CN106477566A - A kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing - Google Patents
A kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing Download PDFInfo
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Abstract
A kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing, is gathered with the armaticity rigid macromolecule material of high nitrogen-containing（2,5 benzimidazoles）（ABPBI）For carbon source and nitrogen source, with Fe (OH)3Or Fe2O3）Nano-particle is template, and the rigid benzimidazole of the armaticity in macromolecular chain is regularly arranged to be pyrolyzed under argon protection on template surface, forms three-dimensional nitrogen-doped graphene structure.Nitrogen-atoms in ABPBI molecule and iron oxides（Or hydroxide）The iron ion on surface generates coordinate bond, plays the effect of fixed nitrogen.Require：ABPBI viscosity-average molecular weight 1 ~ 30,000；Fe(OH)3Or Fe2O3）Particle diameter is 5 ~ 50nm, ABPBI and Fe (OH)3Or Fe2O3）The mass ratio of the two is 3:1~1:3；Pyrolysis temperature is 600 ~ 1200 DEG C, is pyrolyzed 2 ~ 3h, is washed with dilute hydrochloric acid 3 times, deionized water wash 3 times.The three-dimensional nitrogen-doped graphene of preparation is used for oxygen reduction catalyst, oxygen separates out catalyst, for the storage of the electrochemical energies such as fuel cell, metal-air battery and ultracapacitor and switching device.
Description
Technical field
Belong to field of nano material preparation, the negative electrode for the fuel cell in clean energy resource field, metal-air battery is urged
Agent, is electrolysed water catalyst, the field such as electrode material for super capacitor and electrochemical sensor.
Background technology
Graphene be a kind of by carbon atom with sp2The hexangle type of hybrid orbital composition is in two wieners of honeycomb crystal lattice structure
Rice material.Graphene is with its distinctive stable in properties, the excellent physical chemistry such as electric conductivity is good, specific strength is big, specific surface area is big
Property causes the extensive research interest of people.Two-dimensional graphene, due to easy genetic horizon-layer stacking, obtains graphite-structure, it is excellent
More property can not be embodied well.In order to solve this difficult problem, people have transferred to research focus on three-dimensional grapheme
(Chen L, et al. Small（Little）, 2015, 11(12): 1423).It is solid that three-dimensional grapheme material not only has Graphene
Some physicochemical properties, its three-dimensional porous micro nano structure so that it is had concurrently specific surface area is big, high mechanical strength, electronic conductivity
Energy is good and strengthens the good characteristics such as mass transfer, and these unique properties make three-dimensional grapheme and its composite in material science
Receive much concern.Research finds, three-dimensional grapheme is applied to the field such as catalytic reaction, fuel cell, sensor, ultracapacitor table
Reveal excellent performance (Dong H, et al. Sci Rep (scientific report), 2015,5: 17542; Cao X, et
Al. Energy Environ. Sci. (energy environment science), 2014,7:1850).Research shows, after material with carbon element doping,
All show obvious oxygen reduction catalytic activity.In all kinds of Heteroatom doping Graphenes, nitrogen-doped graphene most study.Two dimension
The easy stacked in multi-layers of nitrogen-doped graphene makes active sites reduce, and so that its performance is reduced due to lacking mass transfer channel.And it is three-dimensional
Nitrogen-doped graphene can make active sites be exposed on the three phase boundary of reaction, improves reaction efficiency, and can improve reaction
Thing and the mass-transfer efficiency of product.The preparation method of three-dimensional nitrogen-doped graphene has a lot, such as using soft template method (Ding W, et
Al. J Am Chem Soc (JACS), 2015,137 (16): 5414)；Using hard template method (Meng Y,
Et al. J Am Chem Soc (JACS), 2014,136 (39): 13554)；Lithium nitride and carbon tetrachloride and
Cyanuric Chloride, lithium nitride, carbon tetrachloride solvent thermal response prepare nitrogen-doped graphene (Deng D, Chem. Mater. (chemistry
Material), 2011,23 (5): 1188)；With polypyrrole and graphene oxide pyrolysis preparation 3D nitrogen-doped graphene (Lin Z,
Et al. Nano Energy (the nanometer energy), 2013,2 (2):241) etc..
