CN106477566B - 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 carbon source and nitrogen source with the armaticity rigid macromolecule material of high nitrogen-containing poly- (2,5- benzimidazole) (ABPBI), with Fe (OH)3Or Fe2O3) nano particle is template, the rigid benzimidazole of the armaticity in macromolecular chain is regularly arranged to be pyrolyzed under protection of argon gas on template surface, forms three-dimensional nitrogen-doped graphene structure.The iron ion of nitrogen-atoms and ferriferous oxide (or hydroxide) surface in ABPBI molecule generates coordinate bond, plays the role of fixed nitrogen.It is required that: ABPBI viscosity average molecular weigh 1 ~ 30,000；Fe(OH)3Or Fe2O3) partial size be 5 ~ 50nm, ABPBI and Fe (OH)3Or Fe2O3) both mass ratio be 3:1 ~ 1:3；Pyrolysis temperature is 600 ~ 1200 DEG C, is pyrolyzed 2 ~ 3h, is washed 3 times with dilute hydrochloric acid, and deionized water is washed 3 times.Catalyst is precipitated for oxygen reduction catalyst, oxygen in the three-dimensional nitrogen-doped graphene of preparation, for the storage of the electrochemical energies such as fuel cell, metal-air battery and supercapacitor and switching device.
Description
Technical field
Belong to field of nano material preparation, is urged for the fuel cell in clean energy resource field, the cathode of metal-air battery
Agent, electrolysis water catalyst, the fields such as electrode material for super capacitor and electrochemical sensor.
Background technique
Graphene be one kind by carbon atom with sp2The hexangle type of hybridized orbit composition is in two wieners of honeycomb crystal lattice structure
Rice material.Graphene is with the excellent physicals chemistry such as its distinctive property stable, electric conductivity is good, specific strength is big, large specific surface area
Property causes the extensive research interest of people.Two-dimensional graphene is folded since layer-layer heap easily occurs, and obtains graphite-structure, excellent
More property cannot be embodied well.In order to solve this problem, research focus has been transferred on three-dimensional grapheme by people
(Chen L, et al. Small(is small), 2015,11 (12): 1423).Three-dimensional grapheme material is not only solid with graphene
Some physicochemical properties, three-dimensional porous micro nano structure also make it have both large specific surface area, high mechanical strength, electronic conductivity
It can get well and strengthening good characteristics, these unique properties such as mass transfer makes three-dimensional grapheme and its composite material in materials science field
It is concerned.The study found that three-dimensional grapheme is applied to the fields tables such as catalysis reaction, fuel cell, sensor, supercapacitor
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).Studies have shown that after carbon material doping,
All show apparent oxygen reduction catalytic activity.In all kinds of Heteroatom doping graphenes, nitrogen-doped graphene most study.Two dimension
Nitrogen-doped graphene, which is easy stacked in multi-layers, reduces active sites, and makes its reduced performance due to lacking mass transfer channel.And it is three-dimensional
Nitrogen-doped graphene can be such that active sites are exposed on the three phase boundary of reaction, improve reaction efficiency, and reaction can be improved
The mass-transfer efficiency of object and product.The preparation method of three-dimensional nitrogen-doped graphene has very much, such as uses soft template method (Ding W, et
Al. J Am Chem Soc (American Chemical Society), 2015,137 (16): 5414)；Using hard template method (Meng Y,
Et al. J Am Chem Soc (American Chemical Society), 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 often prepare carbon material with pyrolysis such as phenolic resin, pollopas and melamine resins, more in pyrolysis preparation
Hole carbon material or graphite alkenes non-metal catalyst.
Poly- 2,5- benzimidazole (ABPBI) is simplest one kind in PBI family, is using 3,4- diaminobenzoic acid
Raw material, under inert gas argon gas shielded, condensation polymerization is made under the conditions of 200 DEG C in polyphosphoric acids (PPA).It prepares reaction
Equation is as follows:
As nitrogen containing polymer material, polybenzimidazoles (PBI) imidazole ring structure high with nitrogen content.Made using PBI
For a kind of nitrogenous high intermediate, the catalyst electrocatalysis characteristic with higher of preparation.Contain miaow in molecule on imidazole ring
Azoles nitrogen is doped according to metal ion (such as Cu, Mn, Fe, Ru, Ti, Mo and Os), prepares metal nitrogen C catalyst,
It can further improve electro catalytic activity and stability (Cameron C G, et al. J Phys Chem B, ((U.S.) physics
Chemical journal B) 2001,105:8838).The synthetic method of PBI can be divided into 5 kinds: tetramine and dintrile, tetramine and diester, four
Amine and diacid, tetramine and diamides, tetramine and dialdehyde, wherein tetramines aromatic and reacting for aromatic diacid are the most frequently used.D
Archivio is to the preparation method of porous PBI resin material, performance and its prepares catalyst with metallic ion coordination and is ground
Study carefully (Archivio D, et al. Chem-A Eur J, (European The Chemicals) 2000,6 (5): 794).
