CN106744851A - The method that the two-dimentional nitrogen-doped graphene of high nitrogen-containing is prepared with polybenzimidazoles - Google Patents
The method that the two-dimentional nitrogen-doped graphene of high nitrogen-containing is prepared with polybenzimidazoles Download PDFInfo
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Abstract
The present invention is the polybenzimidazoles with full armaticity(PBI)The preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing is prepared for carbon source and nitrogen source.It is raw material with PBI, the hydrophobic stratified material formed with cationic surfactant modified montmorillonoid is template, with the method for vacuum aided, PBI solution is filled into stratiform template interlayer and is regularly arranged, after removal solvent, under an inert gas, it is pyrolyzed, goes after template agent removing to obtain the two-dimentional nitrogen-doped graphene of high nitrogen-containing.PBI selects the soluble oligomer of full armaticity;Distance between stratiform template interlayer can be adjusted by changing its alkyl chain size of cationic surfactant adsorbed etc., and interlamellar spacing is between 0.2~0.6 nm;PBI is 2 with stratiform template mass ratio:1~1:3;Pyrolysis temperature is 700 ~ 1100 DEG C.The two-dimentional 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, for the redox reaction catalyst in Chemical Manufacture, clean energy resource field
Fuel cell, the cathod catalyst of metal-air battery, electrolysis water catalyst, lithium ion battery material, super capacitor electrode
The field such as pole material and electrochemical sensor.
Background technology
Polybenzimidazoles(PBI)It is the macromolecular material of a class excellent performance, because minute is contained within benzimidazole ring category
In the stiffening ring of armaticity, contain imidazoles nitrogen in molecule on imidazole ring, belong to the aroma type high molecular polymer rich in nitrogen.Institute
So that its pyrolysis can prepare the carbon material of N doping, if using suitable template, allow it to add between small interlayer, heat
Solution, can obtain nitrogen-doped graphene.The PBI of full aroma type, e.g., poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmale]
(mPBI), the polybenzimidazoles of pyridine groups(PPBI)With the polybenzimidazoles with pyrazine group(PzPBI)Etc., its structure
Formula is respectively:
The structural formula of mPBI
The structural formula of PPBI
The structural formula of PzPBI
The design feature of the PBI of full aroma type to form high molecular all atoms in one plane, each atom of intramolecular it
Between form a big π key, molecule belongs to rigid, easily plane superposition and assembles between molecule, if regulation and control well its receiving
The mass ratio of rice template, can be such that it is regularly arranged on template surface, if under inert gas shielding, pyrolysis, meeting
The a series of thermal chemical reactions such as generation dehydrogenation-cyclisation-carbonization, finally give multilayer nitrogen-doped graphene structural material.
Hetero atom(N, P, B and S etc.)Graphene performance after doping is more protruded, it is also possible to codope or three doping etc..
In all kinds of Heteroatom doping Graphenes, nitrogen-doped graphene(NG)Most study, the structure of the nitrogen in NG has diversified forms,
Wherein, pyridine type nitrogen and pyrroles's type nitrogen are planar structures, with catalytic oxidation-reduction activity(Nie Yao etc., Journal of Chemical Industry and Engineering), 2015,
66: 3305), conversely, the nitrogen-atoms of three-dimensional structure is without activity, so, the good nitrogen-doped graphene of catalytic performance is prepared first
It is required that nitrogen content is high, and then requires that pyridine type nitrogen and the content of pyrroles's type nitrogen want height, so, the preparation side of nitrogen-doped graphene
Method has lot of documents to report:Graphite oxide reducing process, heat-treatment oxidation Graphene (Li X, the et al. J under ammonia atmosphere
Am Chem Soc(JACS)2009, 131: 15939);Chemical vapour deposition technique(CVD)(Jin Z, et al.
ACS Nano (American Chemical Society-nanometer), 2011,5 (5):4112) etc..Also useful pollopas, melmac,
The nitrogen containing polymer compound such as polyaniline and polypyrrole prepares the report of nitrogen-doped graphene.
Template is done with stratified material, aniline prepares polyaniline in stratiform template internal-response, and pyrolysis prepares two-dimentional nitrogen and mixes
Miscellaneous Graphene had been reported that (Ding W, et al. Angew Chem Int Ed (German applied chemistry-world version),
2013, 52: 1175), the polyaniline planar alignment of its synthesis, being pyrolyzed the two-dimentional nitrogen-doped graphene for preparing can be containing more
Pyridine nitrogen and pyrroles's nitrogen, it shows excellent catalytic oxidation-reduction performance.Specific method is template montmorillonite modified using acid
Prepare H+The montmorillonite of type, obtains the interlayer of hydrophilic;Aniline generates the anilinechloride of hydrophilic in acid condition, favorably
In the interlayer of insertion hydrophilic, because aniline belongs to small molecule, it is also easy to enter in interlayer;Aniline is polymerized in interlayer
Reaction obtains polyaniline due to by the control of vertical direction area size so that polyaniline is the molecule of plane, in indifferent gas
The lower pyrolysis of body protection, obtains the Graphene of two-dimentional N doping.