People commonly use the pyrolysis such as phenolic resin, pollopas and melmac and prepare material with carbon element, many in pyrolysis preparation
Hole material with carbon element or graphite alkenes non-metal catalyst.
Poly- 2,5- benzimidazole (ABPBI）It is simplest one kind in PBI family, adopt 3, the 4- diaminobenzoic acid to be
Raw material, under inert gas argon gas shielded, 200 DEG C in polyphosphoric acids (PPA) under the conditions of condensation polymerization be obtained.Its preparation reaction
Equation is as follows：
As nitrogen containing polymer material, polybenzimidazoles（PBI）There is the high imidazole ring structure of nitrogen content.Using PBI as one
Plant nitrogenous high intermediate, the catalyst of its preparation has higher electrocatalysis characteristic.Imidazoles nitrogen is contained on imidazole ring in molecule,
According to metal ion（As Cu, Mn, Fe, Ru, Ti, Mo and Os etc.）It is doped, prepares metal nitrogen C catalyst, one can be entered
Step improve electro catalytic activity and stability (Cameron C G, et al. J Phys Chem B,（（The U.S.）Physical chemistry
Report B）2001, 105:8838).The synthetic method of PBI can be divided into 5 kinds：Tetramine and dintrile, tetramine and diester, tetramine and two
Acid, tetramine and diamides, tetramine and dialdehyde, wherein, tetramines aromatic is the most frequently used with the reaction of aromatic diacid.D Archivio is to many
The preparation method of hole PBI resin material, performance and its prepare catalyst with metallic ion coordination and studied（Archivio
D, et al. Chem-A Eur J, (European The Chemicals) 2000,6 (5): 794）.
This invention be by the use of armaticity benzimidazole as the raw material providing carbon and nitrogen, under inert gas argon gas shielded
Nitrogenous material with carbon element is prepared in pyrolysis.Synthesis is controlled by the size of the ratio of feed change and hard template, Control architecture granule
The parameter such as the number of plies in the aperture of nitrogenous material with carbon element, porosity and Graphene, finally give preferable multi-layer three-dimension N doping stone
Black alkene.
Compared with phenolic resin, pollopas Polymer material, the difference of ABPBI is that it contains armaticity
Stiffening ring benzimidazole ring, and the imidazoles nitrogen on imidazole ring makes its nitrogen content abundanter.Therefore high temperature pyrolysis ABPBI can obtain
To the material with carbon element of N doping, and by introducing the orientation of the fragrant plane of a loop of suitable template or control molecule, through heat
The material of the graphene-structured of multilamellar N doping can be obtained respectively after solution.
Compared with preparing nitrogen-doped graphene with the material such as polyaniline and polypyrrole, ABPBI can dissolve it is easy to cover with paint, lacquer, colour wash, etc. in template
Agent surface, and polyaniline, polypyrrole etc. are not dissolved it is impossible to be mixed with template.
Content of the invention
The present invention, has invented a kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing.By selecting nitrogen content
The ABPBI of high armaticity rigidity is nitrogen source and carbon source, after ABPBI dissolving, because it is rigid molecule, it can regularly arranged,
It is coated on template surface, it is pyrolyzed and can obtain nitrogen-doped graphene.By controlling ABPBI and template（Nanometer Fe
(OH)3Or Fe2O3Powder body）Mass percent, template particle diameter, the method such as coating method and pyrolytic process to be regulating and controlling the 3D of preparation
The aperture of nitrogen-doped graphene, porosity, specific surface area and the number of plies generating Graphene.This materials application is in redox reaction
Catalyst, oxygen reduction catalyst, electrolysis water oxygen separates out catalyst and carrier, ultracapacitor, and electrolysis, sensor material etc. are led
Domain.Template in the present invention, iron oxides（Or hydroxide）The iron ion of nano grain surface can with ABPBI molecule in
Nitrogen-atoms coordination generate coordinate bond, such that it is able to prevent the loss of nitrogen in ABPBI pyrolytic process, play the effect of fixed nitrogen so that
The content of the nitrogen of three-dimensional nitrogen-doped graphene material arriving improves.