The invention is using the benzimidazole of armaticity as the raw material of offer carbon and nitrogen, under inert gas argon gas shielded
Pyrolysis prepares nitrogenous carbon material.Synthesis is controlled by the ratio of feed change and hard template, the size of control template particles
The aperture of nitrogenous carbon material, porosity and graphene the parameters such as the number of plies, finally obtain ideal multi-layer three-dimension N doping stone
Black alkene.
Compared with the high molecular materials such as phenolic resin, pollopas, ABPBI is the difference is that it contains armaticity
Stiffening ring benzimidazole ring, and the imidazoles nitrogen on imidazole ring keeps its nitrogen content more abundant.Therefore high temperature pyrolysis ABPBI can be obtained
To the carbon material of N doping, and the orientation of the fragrant plane of a loop by introducing suitable template or control molecule, through heat
The material of the graphene-structured of available multilayer N doping is distinguished after solution.
Compared with the materials such as polyaniline and polypyrrole prepare nitrogen-doped graphene, ABPBI be can dissolve, and be easy to cover with paint, lacquer, colour wash, etc. in template
Agent surface, and polyaniline, polypyrrole etc. are insoluble, can not mix with template.
Summary 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 be nitrogen source and carbon source, ABPBI dissolution after, due to its be rigid molecule, it can it is regularly arranged,
It is coated on template surface, available nitrogen-doped graphene is pyrolyzed to it.Pass through control ABPBI and template (nanometer Fe
(OH)3Or Fe2O3Powder) the methods of mass percent, template partial size, coating method and pyrolytic process regulate and control the 3D of preparation
Aperture, porosity, specific surface area and the number of plies for generating graphene of nitrogen-doped graphene.The material is applied to redox reaction
Catalyst and carrier, supercapacitor, the neck such as electrolysis, sensor material is precipitated in catalyst, oxygen reduction catalyst, electrolysis water oxygen
Domain.Template in the present invention, the iron ion of ferriferous oxide (or hydroxide) nano grain surface can in ABPBI molecule
Nitrogen-atoms coordination generates coordinate bond and plays the role of fixed nitrogen so as to prevent the loss of nitrogen in ABPBI pyrolytic process, so that
The content of the nitrogen of the three-dimensional nitrogen-doped graphene material arrived improves.
The high molecular materials such as ABPBI and the above phenolic resin, pollopas and melamine resin difference is: ABPBI
Benzimidazole ring belongs to the stiffening ring of armaticity in molecule, contains imidazoles nitrogen in molecule on imidazole ring, belongs to the aroma type of rich nitrogen
High molecular polymer.Therefore, it is pyrolyzed the carbon material of available N doping, if can obtain under suitable template action
To the grapheme material of multilayer N doping.If controlling the plane of the aromatic rings of molecule at templating nanoparticles Fe (OH)3Or Fe2O3?
Grain surface is evenly distributed according to a direction, is pyrolyzed the graphene-structured of available three-dimensional N doping.With polyaniline, poly-
Unlike the high molecular materials such as (o-phenylenediamine), polypyrrole: it is organic that ABPBI class macromolecule is soluble in DMAc, DMSO etc.
It in solvent, is easily sufficiently mixed with template, not split-phase, due to its solubility, in preparation 3D nitrogen-doped graphene nano material
When have well operability.However, the high molecular materials such as polyaniline compound, polypyrrole are insoluble, template table can not be covered with paint, lacquer, colour wash, etc.
Face is blended with template.
ABPBI is that viscosity average molecular weigh prepared by solid phase method or liquid phase method is soluble in DMAC between 10,000~30,000,
DMF, DMSO, in N-Methyl pyrrolidone equal solvent.Molecular weight is too big, and the solubility property of ABPBI is deteriorated；Molecular weight too small its glues
Degree is too small, is unable to coated die plate agent.