The present invention is the macromolecular material using the benzimidazole unit of full aroma type, e.g., is gathered(2,5- benzimidazoles)
(ABPBI), poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmale] (mPBI), the polybenzimidazoles of pyridine groups(PPBI)
With the polybenzimidazoles with pyrazine group(PzPBI)Deng being carbon source and nitrogen source, cationic surfactant modified montmorillonoid is used
Stratified material obtains hydrophobic interlayer and does template, makes rigid PBI molecules regularly arranged in interlayer, occurs without a large amount of stackings, volume
Song etc. is unfavorable for that the situation for generating Graphene occurs to prepare multilayer two-dimension nitrogen-doped graphene.The present invention and document difference
Innovative point be:First, to increase interlamellar spacing, then cation surface activating is used to stratiform mould material acid modification
Agent is modified treatment, its interlayer is become hydrophobic, and interlamellar spacing becomes big, with the long alkyl chain of cationic surfactant
To regulate and control the hydrophobic strong and weak and interlamellar spacing of interlayer;Only the sufficiently large interlamellar spacing of hydrophobic type, can just make the macromolecule of hydrophobic type
It is inserted into interlayer, and it is regularly arranged;Secondly, macromolecule ABPBI molecules are allow to enter folder using the method for vacuum aided
In layer;Third, rigid PBI molecules are dried in interlayer, under the double action of hydrophobic interlayer and vacuum aided, can just reach
To high molecular regularly arranged, be conducive to the situation for preventing a large amount of stackings, curling etc. to be unfavorable for generating Graphene, after insertion PBI
It is pyrolyzed under inert gas shielding, it may occur that a series of thermal chemical reaction such as dehydrogenation-cyclisation-carbonization, finally gives multilayer nitrogen
Doped graphene structural material, obtains the Graphene of two-dimentional N doping by removing template agent removing.
And the method for document is the modified H of template use acid+The montmorillonite of type, obtains the interlayer of hydrophilic;Small molecule benzene
Amine generates water-soluble anilinechloride in acid condition, be conducive to insert hydrophilic interlayer in;Furthermore, small molecule
In easily entering interlayer, it is not necessary to carry out the operation of complexity;There is polymerisation in aniline, obtain polyaniline in interlayer, and it gathers
The process of conjunction is just controlled by area size.The molecule of the polyaniline plane for obtaining, is pyrolyzed under inert gas shielding, 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 PBI molecules and rule row
The factors such as the proportioning of row and PBI and template.Hydrophobic treatment be macromolecule insertion basis, interlamellar spacing control and template and
PBI proportionings decide the regular degree of macromolecule arrangement and obtain the number of plies of Graphene.
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 template, Control architecture interlamellar spacing are come
The number of plies and performance of the nitrogen-doped graphene of preparation are controlled, preferable multilayer two-dimension nitrogen-doped graphene is finally given.
It is conventional method that macromolecular material method for pyrolysis prepares carbon material, such as with phenolic resin, pollopas and trimerization
The pyrolysis such as melamine resin prepare carbon material.Compared with phenolic resin, pollopas and melmac Polymer material,
The difference of PBI is the stiffening ring benzimidazole ring that it contains armaticity, and imidazoles nitrogen on imidazole ring makes its nitrogenous
Amount is more enriched.Therefore high temperature pyrolysis PBI can obtain the carbon material of the N doping of high content, and by introducing suitable template
Or the orientation of the fragrant plane of a loop of control molecule, the grapheme material of multilayer N doping can be obtained after pyrolysis.With it is poly-
Aniline is compared with polypyrrole Polymer material, and PBI can dissolve, it is easy to be inserted into template interlayer, and polyaniline, polypyrrole
Deng insoluble, it is impossible to be inserted into the interlayer of template.