ABPBI with above phenolic resin, pollopas and melmac Polymer material difference is：ABPBI
In molecule, benzimidazole ring belongs to the stiffening ring of armaticity, imidazole ring in molecule contains imidazoles nitrogen, belongs to the aroma type of rich nitrogen
High molecular polymer.Therefore, its pyrolysis can obtain the material with carbon element of N doping, if under suitable template action, can obtain
Grapheme material to multilamellar N doping.If the plane controlling the aromatic rings of molecule is at templating nanoparticles Fe (OH)3Or Fe2O3?
Grain surface is evenly distributed according to a direction, and its pyrolysis can obtain the graphene-structured of three-dimensional N doping.With polyaniline, poly-
（O-phenylenediamine）, unlike polypyrrole Polymer material：It is organic that ABPBI family macromolecule is soluble in DMAc, DMSO etc.
In solvent, easily it is sufficiently mixed with template, not split-phase, due to its solubility, it is in preparation 3D nitrogen-doped graphene nano material
When there is good operability.However, polyaniline compound, polypyrrole Polymer material soluble it is impossible to cover with paint, lacquer, colour wash, etc. template table
Face, it is blended with template.
ABPBI is that the viscosity-average molecular weight of solid phase method or liquid phase method preparation is soluble in DMAC between 10,000～30,000,
DMF, DMSO, in N-Methyl pyrrolidone equal solvent.Molecular weight is too big, and the solubility property of ABPBI is deteriorated；Too little its of molecular weight glues
Degree too little it is impossible to coated die plate agent.
The method of the preparation of the Graphene of three-dimensional N doping is：Prepare the suitable ABPBI of the degree of polymerization first, ABPBI is molten
Solution forms solution in a solvent, adds the nanometer Fe (OH) that appropriate particle diameter is 5 ~ 50nm in solution3Or Fe2O3Powder body does mould
Plate agent, stirring makes it be sufficiently mixed uniformly.Under agitation, heat, steam solvent at leisure to closely dry, proceed in vacuum drying oven
Dry at 60 ~ 120 DEG C.Finely ground in mortar, it is laid in porcelain boat bottom, puts in electric tube furnace, under argon protection, 600
At～1200 DEG C, it is pyrolyzed 2 ~ 3h.Treat that furnace temperature is cooled to room temperature, take out, repeatedly washed to remove templating nanoparticles Fe with dilute hydrochloric acid
(OH)3Or Fe2O3, sucking filtration, deionized water is cleaned, and dries to obtain product.
In the present invention, template is nano level Fe (OH)3Or Fe2O3Granule.Three-dimensional N doping graphite can be prepared
Alkene, the particle diameter of template and addition are crucial：The particle diameter of template determines the aperture of the material with carbon element of preparation；Template plus
Enter the number of plies of Graphene and the performance that amount determines preparation, addition very little, can only obtain porous carbon materials；Add excessive, obtain
The three-dimensional grapheme number of plies arriving very little, after removing template agent removing, is easily subsided, and can only obtain Graphene or graphite after broken superposition
Fragment.The granularity of template has a certain impact to the amount adding template, and granularity is little, and its surface area is big, the mould of needs
The amount of plate agent is just few；Whereas if granularity is big, the amount of the template of needs is just many.The consumption of template is：ABPBI and mould
The mass ratio of plate agent is 3:1～1:3；Ratio change is relevant with the granularity of template.Granularity is from 5 ~ 50nm.Protect in noble gases
Shield is lower to be pyrolyzed, and pyrolysis temperature is：600～1200 DEG C；Washing dilute hydrochloric acid, after repeatedly washing, is washed with deionized to neutrality
?.
