CN106744851B - The method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing is prepared with polybenzimidazoles - Google Patents
The method of 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 with the polybenzimidazoles (PBI) of full armaticity be the two-dimentional nitrogen-doped graphene that carbon source and nitrogen source prepare high nitrogen-containing preparation method.It is raw material with PBI, it is template with the hydrophobic stratified material that cationic surfactant modified montmorillonoid is formed, with the method for vacuum aided, PBI solution is filled into stratiform template interlayer and is regularly arranged, after removing solvent, under an inert gas, it is pyrolyzed, obtains the two-dimentional nitrogen-doped graphene of high nitrogen-containing after removing template agent removing.PBI selects the soluble oligomer of full armaticity；Distance between stratiform template interlayer can be adjusted by changing alkyl chain size of cationic surfactant of its absorption etc., and interlamellar spacing is between 0.2~0.6 nm；PBI and stratiform template mass ratio are 2:1~1:3；Pyrolysis temperature is 700 ~ 1100 DEG C.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 two-dimentional nitrogen-doped graphene of preparation.
Description
Technical field
Belong to field of nano material preparation, for the redox reaction catalyst in Chemical Manufacture, clean energy resource field
Fuel cell, metal-air battery cathod catalyst, electrolysis water catalyst, lithium ion battery material, super capacitor electrode
The fields such as pole material and electrochemical sensor.
Background technique
Polybenzimidazoles (PBI) is a kind of high molecular material haveing excellent performance, due to containing benzimidazole ring category in minute
Contain imidazoles nitrogen on imidazole ring in the stiffening ring of armaticity, molecule, belongs to the aroma type high molecular polymer rich in nitrogen.Institute
With, pyrolysis can prepare the carbon material of N doping, if allowing it to be added between small interlayer with suitable template, heat
Solution, available nitrogen-doped graphene.The PBI of full aroma type, it is e.g., poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmales]
(mPBI), the polybenzimidazoles (PPBI) of pyridine groups and the polybenzimidazoles (PzPBI) with pyrazine group etc., structure
Formula is respectively as follows:
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 is to form high molecular all atoms in one plane, each original of intramolecular
A big pi bond is formed between son, molecule belongs to rigid, easily plane superposition and aggregation between molecule, if regulation it is good its
In the mass ratio of nano template, it can be made to be regularly arranged on template surface, if under inert gas protection, heat
Solution, it may occur that a series of thermal chemical reaction such as dehydrogenation-cyclisation-carbonization finally obtains multilayer nitrogen-doped graphene structural material.
Graphene performance after hetero atom (N, P, B and S etc.) doping is more prominent, can also be adulterated with codope or three etc..
In all kinds of Heteroatom doping graphenes, nitrogen-doped graphene (NG) most study, the structure of the nitrogen in NG there are many form,
Wherein, pyridine type nitrogen and pyrroles's type nitrogen are planar structures, active (Nie Yao etc., Journal of Chemical Industry and Engineering) with catalytic oxidation-reduction, 2015,
66:3305), on the contrary, the nitrogen-atoms of three-dimensional structure is without activity, so, the good nitrogen-doped graphene preparation of catalytic performance is first
It is required that nitrogen content wants high, and then requires the content of pyridine type nitrogen and pyrroles's type nitrogen to want high, so, the preparation side of nitrogen-doped graphene
Method has lot of documents report: graphite oxide reduction method, heat-treatment oxidation graphene (Li X, the et al. J under ammonia atmosphere
Am Chem Soc(American Chemical Society) 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, melamine resin,
The nitrogen containing polymers 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, synthesized, the two-dimentional nitrogen-doped graphene for being pyrolyzed preparation can be containing more
Pyridine nitrogen and pyrroles's nitrogen show excellent catalytic oxidation-reduction performance.Specific method is that template montmorillonite is 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, since aniline belongs to small molecule, it is also easy to enter in interlayer；Aniline polymerize in interlayer
Reaction obtains polyaniline due to being controlled by 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 high molecular material for utilizing the benzimidazole unit of full aroma type, e.g., poly- (2,5- benzimidazole)
(ABPBI), the polybenzimidazoles (PPBI) of poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmales] (mPBI), pyridine groups
It is carbon source and nitrogen source with the polybenzimidazoles (PzPBI) etc. with pyrazine group, with cationic surfactant modified montmorillonoid
Stratified material obtains hydrophobic interlayer and does template, keeps rigid PBI molecule regularly arranged in interlayer, does not occur largely stacking, roll up
Song etc. is unfavorable for the case where generating graphene generation, to prepare multilayer two-dimension nitrogen-doped graphene.The present invention and document difference
Innovative point be: firstly, to increase interlamellar spacing, then to use cation surface activating to the sour modification of stratiform mould material