The content of the invention
The present invention is the macromolecular material using the benzimidazole unit of full aroma type, e.g., is gathered(2,5- benzimidazoles)
(ABPBI), poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmale] (mPBI), the polybenzimidazoles of pyridine groups(PPBI)
With the polybenzimidazoles with pyrazine group(PzPBI)Deng being carbon source and nitrogen source, cationic surfactant is used(C8~C16Alkyl
Pyridinium bromide salt etc.).Modified montmorillonoid stratified material obtains hydrophobic interlayer and does template, makes rigid PBI molecules in interlayer
It is regularly arranged, occur without a large amount of stackings, curling etc. and be unfavorable for that the situation for generating Graphene occurs to prepare multilayer two-dimension N doping
Graphene.The present invention is with the innovative point of document difference:First, be to stratiform mould material acid modification, to increase
Interlamellar spacing, then treatment is modified with cationic surfactant, its interlayer is become hydrophobic, and interlamellar spacing becomes big, uses
The long alkyl chain of cationic surfactant regulates and controls the hydrophobic strong and weak and interlamellar spacing of interlayer;The only sufficiently large layer of hydrophobic type
Spacing, can just be such that the macromolecule of hydrophobic type is inserted into interlayer, and regularly arranged;Secondly, the method using vacuum aided makes
Macromolecule ABPBI molecules can enter in interlayer;Third, rigid PBI molecules are dried in interlayer, in hydrophobic interlayer and vacuum
Under the double action of auxiliary, can just reach high molecular regularly arranged, be conducive to preventing a large amount of stackings, curling etc. to be unfavorable for life
Into the situation of Graphene, it is regularly arranged after insertion PBI in the case of, be pyrolyzed under inert gas shielding, it may occur that dehydrogenation-ring
The a series of thermal chemical reactions such as change-carbonization, finally give multilayer nitrogen-doped graphene structural material, are obtained by removing template agent removing
To the Graphene of two-dimentional N doping.
And the method for document is the modified H of template use acid+The montmorillonite of type, obtains the interlayer of hydrophilic;Small molecule benzene
Amine generates water-soluble anilinechloride in acid condition, be conducive to insert hydrophilic interlayer in;Furthermore, small molecule
In easily entering interlayer, it is not necessary to carry out the operation of complexity;There is polymerisation in aniline, obtain polyaniline in interlayer, and it gathers
The process of conjunction is just controlled by area size.The molecule of the polyaniline plane for obtaining, is pyrolyzed under inert gas shielding, 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 PBI molecules and rule row
The factors such as the proportioning of row and PBI and template.Hydrophobic treatment be macromolecule insertion basis, interlamellar spacing control and template and
PBI proportionings decide the regular degree of macromolecule arrangement and obtain the number of plies of Graphene.
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 template, Control architecture interlamellar spacing are come
The number of plies and performance of the nitrogen-doped graphene of preparation are controlled, preferable multilayer two-dimension nitrogen-doped graphene is finally given.
It is conventional method that macromolecular material method for pyrolysis prepares carbon material, such as with phenolic resin, pollopas and trimerization
The pyrolysis such as melamine resin prepare carbon material.PBI is compared with phenolic resin, pollopas and melmac Polymer material
Difference is the stiffening ring benzimidazole ring that PBI contains armaticity, and imidazoles nitrogen on imidazole ring makes its nitrogen content more
Plus it is abundant, whole molecule is the rigid molecule of armaticity.By the fragrant plane of a loop for introducing suitable template or control molecule
Orientation, can obtain the grapheme material of multilayer N doping respectively after pyrolysis.With the macromolecule such as polyaniline and polypyrrole
Material is compared, and PBI can dissolve, it is easy to be inserted into template interlayer, and polyaniline, polypyrrole etc. are insoluble, it is impossible to be inserted into
In the interlayer of template.
The difference being polymerized after being added with literature method acid type montmorillonite aniline is, used as hydrophobic macromolecular material
PBI can not use this method, because, first, acid type montmorillonite is hydrophilic;Second, the interlamellar spacing of acid type montmorillonite is too small,
Macromolecule cannot be introduced into;PBI can not be regularly arranged under 3rd free state, is conducive to hydrophobic environment under the conditions of vacuum aided
PBI's is regularly arranged.There are a series of heat such as dehydrogenation-cyclisation-carbonization when being pyrolyzed under argon gas protection in only regularly arranged PBI
Chemical reaction could form nitrogen-doped graphene structure.
First with liquid phase method or the PBI of the full armaticity of Solid phase synthesis, such PBI macromolecular chain is by the rigidity of armaticity
Benzimidazole is constituted, and containing imidazole ring and Amino End Group rich in nitrogen in molecule, chooses viscosity average molecular weigh 10,000~30,000
Between be soluble in DMAc, DMF, DMSO, the oligomer in 1-METHYLPYRROLIDONE equal solvent.Molecular weight is too big, PBI's
Solubility property is deteriorated;Graphene performance prepared by too small its pyrolysis of molecular weight is not good enough.
The method of the preparation of the Graphene of two-dimentional N doping is:Montmorillonite first carries out acidification, cleans drying, is separately added into
The cationic surfactant C of different alkyl chains8~C16Cetylpyridinium bromide salt is modified, and the illiteracy for preparing hydrophobic interlayer takes off
Soil is used as template.A certain amount of template is put into the container that can be vacuumized, a certain amount of PBI dissolvings in a solvent
Solution is formed, wait after the min of container vacuum-pumping 30 for filling template, valve is closed, it is appropriate to being injected in container with syringe
The solution of PBI, after after solution submergence template, is begun to warm up, vacuumizes, and solvent is steamed at leisure near dry, so repeatedly many
It is secondary until the solution of PBI is finished.Take out, dried at 60 ~ 120 DEG C in the drying box.It is finely ground in mortar, it is laid in porcelain boat bottom
Portion, is put into electric tube furnace, under argon gas protection, at 700~1100 DEG C, is pyrolyzed 2 ~ 3h.Treat that furnace temperature is cooled to room temperature, take
Go out, repeatedly washed with hydrofluoric acid to go removing template montmorillonite, suction filtration is washed with deionized water net, drying, obtains two-dimentional N doping graphite
Alkene.