The Graphene characterizing method of three-dimensional N doping is：Aperture, porosity, pore volume and specific surface area nitrogen adsorption instrument
（BET）, the Morphology analysis scanning electron microscope of product（SEM）And projection electron microscope（TEM）, the Graphene number of plies
High power projection electron microscope can be passed through（HRTEM）To characterize.The degree of graphitization of product, graphene-structured and the number of plies are permissible
Use X-ray powder diffraction（XRD）, Raman spectrum to be characterizing.Product elementary composition, 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 lie prostrate
Peace（LSV）, Tafel curve and charge-discharge performance to be testing.Product can use CV, LSV as the durability test of catalyst
And chronoa mperometric plot（i-t）.The catalytic performance of product finally needs to assemble metal-air battery, hydrogen-oxygen fuel cell, electrolysis
The electrolyzer of water, ultracapacitor and sensor are testing its performance.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 600～1200 DEG C, preferably 700～1000 DEG C.Temperature is too low
ABPBI can not be pyrolyzed, and the electric conductivity obtaining product is poor；After pyrolysis temperature reaches optimum temperature, then raise its property of pyrolysis temperature
Can be constant, so pyrolysis temperature is unsuitable too high.
Specific embodiment
The preparation of [embodiment 1] ABPBI（Method one, solid phase method）：Take appropriate 3,4- diaminobenzoic acid（DABA）In
In mortar, transfer to equipped with electric stirring, inert gas shielding there-necked flask after being fully ground, logical nitrogen 15min is to arrange
Air to the greatest extent in flask.N2Protection, under stirring, 225 DEG C of heating of oil bath, keep 3h.Take out after cooling, finely ground, N2Under protection, electricity
In stove, heating, is warmed up to 270-275 DEG C, keeps 3h.It is cooled to room temperature, product is taken out, finely ground, that is, obtain ABPBI, use Ubbelohde
Viscometer measures the molecular weight of ABPBI.
The preparation of [embodiment 2] ABPBI（Method two, liquid phase method）：Polyphosphoric acids (PPA) (50g) are added to three mouthfuls
In flask, under nitrogen protection, stirring, 160 DEG C of 1 h are to remove moisture and air.Addition 3,4- diaminobenzoic acid (6 g,
39.5 mmol) and temperature is increased to 190 DEG C, control N2Flow velocity, prevents DABA oxidized, stirring reaction 3h at 200 DEG C,
It is dividedly in some parts about 5g P in course of reaction2O5With the water generating during absorbing reaction.With the increase in response time, polymer
System gradually becomes sticky.Reaction mixture is slowly transferred in deionized water, reels off raw silk from cocoons, and forms fibrous black solid, takes out and dry
Dry, pulverize, washing is to remove the polyphosphoric acids in reactant mixture and unreacted raw material.Obtain ABPBI product.Glued with Ubbelohde
Degree meter measures the molecular weight of ABPBI.