Agent is modified processing, so that its interlayer is become hydrophobic, and interlamellar spacing becomes larger, with the long alkyl chain of cationic surfactant
To regulate and control the hydrophobic strong and weak and interlamellar spacing of interlayer；The only sufficiently large interlamellar spacing of hydrophobic type, can just make the macromolecule of hydrophobic type
It is inserted into interlayer, and regularly arranged；Secondly, alloing macromolecule ABPBI molecule to enter folder using the method for vacuum aided
In layer；Third, the PBI molecule of rigidity is dry in interlayer, under the double action of hydrophobic interlayer and vacuum aided, can just reach
To high molecular regularly arranged, it is beneficial to prevent a large amount of stackings, curling etc. and is unfavorable for the case where generating graphene, after being inserted into PBI
It is pyrolyzed under inert gas protection, it may occur that a series of thermal chemical reaction such as dehydrogenation-cyclisation-carbonization finally obtains multilayer nitrogen
Doped graphene structural material goes template agent removing that the graphene of two-dimentional N doping can be obtained.
And the method for document is template using the modified H of acid+The montmorillonite of type obtains the interlayer of hydrophilic；Small molecule benzene
Amine generates water-soluble anilinechloride in acid condition, is conducive to be inserted into the interlayer of hydrophilic；Furthermore small molecule
It easily enters in interlayer, does not need to carry out complicated operation；Polymerization reaction occurs in interlayer for aniline, obtains polyaniline, gathers
The process of conjunction is just controlled by area size.The molecule of obtained polyaniline plane, is pyrolyzed under inert gas protection, 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 molecule and rule row
The factors such as the proportion of column and PBI and template.Hydrophobic treatment be macromolecule insertion basis, interlamellar spacing control and template and
PBI proportion decides the regular degree of macromolecule arrangement and obtains the number of plies of graphene.
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 template, control template interlamellar spacing are come
The number of plies and performance for controlling the nitrogen-doped graphene of preparation, finally obtain ideal multilayer two-dimension nitrogen-doped graphene.
It is common method that high molecular material method for pyrolysis, which prepares carbon material, such as uses phenolic resin, pollopas and trimerization
The pyrolysis such as melamine resin prepare carbon material.Compared with the high molecular materials such as phenolic resin, pollopas and melamine resin,
PBI is the difference is that it contains the stiffening ring benzimidazole ring of armaticity, and the imidazoles nitrogen on imidazole ring keeps its nitrogenous
Amount is more abundant.Therefore the carbon material of the N doping of the available high-content of high temperature pyrolysis PBI, and by introducing suitable template
Or the orientation of the fragrant plane of a loop of control molecule, the grapheme material of available multilayer N doping after pyrolysis.With it is poly-
Aniline is compared with high molecular materials such as polypyrroles, and PBI can dissolve, and is inserted easily into template interlayer, and polyaniline, polypyrrole
Deng insoluble, can not be inserted into the interlayer of template.
Summary of the invention
The present invention is the high molecular material for utilizing the benzimidazole unit of full aroma type, e.g., poly- (2,5- benzimidazole)
(ABPBI), the polybenzimidazoles (PPBI) of poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmales] (mPBI), pyridine groups
It is carbon source and nitrogen source with the polybenzimidazoles (PzPBI) etc. with pyrazine group, with cationic surfactant (C8~C16Alkyl
Pyridinium bromide salt etc.).Modified montmorillonoid stratified material obtains hydrophobic interlayer and does template, makes rigid PBI molecule in interlayer
It is regularly arranged, do not occur largely stacking, crimping etc. being unfavorable for the case where generating graphene generation, to prepare multilayer two-dimension N doping
Graphene.The present invention and the innovative point of document difference are: firstly, will be to the sour modification of stratiform mould material, to increase
Interlamellar spacing, then it is modified processing with cationic surfactant, so that its interlayer is become hydrophobic, and interlamellar spacing becomes larger, 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 just can be such that the macromolecule of hydrophobic type is inserted into interlayer, and regularly arranged；Secondly, the method using vacuum aided makes
Macromolecule ABPBI molecule can enter in interlayer；Third, the PBI molecule of rigidity is dry in interlayer, in hydrophobic interlayer and vacuum
It under the double action of auxiliary, just can achieve high molecular regularly arranged, be beneficial to prevent a large amount of stackings, curling etc. and be unfavorable for giving birth to
The case where at graphene, be inserted into PBI after it is regularly arranged in the case where, be pyrolyzed under inert gas protection, it may occur that dehydrogenation-ring
The a series of thermal chemical reaction such as change-carbonization finally obtains multilayer nitrogen-doped graphene structural material, goes template agent removing that can obtain
To the graphene of two-dimentional N doping.