In the present invention:The optional C of cationic surfactant8~C16Cetylpyridinium bromide salt etc., the length of its alkyl is not
But the hydrophobicity of interlayer can be controlled strong and weak, and the interlamellar spacing of interlayer can be adjusted.Alkyl carbon chain is more long, the hydrophobicity of interlayer
Stronger, interlamellar spacing is bigger, and vice versa.The interbedded distance of template determines the amount that can inject PBI, and then determines
The number of plies of prepared Graphene.In the case of PBI insertions sufficiently, interlamellar spacing is wider, more, the graphite for obtaining of PBI insertions
The number of plies of alkene is also more.Therefore, the modification of cationic surfactant is extremely important.Another key technology of the invention is
Fillings and arranging situation of the PBI in interlayer:The full interlayer of PBI fillings is required first;Secondly, it is desirable to PBI rule rows in interlayer
Row.Only in this way can just obtain complete two-dimentional nitrogen-doped graphene.This requires that PBI solution is repeatedly sucked, and waits a moment and drains slowly
After repeat repeatedly.PBI is 2 with the mass ratio of template modified montmorillonoid:1~1:3.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 700~1100 DEG C.The too low PBI of temperature can not be pyrolyzed, and obtain product
Electric conductivity it is poor;After pyrolysis temperature reaches optimum temperature, then to raise pyrolysis temperature its performance constant, so pyrolysis temperature is unsuitable
It is 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.
Specific embodiment
The preparation of [embodiment 1] mPBI:Polyphosphoric acids is added in the there-necked flask protected equipped with electric stirring and nitrogen
(PPA) (100g), lower 160 DEG C of nitrogen protection stirs 1h to remove unnecessary moisture and air.By DABz (4g, 18.7
Mmol) and M-phthalic acid (3.1g, 18.7 mmol) is well mixed, it is slowly added in there-necked flask.Control nitrogen
Flow velocity, prevents DABz to be oxidized, while reaction temperature being lifted to 200 DEG C and continuing insulation, stirring reaction 5-8h.With reaction
The increase of time, polymerization system gradually becomes sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred to largely
Reeled off raw silk from cocoons in deionized water, clean, dry, crushed, deionized water is repeatedly washed to remove polyphosphoric acids and unreacted reactant, i.e.,
MPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
The preparation of [embodiment 2] PPBI:Poly phosphorus is added in the there-necked flask protected equipped with electric stirring and nitrogen
Sour (PPA) (100g), lower 160 DEG C of nitrogen protection stirs 1h to remove unnecessary moisture and air.By DABz (4.00g,
18.7 mmol) and 2,6- pyridinedicarboxylic acid (3.12g, 18.7 mmol) it is well mixed, be slowly added to there-necked flask
In.Control nitrogen flow rate, prevents DABz to be oxidized, while reaction temperature being lifted to 200 DEG C and continuing insulation, stirring reaction 5-
8h.With the increase in reaction time, polymerization system gradually becomes sticky.Stop reaction when viscosity is suitable, reaction mixture is slow
Slow-speed is reeled off raw silk from cocoons in moving on to a large amount of deionized waters, is cleaned, drying, is crushed, deionized water repeatedly washing removing polyphosphoric acids and not
Reaction response thing, that is, obtain PPBI, with the molecular weight of determination of ubbelohde viscometer PPBI.
The preparation method of other PBI with pyridine groups:With the method for embodiment 2, simply by 2,6- pyridinedicarboxylic acids point
Do not change 3,5- pyridinedicarboxylic acids, 2,3- pyridinedicarboxylic acids, 2,5- pyridinedicarboxylic acids or 3,4- pyridinedicarboxylic acid into, other behaviour
Make with embodiment 2, you can obtain the PPBI containing different pyridine groups, product is designated as respectively:3,5-PPBI、2,3-PPBI、2,
5-PPBI and 3,4-PPBI.