[embodiment 3] uses the nano level Fe (OH) of particle diameter 30nm3Or Fe2O3Granule is mixed with ABPBI for template, with
ABPBI and nano level Fe (OH)3Template mass ratio is 1:As a example 1：In the beaker of 250mL, add the ABPBI of 1g（Viscous
Average molecular weight 2 ~ 30,000）With 20mL DMAc, heat, stirring makes it dissolve, and is slowly added into 1g Fe (OH) under agitation3Particle diameter is
The nano-particle of 30nm makes it be uniformly dispersed.The viscous liquid obtaining heat under agitation be concentrated into closely dry, vacuum drying
It is dried at 60 ~ 120 DEG C in case, solid is finely ground in mortar, transfers in porcelain boat, under argon protection, 900 in high-temperature electric resistance furnace
It is pyrolyzed at DEG C, is incubated 2h, terminate heating, treat that furnace temperature is down to room temperature, take out, finely ground, obtain black powder solid, transfer to
In 250mL conical flask, add the 3mol/L hydrochloric acid of 70mL, heating, stirring 8h, sucking filtration, so wash three times, washing with dilute hydrochloric acid
To neutral, it is dried to obtain black powder solid product 0.67g.BET test shows, its pore-size distribution is 30nm, 982.5 m2
g-1, SEM test show, the product obtaining be porous foam shape material with carbon element, TEM and HRTEM analysis shows, product be three-dimensional graphite
Alkene structure material with carbon element, aperture is 30nm, and Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD and Raman spectrum test show, produce
Product are 2 ~ 4 layers of graphene-structured；XPS analysis show, product nitrogen content is 7.5%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.
Illustrate, product is the material of the three-dimensional grapheme structure of N doping.In its 0.1mol/LKOH solution, catalytic oxidation-reduction performance, rises
Beginning hydrogen reduction current potential is 0.96V vs RHE, and electron transfer number is 3.96, and durability is good；Magnesium air cell performance reaches 96 mW/
cm2.It is 468.7 mW/cm for its peak power of hydrogen-oxygen fuel cell2, in the sulfuric acid solution of 0.5mol/L, oxygen separates out take-off potential
For 1.53 V vs RHE, limiting current density reaches 110 mA/cm2.Ultracapacitor is 351 F g than electric capacity-1, can follow
Ring 10000 times still holding capacitor value 97%.
[embodiment 4] as described in Example 3, other conditions are identical, simply change pyrolysis temperature and are changed to 700 DEG C.Obtain
Product be 0.74g black powder, test result shows, its product remains as 2 ~ 4 layers of porous three-dimensional nitrogen-doped graphene knot
The material of structure, only because its degree of graphitization is relatively low, its electronic conductivity is slightly worse, so its chemical property is slightly worse：Its
In 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.82 V vs RHE, and electron transfer number is
3.53, durability is good；Magnesium air cell performance reaches 68 mW/cm2.It is 228 mW/ for its peak power of hydrogen-oxygen fuel cell
cm2, in the sulfuric acid solution of 0.5mol/L, oxygen separates out take-off potential is 1.59 V vs RHE, and limiting current density reaches 40 mA/
cm2.Ultracapacitor is 171 F g than electric capacity-1, 10000 times capable of circulation still holding capacitor value 91%.
[embodiment 5] as described in Example 3, other conditions are identical, simply change pyrolysis temperature and are changed to 1000 DEG C, its
His condition ibid, simply changes pyrolysis temperature.The product obtaining is 0.66g black powder, and test result shows, its product is still
The material of the porous three-dimensional nitrogen-doped graphene structure for 2 ~ 4 layers, its chemical property is similar with applying example 3.
[embodiment 6] as described in Example 3, other conditions are identical, simply change pyrolysis temperature, and pyrolysis temperature is
1200℃.The product obtaining is 0.61g black powder, and test result shows, the porous three-dimensional nitrogen that its product remains as 2 ~ 4 layers is mixed
The material of miscellaneous graphene-structured, its chemical property is not so good as embodiment 3.
[embodiment 7] as described in Example 3, other conditions are identical, simply ABPBI and nano level Fe (OH)3Matter
Quantitative change is 2：1, it is similarly obtained the pressed powder of black.BET test shows, its pore-size distribution is still 30 nm, but its specific surface
Long-pending then be reduced to 825 m2g-1, itself SEM and TEM test shows, for material with carbon element of loose structure inside it, surface is Multi-layer graphite
Alkene structure, XRD and Raman data show, 7 ~ 8 layers of the number of plies of its Graphene.XPS data is similar with the product of embodiment 3.Its
In 0.1mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.83 V vs RHE, and electron transfer number is
3.52, durability is good；Magnesium air cell performance reaches 61mW/cm2.It is 156 mW/cm for its peak power of hydrogen-oxygen fuel cell2,
In the sulfuric acid solution of 0.5mol/L, oxygen separates out take-off potential is 1.64 V vs RHE, and limiting current density reaches 65 mA/cm2.