The method of the preparation of the graphene of three-dimensional N doping are as follows: degree of polymerization ABPBI appropriate is prepared first, ABPBI is molten
Solution forms solution in a solvent, and the nanometer Fe (OH) that suitable partial size is 5 ~ 50nm is added into solution3Or Fe2O3Powder does mould
Plate agent, stirring mix them thoroughly uniformly.Under stiring, it heats, steams solvent at leisure and done to close, is transferred in vacuum oven
It is dried at 60 ~ 120 DEG C.It is finely ground in mortar, it is laid in porcelain boat bottom, is put into electric tube furnace, under protection of argon gas, 600
At~1200 DEG C, it is pyrolyzed 2 ~ 3h.It is cooled to room temperature to furnace temperature, takes out, repeatedly washed with dilute hydrochloric acid to remove templating nanoparticles Fe
(OH)3Or Fe2O3, filter, be washed with deionized water, dry to obtain product.
In the present invention, template is nanoscale Fe (OH)3Or Fe2O3Particle.Three-dimensional N doping graphite can be prepared
Alkene, the partial size and additional amount of template are crucial: the partial size of template determines the aperture of the carbon material of preparation；Template adds
Enter the number of plies and performance that amount determines the graphene of preparation, additional amount is very little, can only obtain porous carbon materials；It is added excessively, obtains
The three-dimensional grapheme number of plies arrived is very little, after removing template agent removing, is easy to collapse, and can only obtain graphene or graphite after broken superposition
Fragment.The granularity of template has a certain impact to the amount that template is added, and granularity is small, and surface area is big, the mould needed
The amount of plate agent is just few；, whereas if granularity is big, the amount of the template needed is just more.The dosage of template are as follows: ABPBI and mould
The mass ratio of plate agent is 3:1~1:3；Ratio variation is related with the granularity of template.Granularity is from 5 ~ 50nm.It is protected in inert gas
The lower pyrolysis of shield, pyrolysis temperature are as follows: 600~1200 DEG C；Washing dilute hydrochloric acid is washed with deionized repeatedly after washing to neutrality
?.
The graphene characterizing method of three-dimensional 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 projection 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.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 600~1200 DEG C, preferably 700~1000 DEG C.Temperature is too low
ABPBI cannot be pyrolyzed, and the electric conductivity for obtaining product is poor；After pyrolysis temperature reaches optimum temperature, then increase its property of pyrolysis temperature
Can be constant, so pyrolysis temperature is unsuitable excessively high.
Specific embodiment
The preparation (method one, solid phase method) of [embodiment 1] ABPBI: take suitable 3,4- diaminobenzoic acid (DABA) in
In mortar, it is transferred to after being fully ground equipped in electric stirring, inert gas shielding three-necked flask, logical nitrogen 15min is to arrange
Air to the greatest extent in flask.N2Protection, under stirring, 225 DEG C of oil bath heating keep 3h.It is taken out after cooling, finely ground, N2Under protection, electricity
Heating in furnace, is warming up to 270-275 DEG C, keeps 3h.It is cooled to room temperature, product is taken out, is finely ground to get ABPBI is arrived, uses Ubbelohde
The molecular weight of viscosimeter measurement ABPBI.
The preparation (method two, liquid phase method) of [embodiment 2] ABPBI: polyphosphoric acids (PPA) (50g) is added to three mouthfuls
In flask, under nitrogen protection, 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 to be oxidized, and is stirred to react 3h at 200 DEG C,
About 5g P is added portionwise in reaction process2O5With the water generated during absorbing reaction.With the increase in reaction time, condensate
System gradually becomes sticky.Reaction mixture is slowly transferred in deionized water, is reeled off raw silk from cocoons, and is formed fibrous black solid, is taken out and dry
It is dry, it crushes, washs to remove the polyphosphoric acids and unreacted raw material in reaction mixture.Obtain ABPBI product.It is viscous with Ubbelohde
The molecular weight of degree meter measurement ABPBI.