The preparation of [embodiment 3] PzPBI:Poly phosphorus is added in the there-necked flask protected equipped with electric stirring and nitrogen
Sour (PPA) (100g), lower 160 DEG C of nitrogen protection stirs 1h to remove unnecessary moisture and air.By DABz (4.00g,
18.7 mmol) and 2,6- pyrazinedicarboxylicacid (3.14g, 18.7 mmol) it is well mixed, be slowly added to there-necked flask
In.Control nitrogen flow rate, prevents DABz to be oxidized, while reaction temperature being lifted to 200 DEG C and continuing insulation, stirring reaction 5-
8h.With the increase in reaction time, polymerization system gradually becomes sticky.Stop reaction when viscosity is suitable, reaction mixture is slow
Slow-speed is reeled off raw silk from cocoons in moving on to a large amount of deionized waters, is cleaned, drying, is crushed, deionized water repeatedly washing removing polyphosphoric acids and not
Reaction response thing, that is, obtain PzPBI, with the molecular weight of determination of ubbelohde viscometer PzPBI.
The preparation method of other PBI with pyrazine group:With the method for embodiment 3, simply by 2,6- pyrazinedicarboxylicacids point
Do not change 2,5- pyrazinedicarboxylicacids or 2,3- pyrazinedicarboxylicacid into, other operations are with embodiment 3, you can obtain containing different pyrroles
The PzPBI of piperidinyl group, product is designated as respectively:3,5-PzPBI or 2,3-PzPBI.
Sour modification and the cationic surfactant modification of [embodiment 4] montmorillonite.
The acid of montmorillonite is modified:Take 10 g montmorillonites(Na-MMT)It is put into 1000mL beakers, adds 600 mL 0.1
The HCl of mol/L, under stirring, immersion 2 days, suction filtration is repeatedly washed, suction filtration with substantial amounts of deionized water, and 60 DEG C sour modifiedly dry
Montmorillonite(H-MMT).Its ion exchange capacity is determined for 0.25 meq/g.
Cationic surfactant C8~C16Cetylpyridinium bromide salt, first from C16Cetylpyridinium bromide salt
(C16P)Modified montmorillonite is designated as MMTC16P, experimental procedure is as follows:Weigh 5 g H-MMT(0.25 meq/g), at 120 ~ 220 DEG C
The lower h of drying 2, to remove the impurity such as its water for adsorbing, 0.5 g is slowly added under agitation uses C16Cetylpyridinium bromide salt
(C16P)Cationic surfactant is dissolved in 300 mL deionized water solutions, and 4h is sufficiently stirred in 60 DEG C of water-baths, makes it
It is uniformly dispersed, stands overnight, suction filtration is cleaned to without bromide ion with deionized water, is dried at 120 DEG C, and grinding obtains using C16Alkyl
Pyridinium bromide salt(C16P)MMT be abbreviated as MMTC16P。
C can be carried out in aforementioned manners8~C15Cetylpyridinium bromide salt(CXP)The modification of cationic surfactant
Montmorillonite, is abbreviated as MMTCXP, wherein X is the carbon number of alkyl.
[embodiment 5] uses MMTC16PIt is 1 with mPBI and template mass ratio as template:As a example by 1:250 mL's
In beaker, the mPBI of 1 g is added(Viscosity average molecular weigh 1 ~ 30,000)With 20 mL DMAc, heating, stirring dissolve it, solution suction filtration,
It is standby to remove insoluble matter.In the bottle,suction of 250 mL for being connected with vavuum pump, 1 g MMT are addedC16PIt is set to be laid in bottle
Bottom, after vacuumizing 30 min, closes valve, stops vacuumizing, and the DMAc solution of mPBI is added with syringe, it is fully soaked
Template, heating continues to vacuumize to remove solvent, it is to be dried after, repeat more than operate, it is repeated multiple times until mPBI's
DMAc solution is all added, and after draining, is taken out, and in 60~120 DEG C of ageings, cold taking-up is treated in drying, finely ground, porcelain boat is put into, in height
2~3h is pyrolyzed at argon gas protection is lower 900 DEG C in warm stove, cooling is taken out, repeatedly washed with hydrofluoric acid, to remove template agent removing, spends
Ion is washed to neutrality, and the g of black powder solid 0.67 is obtained in vacuum drying.BET tests show that its surface area is 486
m2 g-1, aperture is 16 ~ 23 nm, and SEM tests show, the product for obtaining is porous material, TEM and HRTEM analysis shows are produced
Product are multi-layer graphene structural material, and Graphene is drawn a bow to the full back as 3 ~ 4 layer graphenes.XRD and Raman spectrum test show, product be 3 ~
4 layers of graphene-structured;XPS analysis show that product nitrogen content is 7.0%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, produce
Product are the two-dimensional graphenes of N doping.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, initial hydrogen reduction current potential is
0.99 V vs RHE, electron transfer number is 3.98, and durability is good;Magnesium air cell performance is up to 102 mW/cm2.For hydrogen-oxygen
Its peak power of fuel cell is 478 mW/cm2, it is 1.56 Vvs that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
RHE, limiting current density reaches 90 mA/cm2.Ultracapacitor specific capacitance is 369 F/g, is recycled 10000 times and still protects
Hold the 97% of capacitance.