Ultracapacitor is 223 F g than electric capacity-1, 10000 times capable of circulation still holding capacitor value 92%.
[embodiment 8] as described in Example 3, other conditions are identical, simply ABPBI and nano level Fe (OH)3Matter
Quantitative change is 1：2, it is similarly obtained the pressed powder of black.BET test shows, its pore size distribution range 30 ~ 60 nm, but its ratio
Surface area is then reduced to 837 m2g-1, itself SEM and TEM test shows, for material with carbon element of loose structure inside it, surface is multilamellar
Graphene-structured, XRD and Raman data show, 6 ~ 7 layers of the number of plies of its Graphene.XPS data is similar with the product of embodiment 3.
In its 0.1mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.85 V vs RHE, electron transfer
Number is 3.66, and durability is good；Magnesium air cell performance reaches 79 mW/cm2.It is 312 for its peak power of hydrogen-oxygen fuel cell
mW/cm2, in the sulfuric acid solution of 0.5 mol/L, oxygen separates out take-off potential is 1.59 V vs RHE, and limiting current density reaches 52
mA/cm2.Ultracapacitor is 365 F g than electric capacity-1, 10000 times capable of circulation still holding capacitor value 94%.
[embodiment 10] as described in Example 3, other conditions are identical, are simply the nano level Fe of 5nm with particle diameter
(OH)3Granule does template, and at this moment because the particle diameter of template diminishes, its surface area increases, and the consumption of ABPBI increases, then
ABPBI is changed to as 3 with the mass ratio of template:1, the product obtaining, with embodiment 3, is its pore-size distribution in 5 ~ 10 nm, than
Surface area is 1432 m2g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material.In its 0.1 mol/ LKOH solution, it is catalyzed oxygen
Reduction take-off potential is 0.92V vs RHE, and electron transfer number is 3.96, and durability is good；Magnesium air cell performance reaches 88 mW/
cm2.It is 358 mW/cm for its peak power of hydrogen-oxygen fuel cell2, in the sulfuric acid solution of 0.5mol/L, oxygen precipitation take-off potential is
1.54 V vs RHE, limiting current density reaches 75 mA/cm2.Ultracapacitor is 412 F g than electric capacity-1, capable of circulation
10000 times still holding capacitor value 94%.
[embodiment 11] as described in Example 3, other conditions are identical, simply use particle diameter to be the nano level Fe of 50 nm
(OH)3Granule does template, and at this moment because the particle diameter of template increases, its surface area reduces, and the consumption of ABPBI reduces, then
ABPBI is changed to as 1 with the mass ratio of template:3, the product obtaining with embodiment 3, be its pore-size distribution in 50 ~ 100 nm,
Specific surface area is 654 m2g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.83V
Vs RHE, electron transfer number is 3.74, and durability is good；Magnesium air cell performance reaches 77 mW/cm2.For hydrogen-oxygen fuel cell
Its peak power is 256 mW/cm2, in the sulfuric acid solution of 0.5 mol/L, oxygen separates out take-off potential is 1.57 V vs RHE, the limit
The inside reach 62mA/cm2.Ultracapacitor is 138 F g than electric capacity-1, capable of circulation 10000 times still holding capacitor values
93%.
[embodiment 12] as described in Example 3, other conditions are identical, simply use 30 nanometer Fe2O3Granule is template.