[embodiment 3] uses the nanoscale Fe (OH) of partial size 30nm3Or Fe2O3Particle is that template is mixed with ABPBI, with
ABPBI and nanoscale Fe (OH)3For template mass ratio is 1:1: in the beaker of 250mL, the ABPBI(that 1g is added is viscous
Ten thousand) average molecular weight 2 ~ 3 with 20mL DMAc, heats, stirs to dissolve, be slowly added into 1g Fe (OH) under stiring3Partial size is
The nano particle of 30nm makes it be uniformly dispersed.Obtained viscous liquid is heated to be concentrated under stiring and closely be done, and is being dried in vacuo
Dry at 60 ~ 120 DEG C in case, solid is finely ground in mortar, is transferred in porcelain boat, under protection of argon gas, 900 in high-temperature electric resistance furnace
It is pyrolyzed at DEG C, keeps the temperature 2h, terminated heating, be down to room temperature to furnace temperature, taken out, it is finely ground, black powder solid is obtained, is transferred to
In 250mL conical flask, be added the 3mol/L hydrochloric acid of 70mL, heating, stirring 8h filter, in this way with dilute hydrochloric acid wash three times, wash
To neutrality, it is dried to obtain black powder solid product 0.67g.BET test shows that its pore-size distribution is 30nm, 982.5 m2
g-1, the product that shows of SEM test be porous foam shape carbon material, TEM and HRTEM analysis shows, product is three-dimensional graphite
Alkene structure carbon material, aperture 30nm, graphene, which is drawn a bow to the full back, is shown to be 2 ~ 4 layers of graphene.XRD and Raman spectrum test show to produce
The graphene-structured that product are 2 ~ 4 layers；XPS analysis shows that 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 is risen
Beginning hydrogen reduction current potential is 0.96V vs RHE, and electron transfer number 3.96, durability is good；Magnesium air battery performance is up to 96 mW/
cm2.It is 468.7 mW/cm for its peak power of hydrogen-oxygen fuel cell2, take-off potential is precipitated in oxygen in the sulfuric acid solution of 0.5mol/L
For 1.53 V vs RHE, limiting current density reaches 110 mA/cm2.Supercapacitor specific capacitance is 351 F g-1, can follow
The 97% of the still holding capacitor value of ring 10000 times.
[embodiment 4] as described in Example 3, other conditions are identical, only change pyrolysis temperature and are changed to 700 DEG C.It obtains
Product be 0.74g black powder, test result shows that 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 lower, 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 battery performance is up to 68 mW/cm2.It is 228 mW/ for its peak power of hydrogen-oxygen fuel cell
cm2, it is 1.59 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches 40 mA/
cm2.Supercapacitor specific capacitance is 171 F g-1, be recycled 10000 times still holding capacitor value 91%.
[embodiment 5] as described in Example 3, other conditions are identical, only change pyrolysis temperature and are changed to 1000 DEG C,
He is same as above condition, only changes pyrolysis temperature.Obtained product is 0.66g black powder, and test result shows its product still
For the material of 2 ~ 4 layers of porous three-dimensional nitrogen-doped graphene structure, chemical property is similar with example 3 is applied.
[embodiment 6] as described in Example 3, other conditions are identical, only change pyrolysis temperature, pyrolysis temperature is
1200℃.Obtained product is 0.61g black powder, and test result shows that its product remains as 2 ~ 4 layers of porous three-dimensional nitrogen and mixes
The material of miscellaneous graphene-structured, chemical property are not so good as embodiment 3.
[embodiment 7] as described in Example 3, other conditions are identical, only ABPBI and nanoscale Fe (OH)3Matter
Quantitative change is 2:1, is similarly obtained the solid powder of black.It is 30 nm that BET test, which shows its pore-size distribution still, but its specific surface
It is long-pending then be reduced to 825 m2 g-1, SEM and TEM test show its it is internal be porous structure carbon material, 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 are 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 battery performance reaches 61mW/cm2.It is 156 mW/cm for its peak power of hydrogen-oxygen fuel cell2,
It is 1.64 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches 65 mA/cm2
.Supercapacitor specific capacitance is 223 F g-1, be recycled 10000 times still holding capacitor value 92%.
[embodiment 8] as described in Example 3, other conditions are identical, only ABPBI and nanoscale Fe (OH)3Matter
Quantitative change is 1:2, is similarly obtained the solid powder of black.BET test shows 30 ~ 60 nm of its pore size distribution range, but it compares
Surface area is then reduced to 837 m2 g-1, SEM and TEM test show its it is internal be porous structure carbon material, surface is multilayer
Graphene-structured, XRD and Raman data show 6 ~ 7 layers of the number of plies of its graphene.XPS data are 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, electronics transfer
Number is 3.66, and durability is good；Magnesium air battery performance is up to 79 mW/cm2.It is 312 for its peak power of hydrogen-oxygen fuel cell
mW/cm2, it is 1.59 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 52
mA/cm2.Supercapacitor specific capacitance is 365 F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 10] as described in Example 3, other conditions are identical, are only 5nm nanoscale Fe with partial size
(OH)3Particle does template, and at this moment since the partial size of template becomes smaller, surface area increases, and the dosage of ABPBI increases, then
The mass ratio of ABPBI and template is changed to as 3:1, and obtained product is with embodiment 3, and only its pore-size distribution is in 5 ~ 10 nm, than
Surface area is 1432 m2 g-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 3.96, durability is good；Magnesium air battery performance is up to 88 mW/
cm2.It is 358 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 0.5mol/L
1.54 V vs RHE, limiting current density reach 75 mA/cm2.Supercapacitor specific capacitance is 412 F g-1, it is recycled
10000 times still holding capacitor value 94%.