[embodiment 6] as described in Example 5, other conditions are identical, and simply pyrolysis temperature is changed to 700 DEG C.The product for obtaining
Product are 0.72 g black powders, and test result shows that its product remains as the material of 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, only because its degree of graphitization is relatively low, its electronic conductivity is slightly worse, so its chemical property is slightly worse:It 0.1
In mol/L KOH solutions, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.78 V vs RHE, and electron transfer number is
3.45, durability is slightly worse;Magnesium air cell performance is up to 54 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 154 mW/
cm2, it is 1.68 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 40
mA/cm2.Ultracapacitor specific capacitance be 129 F/g, be recycled 10000 times still holding capacitor value 94%.
[embodiment 7] as described in Example 5, other conditions are identical, simply change pyrolysis temperature and are changed to 1100 DEG C.
The product for arriving is 0.63 g black powders, and test result shows that its product remains as 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential be 0.95 V vs RHE,
Electron transfer number is 3.94, and durability is good;Magnesium air cell performance is up to 86 mW/cm2.For its peak work(of hydrogen-oxygen fuel cell
Rate is 337 mW/cm2, it is 1.62 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and carrying current is close
Degree reaches 60 mA/cm2.Ultracapacitor specific capacitance be 258 F/g, be recycled 10000 times still holding capacitor value 97%.
[embodiment 8] as described in Example 5, other conditions are identical, simply change mPBI and MMTC16PThe ratio of template
Example is 1:2.The product for obtaining is 0.70 g 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 MMTC16PThe increase of amount so that mPBI fillings are not abundant enough, the two-dimentional N doping graphite for obtaining
Alkene lamella diminishes, and its electric conductivity is deteriorated, in its 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction electricity
Position is 0.92 V vs RHE, and electron transfer number is 3.66, and durability is good;Magnesium air cell performance is up to 78 mW/cm2.For
Its peak power of hydrogen-oxygen fuel cell is 254 mW/cm2.It is 1.63 V that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
Vs RHE, limiting current density reaches 40 mA/cm2.Ultracapacitor specific capacitance is 257 F/g, is recycled 10000 times still
The 94% of holding capacitor value.
[embodiment 9] as described in Example 5, other conditions are identical, simply change mPBI and MMTC16PThe ratio of template
Example is 1:3.The product for obtaining is 0.70 g 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 MMTC16PThe increase of amount so that mPBI fillings are not abundant enough, the two-dimentional N doping for obtaining
Graphene sheet layer diminishes, and its electric conductivity is deteriorated.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen starting is also
Former current potential is 0.78 V vs RHE, and electron transfer number is 3.59, and durability is good;Magnesium air cell performance is up to 54 mW/cm2。
For hydrogen-oxygen fuel cell, its peak power is 176 mW/cm2, oxygen precipitation take-off potential is in the sulfuric acid solution of 0.5 mol/L
1.68 vs RHE, limiting current density reaches 40 mA/cm2.Ultracapacitor specific capacitance is 168 F/g, is recycled 10000
The 93% of secondary still holding capacitor value.
[embodiment 10] as described in Example 5, other conditions are identical, simply change mPBI and MMTC16PTemplate
Ratio is 2:1.The product for obtaining is 0.67 g 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 amount of powder shape N doping.This is due to the increase of mPBI amounts so that
In addition to filling interlayer space, also some residual, remaining mPBI forms N doping to mPBI in template Surface coating
Porous carbon materials, its catalytic performance is deteriorated.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction electricity
Position is 0.78 V vs RHE, and electron transfer number is 3.75, and durability is good;Magnesium air cell performance is up to 76 mW/cm2.For
Its peak power of hydrogen-oxygen fuel cell is 237 mW/cm2, it is 1.65 vs that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
RHE, limiting current density reaches 50 mA/cm2.Ultracapacitor specific capacitance is 237 F/g, is recycled 10000 times and still keeps
The 90% of capacitance.
[embodiment 11] as described in Example 5, other conditions are identical, and simply template uses MMT insteadC8P.The product for obtaining
Product are 0.65 g black powders, and test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
With nitrogen-doped carbon material, only because the alkyl carbon chain of cationic surfactant is shorter so that MMTC6PInterlamellar spacing reduces, and makes
The amount of the mPBI that must be added is on the high side, there is part nitrogen-doped carbon material in product.In its 0.1 mol/LKOH solution, catalytic oxidation-reduction
Performance, oxygen initial reduction current potential is 0.81 V vs RHE, and electron transfer number is 3.88, and durability is good;Magnesium air cell
Can be up to 78 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 237 mW/cm2, oxygen is separated out in the sulfuric acid solution of 0.5 mol/L
Take-off potential is 1.58 V vs RHE, and limiting current density reaches 50 mA/cm2.Ultracapacitor specific capacitance is 229 F/g,
Recyclable 10000 times still holding capacitor value 95%.