The product obtaining is 0.76 g black powder, and test result shows, its product remains as 2 ~ 4 layers of porous three-dimensional N doping graphite
The material of alkene structure.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.92 V vs
RHE, electron transfer number is 3.92, and durability is good；Magnesium air cell performance reaches 97 mW/cm2.For hydrogen-oxygen fuel cell its
Peak power is 435 mW/cm2, in the sulfuric acid solution of 0.5 mol/L, oxygen separates out take-off potential is 1.53 V vs RHE, limit electricity
Current density reaches 100 mA/cm2.Ultracapacitor is 351 F g than electric capacity-1, capable of circulation 10000 times still holding capacitor values
95%.
[embodiment 13] as described in Example 3, other conditions are identical, simply use 30 nanometer Fe2O3Granule is template
Consumption is changed to：ABPBI:Template=1:2.The product obtaining is 0.65g black powder, and test result shows, its product remains as
The material of 6 ~ 7 layers of porous three-dimensional nitrogen-doped graphene structure.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen
Gas initial reduction current potential is 0.76 V vs RHE, and electron transfer number is 3.67, and durability is good；Magnesium air cell performance reaches 59
mW/cm2.It is 221 mW/cm for its peak power of hydrogen-oxygen fuel cell2, in the sulfuric acid solution of 0.5 mol/L, oxygen separates out initial electricity
Position is 1.59 V vs RHE, and limiting current density reaches 46 mA/cm2.Ultracapacitor is 185 F g than electric capacity-1, can follow
Ring 10000 times still holding capacitor value 93%.
[embodiment 14] as described in Example 3, other conditions are identical, use 30 nanometer Fe2O3Template consumption is changed to：
ABPBI:Template=1:2.The product obtaining is 0.71g black powder, and test result shows, its product remains as 5 ~ 7 layers many
The material of hole three-dimensional nitrogen-doped graphene structure.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initiates also
Former current potential is 0.85V vs RHE, and electron transfer number is 3.68, and durability is good；Magnesium air cell performance reaches 68 mW/cm2.With
It is 268 mW/cm in its peak power of hydrogen-oxygen fuel cell2, in the sulfuric acid solution of 0.5 mol/L, oxygen separates out take-off potential is 1.59
V vs RHE, limiting current density reaches 64 mA/cm2.Ultracapacitor is 352F g than electric capacity-1, 10000 times capable of circulation
Still the 92% of holding capacitor value.
[embodiment 15] as described in Example 3, other conditions are identical, simply use 5 nanometer Fe2O3Granule is template.
Now ABPBI:Template=3:1.The product obtaining is 0.76g black powder, and test result shows, its product remains as 2 ~ 4 layers
Porous three-dimensional nitrogen-doped graphene structure material.In its 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initiates
Reduction potential is 0.88V vs RHE, and electron transfer number is 3.89, and durability is good；Magnesium air cell performance reaches 86 mW/cm2.
It is 424mW/cm for its peak power of hydrogen-oxygen fuel cell2, in the sulfuric acid solution of 0.5mol/L, oxygen separates out take-off potential is 1.57
V vs RHE, limiting current density reaches 86 mA/cm2.Ultracapacitor is 483F g than electric capacity-1, 10000 times capable of circulation
Still the 93% of holding capacitor value.
[embodiment 16] as described in Example 3, other conditions are identical, use 50 nanometer Fe2O3For template.Now
ABPBI:Template=1:3.The product obtaining is 0.56 g black powder, and test result shows, its product remains as 2 ~ 4 layers
The material of porous three-dimensional nitrogen-doped graphene structure.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initiates
Reduction potential is 0.86V vs RHE, and electron transfer number is 3.85, and durability is good；Magnesium air cell performance reaches 71 mW/cm2.
It is 312 mW/cm for its peak power of hydrogen-oxygen fuel cell2, in the sulfuric acid solution of 0.5mol/L, oxygen separates out take-off potential is 1.59
V vs RHE, limiting current density reaches 52 mA/cm2.Ultracapacitor is 152F g than electric capacity-1, 10000 times capable of circulation
Still the 93% of holding capacitor value.