And the method for document is template using the modified H of acid+The montmorillonite of type obtains the interlayer of hydrophilic；Small molecule benzene
Amine generates water-soluble anilinechloride in acid condition, is conducive to be inserted into the interlayer of hydrophilic；Furthermore small molecule
It easily enters in interlayer, does not need to carry out complicated operation；Polymerization reaction occurs in interlayer for aniline, obtains polyaniline, gathers
The process of conjunction is just controlled by area size.The molecule of obtained polyaniline plane, is pyrolyzed under inert gas protection, 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 molecule and rule row
The factors such as the proportion of column and PBI and template.Hydrophobic treatment be macromolecule insertion basis, interlamellar spacing control and template and
PBI proportion decides the regular degree of macromolecule arrangement and obtains the number of plies of graphene.
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 template, control template interlamellar spacing are come
The number of plies and performance for controlling the nitrogen-doped graphene of preparation, finally obtain ideal multilayer two-dimension nitrogen-doped graphene.
It is common method that high molecular material method for pyrolysis, which prepares carbon material, such as uses phenolic resin, pollopas and trimerization
The pyrolysis such as melamine resin prepare carbon material.PBI is compared with the high molecular materials such as phenolic resin, pollopas and melamine resin
The difference is that PBI contains the stiffening ring benzimidazole ring of armaticity, and the imidazoles nitrogen on imidazole ring makes its nitrogen content more
Add abundant, entire molecule is the rigid molecule of armaticity.Pass through the fragrant plane of a loop of the suitable template of introducing or control molecule
Orientation, the after pyrolysis grapheme material of available multilayer N doping respectively.With the macromolecules such as polyaniline and polypyrrole
Material is compared, and PBI can dissolve, and is inserted easily into template interlayer, and polyaniline, polypyrrole etc. are insoluble, can not be inserted into
In the interlayer of template.
The difference polymerizeing after being added with literature method acid type montmorillonite aniline is, as hydrophobic high molecular material
PBI cannot 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 cannot be regularly arranged under third free state, is conducive under the conditions of vacuum aided with hydrophobic environment
PBI's is regularly arranged.A series of heat such as dehydrogenation-cyclisation-carbonization occur when only regularly arranged PBI is pyrolyzed under protection of argon gas
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 the rigidity by armaticity
Benzimidazole composition, and viscosity average molecular weigh is chosen 10,000~30,000 containing imidazole ring and Amino End Group rich in nitrogen in molecule
Between be soluble in DMAc, DMF, DMSO, the oligomer in N-Methyl pyrrolidone equal solvent.Molecular weight is too big, PBI's
Solubility property is deteriorated；The graphene performance of its too small pyrolysis preparation of molecular weight is not good enough.
The method of the preparation of the graphene of two-dimentional N doping are as follows: montmorillonite carries out acidification first, cleans drying, respectively
The cationic surfactant C of different alkyl chains is added8~C16Cetylpyridinium bromide salt is modified, and prepares hydrophobic interlayer
Montmorillonite is as template.A certain amount of template is put into the container that can be vacuumized, a certain amount of PBI is dissolved in molten
Solution is formed in agent, after 30 min of container vacuum-pumping for filling template, closes valve, is injected with syringe into container suitable
The solution for measuring PBI begins to warm up, vacuumizes after solution submerges template, steams solvent at leisure and does to close, so repeatedly
Repeatedly until the solution of PBI is finished.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
Portion is put into electric tube furnace, under protection of argon gas, at 700~1100 DEG C, is pyrolyzed 2 ~ 3h.It is cooled to room temperature, takes to furnace temperature
Out, it is repeatedly washed with hydrofluoric acid to go removing template montmorillonite, filters, be washed with deionized water, dried, obtain two-dimentional N doping graphite
Alkene.