[embodiment 12] as described in Example 5, other conditions are identical, simply MMTC10P.The product for obtaining is 0.64 g
Black powder, test result shows that its product is the material and part nitrogen-doped carbon of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, only because the alkyl carbon chain of cationic surfactant is shorter so that MMTC10PInterlamellar spacing reduces so that add mPBI
Amount it is on the high side.In its 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.89 V vs RHE,
Electron transfer number is 3.89, and durability is good;Magnesium air cell performance is up to 86 mW/cm2.For its peak work(of hydrogen-oxygen fuel cell
Rate is 292 mW/cm2.It is 1.56 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0. 5mol/L, and carrying current is close
Degree reaches 60 mA/cm2.Ultracapacitor specific capacitance be 283 F/g, be recycled 10000 times still holding capacitor value 95%.
[embodiment 13] as described in Example 5, other conditions are identical, simply MMTC14P.The product for obtaining is 0.70 g
Black powder, test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, and it 0.1
In mol/L KOH solutions, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.97 V vs RHE, and electron transfer number is
3.97, durability is good;Magnesium air cell performance is up to 94 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 362 mW/
cm2, it is 1.55 V vs RHE that the sulfuric acid solution oxygen of 0.5 mol/L separates out take-off potential, and limiting current density reaches 90 mA/
cm2.Ultracapacitor specific capacitance be 338 F/g, be recycled 10000 times still holding capacitor value 97%.
[embodiment 14] as described in Example 5, other conditions are identical, simply with PPBI, 900 DEG C of pyrolysis temperature.Obtain
Product be 0.63 g black powders, test result shows that its product remains as 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.98 V vs RHE, electricity
Son transfer number is 3.97, and durability is good;Magnesium air cell performance is up to 115 mW/cm2.For its peak power of hydrogen-oxygen fuel cell
It is 437 mW/cm2, it is 1.54 V vs RHE, limiting current density that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
Reach 90 mA/cm2.Ultracapacitor specific capacitance be 436 F/g, be recycled 10000 times still holding capacitor value 97%.
It is pyrolyzed with the different temperatures of PPBI, the montmorillonite modified with different cationic surfactants(MMTCXP)And with
MMTC1XPDifferent quality than prepare product situation similar to the situation of above-described embodiment, as a result have similar performance.
[embodiment 15] as described in Example 5, other conditions are identical, simply with PzPBI, 900 DEG C of pyrolysis temperature.
The product for arriving is 0.63 g black powders, and test result shows that its product remains as 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential be 0.98 V vs RHE,
Electron transfer number is 3.97, and durability is good;Magnesium air cell performance is up to 115 mW/cm2.For its peak work(of hydrogen-oxygen fuel cell
Rate is 437 mW/cm2, it is 1.54 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and carrying current is close
Degree reaches 90 mA/cm2.Ultracapacitor specific capacitance be 436 F/g, be recycled 10000 times still holding capacitor value 97%.
It is pyrolyzed with the different temperatures of PzPBI, the montmorillonite modified with different cationic surfactants(MMTCXP)And with
MMTCXPDifferent quality than prepare product situation similar to the situation of above-described embodiment, as a result have similar performance.
[embodiment 16] as described in Example 5, other conditions are identical, simply without the method for vacuum aided, direct handle
MMTC16PIt is added in the solution of mPBI, is uniformly dispersed under stirring, steam near dry, is done at 60 ~ 120 DEG C in the vacuum drying chamber
It is dry, it is finely ground, be laid in porcelain boat bottom, under argon gas protection 900 DEG C in high temperature furnace, be pyrolyzed 2 ~ 3h, cooling, it is finely ground, use hydrofluoric acid
Repeatedly washing, removes template agent removing, obtains product for 0.67 g black powders, and test result shows that its product remains as porous nitrogen
The carbon material of doping, in its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.78 V vs
RHE, electron transfer number is 3.55, and durability is good;Magnesium air cell performance is up to 55 mW/cm2.For hydrogen-oxygen fuel cell its
Peak power is 132 mW/cm2, it is 1.68 V vs RHE, carrying current that the sulfuric acid solution oxygen of 0.5 mol/L separates out take-off potential
Density reaches 20 mA/cm2.Ultracapacitor specific capacitance be 135 F/g, be recycled 10000 times still holding capacitor value 90%.