Claims (6)
1. a kind of three-dimensional nitrogen-doped graphene of high nitrogen-containing preparation method it is characterised in that：It is by virtue from macromolecular chain
The rigid benzimidazole composition of fragrance, and contain in molecule imidazole ring rich in nitrogen and Amino End Group solubility poly-（2,
5- benzimidazole）（ABPBI）For carbon source and nitrogen source, with Fe (OH)3、Fe2O3Nano-particle is template, and ABPBI is filled with template
Divide mixing, and keep the plane of the aromatic rings in its molecule unanimously, under inert gas shielding, be pyrolyzed, washed with dilute acid soln
Remove template, the three-dimensional nitrogen-doped graphene of preparation；ABPBI is solubility, in its molecule be rich in nitrogen imidazole ring and
End ammonia, and its benzimidazole ring is rigid armaticity ring, easily forms nitrogen-doped graphene structure, the carboxylic in molecule in pyrolysis
During base pyrolysis, pore-creating effect is played in deacidification；ABPBI solution and different-grain diameter nanometer Fe (OH)3、Fe2O3Template, according to difference
Pyrolysis 2 ~ 3h in mass ratio mixing, the lower high temperature furnace of argon protection, removes, with dilute hydrochloric acid, the three-dimensional N doping graphite that template can obtain
Alkene.
2. ABPBI according to claim 1 it is characterised in that：Macromolecular chain is by the rigid benzimidazole group of armaticity
Become, and in molecule, contain imidazole ring and the Amino End Group rich in nitrogen；Polymer viscosity-average molecular weight between 1～30,000, Ke Yirong
Solution is in dimethyl acetylamide（DMAc）, dimethylformamide（DMF）, dimethyl sulfoxide（DMSO）Have with N-Methyl pyrrolidone etc.
Machine solvent.
3. template according to claim 1 is nanometer Fe (OH)3Or Fe2O3Powder body it is characterised in that particle diameter 5～
50nm, template, iron oxides（Or hydroxide）The iron ion of nano grain surface can be joined with the nitrogen-atoms in ABPBI molecule
Position generate coordinate bond, such that it is able to prevent the loss of nitrogen in ABPBI pyrolytic process, play fixed nitrogen effect so as to get three-dimensional
The content of the nitrogen of nitrogen-doped graphene material improves.
4. ABPBI according to claim 1 and template Fe (OH)3Or Fe2O3Mass ratio be 3:1～1:3；Hybrid mode
For：ABPBI solution and nanometer Fe (OH)3Or Fe2O3Granule mixes, and after being uniformly mixed, the lower heating of stirring steams solvent near
Dry, vacuum drying, finely ground, it is pyrolyzed, with dilute hydrochloric acid acid elution to remove removing template, you can obtain three under argon protection in high temperature furnace
Dimension nitrogen-doped graphene.
5. pyrolysis temperature according to claim 1 is 600～1200 DEG C, preferably 700 ~ 1000 DEG C.
6. three-dimensional nitrogen-doped graphene according to claim 1, is applied to the catalyst of catalytic oxidation-reduction reaction, used in gold
Belong to air cell, fuel cell；Can also be used for the catalyst of catalytic electrolysis water oxygen evolution reaction；Can be additionally used in ultracapacitor
Electrode material.
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| CN107240509A (en) * | 2017-06-01 | 2017-10-10 | 上海应用技术大学 | A kind of preparation method of N doping capsule structure carbon material |
| CN109516450A (en) * | 2018-10-30 | 2019-03-26 | 江苏大学 | A kind of two dimension nitrogen-doped nanometer grapheme material and its application |
| CN112993283A (en) * | 2019-12-18 | 2021-06-18 | 天津天兆御华科技有限公司 | Transition metal nitrogen-doped carbon-based catalyst and preparation method and application thereof |
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