In the present invention: the optional C of cationic surfactant8~C16Cetylpyridinium bromide salt etc., the length of alkyl is not
But the hydrophobicity that can control interlayer is strong and weak, and the interlamellar spacing of adjustable interlayer.Alkyl carbon chain is longer, the hydrophobicity of interlayer
It is stronger, interlamellar spacing is bigger, 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 where PBI is inserted into sufficient situation, interlamellar spacing is wider, more, the obtained graphite of PBI insertion
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
Filling and arranging situation of the PBI in interlayer: PBI is required to fill full interlayer first；Secondly, it is desirable that PBI rule row in interlayer
Column.It only in this way can just obtain complete two-dimentional nitrogen-doped graphene.This requires PBI solution repeatedly to suck, and waits a moment and drains slowly
Repetitive operation is multiple afterwards.The mass ratio of PBI and template modified montmorillonoid is 2:1~1:3.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 700~1100 DEG C.The too low PBI of temperature cannot be pyrolyzed, and obtain product
Electric conductivity it is poor；After pyrolysis temperature reaches optimum temperature, then to increase pyrolysis temperature its performance constant, so pyrolysis temperature is unsuitable
It is 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.
Specific embodiment
The preparation of [embodiment 1] mPBI: polyphosphoric acids is added in the three-necked flask equipped with electric stirring and nitrogen protection
(PPA) (100g), the lower 160 DEG C of stirrings 1h of nitrogen protection is to remove extra moisture and air.By DABz (4g, 18.7
Mmol) and M-phthalic acid (3.1g, 18.7 mmol) is uniformly mixed, and is slowly added in three-necked flask.Control nitrogen
Flow velocity prevents DABz to be oxidized, while reaction temperature being promoted to 200 DEG C and continues to keep the temperature, is stirred to react 5-8h.With reaction
The increase of time, polymerization system gradually become sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred to largely
It reels off raw silk from cocoons in deionized water, cleans, drying, crush, to remove polyphosphoric acids and unreacted reactant, i.e., deionized water is repeatedly washed
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 three-necked flask equipped with electric stirring and nitrogen protection
Sour (PPA) (100g), the lower 160 DEG C of stirrings 1h of nitrogen protection is to remove extra moisture and air.By DABz (4.00g,
18.7 mmol) and 2,6- pyridinedicarboxylic acid (3.12g, 18.7 mmol) is uniformly mixed, and is slowly added to three-necked flask
In.Nitrogen flow rate is controlled, DABz is prevented to be oxidized, while reaction temperature being promoted to 200 DEG C and continues to keep the temperature, is stirred to react 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 moved on in a large amount of deionized waters and is reeled off raw silk from cocoons, and is cleaned, drying, is crushed, and deionized water is repeatedly washed to remove polyphosphoric acids and not
Reaction response object is to get PPBI is arrived, 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, only by 2,6- pyridinedicarboxylic acid point
Do not change 3,5- pyridinedicarboxylic acid, 2,3- pyridinedicarboxylic acid, 2,5- pyridinedicarboxylic acid or 3,4- pyridinedicarboxylic acid, Qi Tacao into
Make the PPBI containing different pyridine groups to can be obtained, product is denoted as respectively with embodiment 2: 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 three-necked flask equipped with electric stirring and nitrogen protection
Sour (PPA) (100g), the lower 160 DEG C of stirrings 1h of nitrogen protection is to remove extra moisture and air.By DABz (4.00g,
18.7 mmol) and 2,6- pyrazinedicarboxylicacid (3.14g, 18.7 mmol) is uniformly mixed, and is slowly added to three-necked flask
In.Nitrogen flow rate is controlled, DABz is prevented to be oxidized, while reaction temperature being promoted to 200 DEG C and continues to keep the temperature, is stirred to react 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 moved on in a large amount of deionized waters and is reeled off raw silk from cocoons, and is cleaned, drying, is crushed, and deionized water is repeatedly washed to remove polyphosphoric acids and not
Reaction response object is to get PzPBI is arrived, 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, only by 2,6- pyrazinedicarboxylicacid point
Do not change 2,5- pyrazinedicarboxylicacid or 2,3- pyrazinedicarboxylicacid into, other operations can be obtained with embodiment 3 containing different pyrroles
The PzPBI of piperidinyl group, product are denoted as respectively: 3,5-PzPBI or 2,3-PzPBI.