Claims (6)
1. polybenzimidazoles is used(PBI)The preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing is prepared for carbon source and nitrogen source,
It is characterized in that:The full armaticity solubilities of PBI are carbon source and nitrogen source, and macromolecular chain is by the rigid benzimidazole group of armaticity
Into, in molecule containing rich in nitrogen imidazole ring and Amino End Group;What the montmorillonite being modified with cationic surfactant was formed
Hydrophobic interlayer is template, and the hydrophobicity of template is strong and weak and interlamellar spacing is adjusted by changing the chain alkyl of cationic surfactant
Section, PBI solution and the stratiform template of different interlamellar spacings, mix according to different quality ratio;The side of PBI solution vacuum aideds
Method, is filled into the interlayer of template several times, and the aromatic rings in PBI molecules is regularly arranged in interlayer;Protected in inert gas
Under shield, pyrolysis, removing template prepare the two-dimentional nitrogen-doped graphene of high nitrogen-containing.
2. PBI according to claim 1, it is characterised in that:Molecule is that the whole macromolecular chain of full armaticity forms one
Big π keys, molecule is made up of the rigid benzimidazole of armaticity, and contains imidazole ring and Amino End Group rich in nitrogen in molecule;
The PBI of full aroma type, e.g., the polyphenyl and miaow of poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmale] (mPBI), pyridine groups
Azoles(PPBI)With the polybenzimidazoles with pyrazine group(PzPBI)Etc., its structural formula is respectively:
The structural formula of mPBI
The structural formula of PPBI
The structural formula of PzPBI
Polymer viscosity average molecular weigh is soluble in dimethylacetylamide between 1~30,000(DMAc), dimethylformamide
(DMF), dimethyl sulfoxide (DMSO)(DMSO)With the organic solvent such as 1-METHYLPYRROLIDONE.
3. template according to claim 1 is the montmorillonite being modified with cationic surfactant, it is characterised in that:Sun
The length of the long alkyl chain of ionic surface active agent can regulate and control the hydrophobic performance of modified montmorillonoid and the interlamellar spacing of hydrophobic interlayer;
The interlamellar spacing of its interlayer is in 0.2~0.6nm;Hydrophobic interlayer is conducive to inserting for hydrophobic polymer PBI molecules;Cation
Surfactant selects C8~C16Cetylpyridinium bromide salt etc..
4. PBI according to claim 1 and the mass ratio of template modified montmorillonoid are 2:1~1:3;Hybrid mode is:
A certain amount of template modified montmorillonoid 120~220 DEG C of heating 2h in high temperature furnace are weighed, is inhaled with removing in multilayer material interlayer
Attached water, gas or impurity, cooling, be transferred in the pressure vessel for being connected with vavuum pump, vacuumize 30~40 min, with syringe to
A certain amount of PBI solution of injection in pressure vessel, makes PBI solution soak template, continues to vacuumize under heating, treats nothing in container
After liquid, continue aforesaid operations, until PBI solution runs out, drain, 60~120 DEG C of ageings in vacuum drying chamber, drying is cold
But, it is finely ground, porcelain boat is put into, 2~3h is pyrolyzed under argon gas protection in high temperature furnace, after cooling, template is washed away with hydrofluoric acid, spend
Ionized water washes away acid, is dried at 80~120 DEG C in the vacuum drying chamber, that is, obtain the two-dimentional nitrogen-doped graphene product of black.
5. pyrolysis temperature according to claim 1 is 700 ~ 1000 DEG C.
6. the two-dimentional nitrogen-doped graphene of high nitrogen-containing according to claim 1, is applied to urging for catalytic oxidation-reduction reaction
Agent, 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.
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CN109775693A (en) * | 2018-06-26 | 2019-05-21 | 郑州大学 | A kind of preparation method of nitrogen-doped graphene material |
CN110492062A (en) * | 2018-05-15 | 2019-11-22 | 宁德时代新能源科技股份有限公司 | Negative electrode material, negative electrode of lithium ion battery and its lithium ion battery |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5618615A (en) * | 1994-07-06 | 1997-04-08 | Matsushita Electric Industrial Co., Ltd. | Graphite layer material |
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 |
-
2016
- 2016-12-28 CN CN201611236549.6A patent/CN106744851B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5618615A (en) * | 1994-07-06 | 1997-04-08 | Matsushita Electric Industrial Co., Ltd. | Graphite layer material |
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 |
Non-Patent Citations (2)
Title |
---|
徐鼐: "《通用级聚乳酸的改性与加工成型》", 31 January 2016, 中国科学技术大学出版社 * |
汪多仁: "《绿色化工助剂》", 31 January 2006, 科学技术文献出版社 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110492062A (en) * | 2018-05-15 | 2019-11-22 | 宁德时代新能源科技股份有限公司 | Negative electrode material, negative electrode of lithium ion battery and its lithium ion battery |
CN110492062B (en) * | 2018-05-15 | 2020-11-20 | 宁德时代新能源科技股份有限公司 | Negative electrode material, lithium ion battery negative electrode and lithium ion battery |
CN109775693A (en) * | 2018-06-26 | 2019-05-21 | 郑州大学 | A kind of preparation method of nitrogen-doped graphene material |
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