[embodiment 11] as described in Example 3, other conditions are identical, are only 50 nm nanoscale Fe with partial size
(OH)3Particle does template, and at this moment since the partial size of template increases, surface area reduces, and the dosage of ABPBI is reduced, then
The mass ratio of ABPBI and template is changed to as 1:3, and obtained product is with embodiment 3, and only its pore-size distribution is in 50 ~ 100 nm,
Specific surface area is 654 m2 g-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 3.74, durability is good；Magnesium air battery performance is up to 77 mW/cm2.For hydrogen-oxygen fuel cell
Its peak power is 256 mW/cm2, it is 1.57 V vs RHE, the limit that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
The inside reach 62mA/cm2.Supercapacitor specific capacitance is 138 F g-1, it is recycled 10000 still holding capacitor values
93%。
[embodiment 12] as described in Example 3, other conditions are identical, only with 30 nanometer Fes2O3Particle is template.
Obtained product is 0.76 g black powder, and test result shows that 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 3.92, durability is good；Magnesium air battery performance is up to 97 mW/cm2.For hydrogen-oxygen fuel cell its
Peak power is 435 mW/cm2, it is 1.53 V vs RHE, limit electricity that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
Current density reaches 100 mA/cm2.Supercapacitor specific capacitance is 351 F g-1, it is recycled 10000 still holding capacitor values
95%.
[embodiment 13] as described in Example 3, other conditions are identical, only with 30 nanometer Fes2O3Particle is template
Dosage is changed to: ABPBI: template=1:2.Obtained product is 0.65g black powder, and test result shows that 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 3.67, durability is good；Magnesium air battery performance is up to 59
mW/cm2.It is 221 mW/cm for its peak power of hydrogen-oxygen fuel cell2, starting electricity is precipitated in oxygen in the sulfuric acid solution of 0.5 mol/L
Position is 1.59 V vs RHE, and limiting current density reaches 46 mA/cm2.Supercapacitor specific capacitance is 185 F g-1, can
Circulation 10000 times still holding capacitor value 93%.
[embodiment 14] as described in Example 3, other conditions are identical, with 30 nanometer Fes2O3Template dosage is changed to:
ABPBI: template=1:2.Obtained product is 0.71g black powder, and test result shows that its product remains as 5 ~ 7 layers more
The material of hole three-dimensional nitrogen-doped graphene structure.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen starting is also
Former current potential is 0.85V vs RHE, and electron transfer number 3.68, durability is good；Magnesium air battery performance is up to 68 mW/cm2.With
In its peak power of hydrogen-oxygen fuel cell be 268 mW/cm2, it is 1.59 that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
V vs RHE, limiting current density reach 64 mA/cm2.Supercapacitor specific capacitance is 352F g-1, it is recycled 10000
The 92% of secondary still holding capacitor value.
[embodiment 15] as described in Example 3, other conditions are identical, only with 5 nanometer Fes2O3Particle is template.
ABPBI at this time: template=3:1.Obtained product is 0.76g black powder, and test result shows that 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 starting
Reduction potential is 0.88V vs RHE, and electron transfer number 3.89, durability is good；Magnesium air battery performance is up to 86 mW/cm2。
It is 424mW/cm for its peak power of hydrogen-oxygen fuel cell2, it is 1.57 that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L
V vs RHE, limiting current density reach 86 mA/cm2.Supercapacitor specific capacitance is 483F g-1, it is recycled 10000
The 93% of secondary still holding capacitor value.
[embodiment 16] as described in Example 3, other conditions are identical, with 50 nanometer Fes2O3For template.At this time
ABPBI: template=1:3.Obtained product is 0.56 g black powder, and test result shows that 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 starting
Reduction potential is 0.86V vs RHE, and electron transfer number 3.85, durability is good；Magnesium air battery performance is up to 71 mW/cm2。
It is 312 mW/cm for its peak power of hydrogen-oxygen fuel cell2, it is 1.59 that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L
V vs RHE, limiting current density reach 52 mA/cm2.Supercapacitor specific capacitance is 152F g-1, it is recycled 10000
The 93% of secondary still holding capacitor value.