The sour modification of [embodiment 4] montmorillonite and cationic surfactant modification.
The acid of montmorillonite is modified: taking 10 g montmorillonites (Na-MMT) to be put into 1000mL beaker, 600 mL 0.1 are added
The HCl of mol/L under stirring, impregnates 2 days, filters, repeatedly washed, filtered with a large amount of deionized water, 60 DEG C of dry sour modifications
Montmorillonite (H-MMT).Measuring its ion exchange capacity is 0.25 meq/g.
Cationic surfactant C8~C16Cetylpyridinium bromide salt, first selection C16Cetylpyridinium bromide salt
(C16P) modified montmorillonite is denoted as MMTC16P, experimental procedure is as follows: weighing 5 g H-MMT(0.25 meq/g), at 120 ~ 220 DEG C
Lower 2 h of drying, to remove the impurity such as water of its absorption, be slowly added into 0.5 g under stiring 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, filter, cleaned with deionized water to no bromide ion, dried at 120 DEG C, grind, obtain using C16Alkyl
The MMT of pyridinium bromide salt (C16P) is abbreviated as MMTC16P。
C can be carried out in aforementioned manners8~C15The modification of cetylpyridinium bromide salt (CXP) cationic surfactant
Montmorillonite is abbreviated as MMTCXP, wherein X is the carbon atom number of alkyl.
[embodiment 5] uses MMTC16PAs template, by taking mPBI and template mass ratio are 1:1 as an example: 250 mL's
In beaker, the mPBI(viscosity average molecular weigh 1 ~ 3 of 1 g being added ten thousand) with 20 mL DMAc, heats, stir to dissolve, solution filters,
It is spare to remove insoluble matter.In the bottle,suction of 250 mL for being connected with vacuum pump, 1 g MMT is addedC16PIt is set to be laid in bottle
Bottom after vacuumizing 30 min, closes valve, stops vacuumizing, the DMAc solution of mPBI is added with syringe, soaks it sufficiently
Template, heating, continues to vacuumize to remove solvent, after to be dried, repeat above operation, repeated multiple times until mPBI's
DMAc solution is all added, and after draining, takes out, is aged at 60~120 DEG C, and drying is finely ground to cold taking-up, porcelain boat is put into, in height
It is pyrolyzed 2~3h at lower 900 DEG C of argon gas protection in warm furnace, it is cooling, it takes out, is repeatedly washed with hydrofluoric acid, to remove template agent removing, spent
Ion is washed to neutrality, obtains 0.67 g of black powder solid in vacuum drying.BET test shows that its surface area is 486
m2 g-1, aperture is 16 ~ 23 nm, the product that shows of SEM test be porous material, TEM and HRTEM analysis shows, produce
Product are multi-layer graphene structural material, and graphene is drawn a bow to the full back as 3 ~ 4 layers of graphene.XRD and Raman spectrum test show product be 3 ~
4 layers of graphene-structured；XPS analysis shows that product nitrogen content is 7.0%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, produces
Product are the two-dimensional graphenes of N doping.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, originating hydrogen reduction current potential is
0.99 V vs RHE, electron transfer number 3.98, durability is good；Magnesium air battery 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 take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
RHE, limiting current density reach 90 mA/cm2.Supercapacitor 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 only pyrolysis temperature is changed to 700 DEG C.Obtained production
Product are 0.72 g black powder, 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 lower, electronic conductivity is slightly worse, so its chemical property is slightly worse: it 0.1
In mol/L KOH solution, 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 battery performance is up to 54 mW/cm2.It is 154 mW/ for its peak power of hydrogen-oxygen fuel cell
cm2, it is 1.68 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 40
mA/cm2.Supercapacitor 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, only change pyrolysis temperature and are changed to 1100 DEG C.?
