogen-doped graphene product of black.
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| CN102502593A (en) * | 2011-10-11 | 2012-06-20 | 中国石油大学(北京) | Preparation method of grapheme or doped graphene or graphene complex |
| CN104108708A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped graphene and preparation method thereof |
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| CN102502593A (en) * | 2011-10-11 | 2012-06-20 | 中国石油大学(北京) | Preparation method of grapheme or doped graphene or graphene complex |
| CN104108708A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped graphene and preparation method thereof |
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