Claims (5)
1. a kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing, it is characterised in that: selecting macromolecular chain is by virtue
The rigid benzimidazole of fragrance forms, and in molecule containing rich in nitrogen imidazole ring and Amino End Group it is soluble it is poly- (2,
5- benzimidazole) (ABPBI) be carbon source and nitrogen source, with Fe (OH)3Or Fe2O3Nano particle is template, ABPBI and template
It is sufficiently mixed, and keeps the plane of aromatic rings in its molecule consistent, under inert gas protection, pyrolysis is washed with dilute acid soln
Template is washed away, three-dimensional nitrogen-doped graphene is prepared；ABPBI be it is soluble, in molecule be rich in nitrogen imidazole ring
With end ammonia, and its benzimidazole ring is rigid armaticity ring, easily forms nitrogen-doped graphene structure in pyrolysis, in molecule
Pore-creating is played the role of in depickling when carboxyl is pyrolyzed；ABPBI solution and different-grain diameter nanometer Fe (OH)3Or Fe2O3Template, according to not
Homogenous quantities are protected in lower high temperature furnace than mixing, argon gas and are pyrolyzed 2 ~ 3h, go template with dilute hydrochloric acid, obtain three-dimensional nitrogen-doped graphene.
2. a kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing according to claim 1, it is characterised in that:
The macromolecular chain of selected ABPBI is made of the rigid benzimidazole of armaticity, and is contained in molecule rich in nitrogen
Imidazole ring and Amino End Group；Polymer viscosity average molecular weigh is dissolved in dimethyl acetamide (DMAC), dimethyl methyl between 1~30,000
In amide (DMF), dimethyl sulfoxide (DMSO) and N-Methyl pyrrolidone organic solvent.
3. a kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing according to claim 1, it is characterised in that:
Template is nanometer Fe (OH)3Or Fe2O3Powder, partial size is in 5~50nm, template, ferriferous oxide or hydroxide nanoparticles table
The iron ion in face can be coordinated with the nitrogen-atoms in ABPBI molecule and generate coordinate bond, to prevent the stream of nitrogen in ABPBI pyrolytic process
It loses, plays the role of fixed nitrogen, the content of the nitrogen of the three-dimensional nitrogen-doped graphene material made improves.
4. a kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing according to claim 1, it is characterised in that:
ABPBI and template Fe (OH)3Or Fe2O3Mass ratio be 3:1~1:3；Hybrid mode are as follows: ABPBI solution and nanometer Fe (OH)3
Or Fe2O3Particle mixes, and after being uniformly mixed, stirs lower heating and steams solvent to closely doing, vacuum drying is finely ground, in high temperature furnace
The interior lower pyrolysis of argon gas protection, with dilute hydrochloric acid acid elution to remove removing template, obtains three-dimensional nitrogen-doped graphene.
5. a kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing according to claim 1, it is characterised in that:
Pyrolysis temperature is 700 ~ 1000 DEG C.
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| CN104108710A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped porous graphene and a preparation method thereof |
| CN104607227A (en) * | 2015-01-23 | 2015-05-13 | 哈尔滨工业大学 | Preparation method for alpha-Fe2O3 mesoporous nanosheet/nitrogen-doped graphene composite material |
| CN105000548A (en) * | 2014-04-22 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of novel three-dimensional nitrogen doped graphene composite material system |
| CN106179446A (en) * | 2016-07-08 | 2016-12-07 | 中国石油大学(北京) | The method of cobalt/nitrating porous carbon composite and preparation method thereof and catalysis silane oxidation |
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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 |
| CN104108710A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped porous graphene and a preparation method thereof |
| CN104607227A (en) * | 2015-01-23 | 2015-05-13 | 哈尔滨工业大学 | Preparation method for alpha-Fe2O3 mesoporous nanosheet/nitrogen-doped graphene composite material |
| CN106179446A (en) * | 2016-07-08 | 2016-12-07 | 中国石油大学(北京) | The method of cobalt/nitrating porous carbon composite and preparation method thereof and catalysis silane oxidation |
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| EP4012809A1 (en) * | 2020-12-09 | 2022-06-15 | Gnanomat SL | Catalyst and metal-air battery |
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