The product arrived is 0.63 g black powder, and test result shows that its product remains as 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.95 V vs RHE,
Electron transfer number is 3.94, and durability is good；Magnesium air battery performance is up to 86 mW/cm2.For its peak function of hydrogen-oxygen fuel cell
Rate is 337 mW/cm2, it is 1.62 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L, and carrying current is close
Degree reaches 60 mA/cm2.Supercapacitor 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, only change mPBI and MMTC16PThe ratio of template
Example is 1:2.Obtained product is 0.70 g 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 MMTC16PThe increase of amount, so that mPBI filling is not enough, obtained two-dimentional N doping graphite
Alkene lamella becomes smaller, and electric conductivity is deteriorated, in 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, and oxygen initial reduction electricity
Position is 0.92 V vs RHE, and electron transfer number 3.66, durability is good；Magnesium air battery 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 take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
Vs RHE, limiting current density reach 40 mA/cm2.Supercapacitor 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, only change mPBI and MMTC16PThe ratio of template
Example is 1:3.Obtained product is 0.70 g 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 MMTC16PThe increase of amount, so that mPBI filling is not enough, obtained two-dimentional N doping
Graphene sheet layer becomes smaller, and 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 3.59, durability is good；Magnesium air battery performance is up to 54 mW/cm2。
It is 176 mW/cm for its peak power of hydrogen-oxygen fuel cell2, oxygen is precipitated take-off potential and is in the sulfuric acid solution of 0.5 mol/L
1.68 vs RHE, limiting current density reach 40 mA/cm2.Supercapacitor 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, only change mPBI and MMTC16PTemplate
Ratio is 2:1.Obtained product is 0.67 g 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 amount of powder shape N doping.This is because the increase of mPBI amount, so that
MPBI is other than filling interlayer gap, and there are also some residual, remaining mPBI coats to form N doping on template surface
Porous carbon materials, catalytic performance are 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 3.75, durability is good；Magnesium air battery 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 take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
RHE, limiting current density reach 50 mA/cm2.Supercapacitor 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 only template uses MMT insteadC8P.Obtained production
Product are 0.65 g black powder, 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 for 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 are 0.81 V vs RHE, and electron transfer number 3.88, durability is good；Magnesium air is cell performance
It can be up to 78 mW/cm2.It is 237 mW/cm for its peak power of hydrogen-oxygen fuel cell2, oxygen is precipitated 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.Supercapacitor 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, only MMTC10P.Obtained product is 0.64 g
Black powder, test result show 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 mPBI is added
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 battery performance is up to 86 mW/cm2.For its peak function of hydrogen-oxygen fuel cell
Rate is 292 mW/cm2.It is 1.56 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0. 5mol/L, and carrying current is close
Degree reaches 60 mA/cm2.Supercapacitor 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, only MMTC14P.Obtained product is 0.70 g
Black powder, test result show that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, 0.1
In mol/L KOH solution, 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 battery performance is up to 94 mW/cm2.It is 362 mW/ for its peak power of hydrogen-oxygen fuel cell
cm2, it is 1.55 V vs RHE that take-off potential, which is precipitated, in the sulfuric acid solution oxygen of 0.5 mol/L, and limiting current density reaches 90 mA/
cm2.Supercapacitor 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, only use PPBI, 900 DEG C of pyrolysis temperature.It obtains
Product be 0.63 g black powder, test result shows that its product remains as 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in 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 battery performance is up to 115 mW/cm2.For its peak power of hydrogen-oxygen fuel cell
For 437 mW/cm2, it is 1.54 V vs RHE, limiting current density that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
Reach 90 mA/cm2.Supercapacitor 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 (MMT modified with different cationic surfactantsCXP) and with
MMTC1XPDifferent quality than preparation product the case where be similar to above-described embodiment the case where, as a result have similar performance.
[embodiment 15] as described in Example 5, other conditions are identical, only use PzPBI, 900 DEG C of pyrolysis temperature.?
The product arrived is 0.63 g black powder, and test result shows that its product remains as 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.98 V vs RHE,
Electron transfer number is 3.97, and durability is good；Magnesium air battery performance is up to 115 mW/cm2.For its peak function of hydrogen-oxygen fuel cell
Rate is 437 mW/cm2, it is 1.54 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L, and carrying current is close
Degree reaches 90 mA/cm2.Supercapacitor 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 (MMT modified with different cationic surfactantsCXP) and with
MMTCXPDifferent quality than preparation product the case where be similar to above-described embodiment the case where, as a result have similar performance.
[embodiment 16] as described in Example 5, other conditions are identical, do not have to the method for vacuum aided, directly handle only
MMTC16PIt is added in the solution of mPBI, is uniformly dispersed, is steamed near dry under stirring, done at 60 ~ 120 DEG C in vacuum oven
It is dry, it is finely ground, it is laid in porcelain boat bottom, under protection of argon gas 900 DEG C in high temperature furnace, is pyrolyzed 2 ~ 3h, it is cooling, finely ground, use hydrofluoric acid
Repeatedly washing, removes template agent removing, and obtaining product is 0.67 g black powder, and test result shows that its product remains as porous nitrogen
The carbon material of doping, in 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.78 V vs
RHE, electron transfer number 3.55, durability is good；Magnesium air battery 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 take-off potential, which is precipitated, in the sulfuric acid solution oxygen of 0.5 mol/L
Density reaches 20 mA/cm2.Supercapacitor specific capacitance be 135 F/g, be recycled 10000 times still holding capacitor value 90%.
Claims (3)
1. it is the preparation method for the two-dimentional nitrogen-doped graphene that carbon source and nitrogen source prepare high nitrogen-containing with polybenzimidazoles (PBI),
It is characterized by: the PBI of full armaticity solubility is carbon source and nitrogen source, the macromolecular chain of PBI is the rigid benzo by armaticity
Imidazoles forms, and imidazole ring and Amino End Group rich in nitrogen are contained in molecule；With the modified montmorillonite of cationic surfactant
For template, the long alkane that the hydrophobicity of the hydrophobic interlayer of template is strong, weak and interlamellar spacing passes through change cationic surfactant
Keynote section, cationic surfactant select C8~C16Cetylpyridinium bromide salt, the interlamellar spacing of template are 0.2~0.6nm；
PBI solution is mixed with template by the mass ratio of 2:1~1:3；The method of PBI solution vacuum aided, is filled into mould several times
In the interlayer of plate agent, the aromatic rings in PBI molecule is regularly arranged in interlayer；Under inert gas protection, at 700~1000 DEG C
It is pyrolyzed 2~3 hours, removes template with hydrofluoric acid wash, prepare the two-dimentional nitrogen-doped graphene of high nitrogen-containing.
It with polybenzimidazoles (PBI) is that carbon source and nitrogen source prepare the two-dimentional nitrogen of high nitrogen-containing and mix 2. according to claim 1
The preparation method of miscellaneous graphene, it is characterised in that: PBI molecule is full armaticity, and entire macromolecular chain forms a big π
Key, molecule are made of the rigid benzimidazole of armaticity, and contain imidazole ring and Amino End Group rich in nitrogen in molecule；Quan Fang
The PBI of odor type: it selects, the polybenzimidazoles of poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmales] (mPBI), pyridine groups
(PPBI) and one of the polybenzimidazoles with pyrazine group (PzPBI), structural formula is respectively as follows:
The structural formula of mPBI
The structural formula of PPBI
The structural formula of PzPBI
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 in any one organic solvent.
It with polybenzimidazoles (PBI) is that carbon source and nitrogen source prepare the two-dimentional nitrogen of high nitrogen-containing and mix 3. according to claim 1
The mass ratio of the preparation method of miscellaneous graphene, PBI and template is 2:1~1:3；Hybrid mode are as follows: weigh a certain amount of mould
Plate agent 120~220 DEG C of heating 2h in high temperature furnace, it is cooling to remove the water adsorbed in multilayer material interlayer, gas or impurity,
It is transferred in the pressure vessel for being connected with vacuum pump, vacuumizes 30~40 min, injected with syringe into pressure vessel a certain amount of
PBI solution, make PBI solution impregnate template, continue to vacuumize under heating, after no liquid in container, continue aforesaid operations,
Until PBI solution runs out, to drain, 60~120 DEG C of ageings in vacuum oven are dried, and it is cooling, it is finely ground, it is put into porcelain boat, in height
In warm furnace under argon gas protection, at 700~1000 DEG C, it is pyrolyzed 2~3h and washes away template after cooling with hydrofluoric acid, use deionization
Acid is removed in washing, dries in vacuum oven at 80~120 DEG C to get the two-dimentional nitrogen-doped graphene product of black is arrived.
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| 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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