CN109678146A - A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application - Google Patents

A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application Download PDF

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CN109678146A
CN109678146A CN201910058107.4A CN201910058107A CN109678146A CN 109678146 A CN109678146 A CN 109678146A CN 201910058107 A CN201910058107 A CN 201910058107A CN 109678146 A CN109678146 A CN 109678146A
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preparation
doping
carbon nano
graphitic carbon
acid
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张林杰
鲁康龙
王瑞虎
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application, which has platelet morphology, N doping amount abundant, big pore volume and mesoporous accounting height, whole in high-graphitized.The carbon nanosheet is using the metal oxide nano-sheet of manganese as template, using metal-organic framework material as carbon source, the two forms the sandwich composite precursor material of a type sandwich type, through being pyrolyzed under anhydrous and oxygen-free atmosphere, acid processing removes template, and annealing is made again after mixing with nitrogen source.The advantages that preparation method is easy to get with raw material, and preparation is simple, and production cost is low, is easy to magnanimity preparation, the two-dimentional doped porous carbon material to prepare high graphitization degree by metal-organic framework material provides the synthetic route of a universality.The invention also discloses the porous class graphitic carbon nano pieces of N doping of this high-ratio surface and rich meso-hole structure to be used for efficient electric catalytic oxygen reduction reaction as no metal catalyst simultaneously.

Description

A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application
Technical field
The present invention relates to the preparation fields of carbon nanomaterial.In particular it relates to a kind of porous class graphitic carbon nano of N doping Piece and its preparation and electro-catalysis application.
Background technique
The advantages that fuel cell high and low due to its energy conversion efficiency pollution, has superior answer in terms of energy conversion Use prospect.But its internal redox reactions rate is excessively slow, needs noble metal platinum etc. as catalyst, this allows for these electricity The preparation cost in pond is expensive.Meanwhile noble metal granule in battery methanol fuel and carbon monoxide product etc. it is more sensitive, connect Easy in inactivation after touch, therefore greatly limit the large-scale production and application of fuel cell and metal-air battery.
And carbon material have good physical and chemical stability, electric conductivity and Structural flexibility, be widely used in the energy, The fields such as catalysis and biologic medical.The study found that it has preferable catalytic activity as redox reactions catalyst, in addition They are insensitive to carbon monoxide and methanol.Furthermore they are from a wealth of sources and cheap, this makes them in electro-catalysis oxygen Reduction aspect has biggish application prospect.But for the take-off potential, half wave potential and the limit of redox reaction electricity For current density, these pure carbon nanomaterials still are apparent not enough.
Introducing N doping and pore structure is a kind of effective way for improving its catalytic activity to its modifying and decorating.Wherein nitrogen is mixed Miscellaneous to be used as active site, pore structure is as substance and electron transmission channel.Therefore, it is needed during preparing carbon nanomaterial Introduce nitrogenous precursor.And metal-organic framework material, since its specific composition assigns its carbon content abundant, certain miscellaneous Atom (such as nitrogen-atoms) and metal ion (such as iron, cobalt, nickel, zinc), it is abundant in the conversion process to nano-carbon material Pore structure, nitrogen-atoms and metallic atom can be largely retained in carbon material.Therefore, nano-carbon material as derived from it is often Metallic site with pore structure abundant, biggish specific surface area and exposure assigns its good reactivity and urges Change performance.In addition, metal-organic framework material structure height is orderly, pattern, size are controllable, using it as the presoma heat of carbonization Solution, it is easy to accomplish to the finely regulating of derived carbon material microstructure.Therefore, metal-organic framework material is considered as constructing tool There is the ideal presoma of high-specific surface area, the adjustable nano-carbon material of Heteroatom doping and duct.
Meanwhile inorganic template is introduced during carbon nanomaterial porous as precursor preparation using metal-organic framework material Object can not only carry out pattern and structure regulating to carbon nanomaterial, can also promote to occur in carbon nanomaterial forming process certain The graphite crystallization of degree: the carbon atom of thermodynamic instability is realized under external catalytic condition by unordered using thermal activation Material is changed into ordered structure by disordered state, makes it have good lead by structure to the transform in order of crystal structure of graphite Electrically.To make it play bigger application potential in fields such as the energy, catalysis and biologic medicals.
The conventional method reported at present is only capable of obtaining with the unformed carbon materials of micro-or nano size derived from organic frame material frame Expect particle, but constructs the ultra-thin carbon nanosheet material of two-dimentional scale using metal-organic framework material as presoma, it is especially conductive Property good almost graphited carbon nanosheet material completely, and biggish pore volume and specific surface area are still maintained, with maximum journey Degree promotes it and applies upper performance in electro-catalysis, is still the huge challenge of carbon nano-functional material research field.Therefore, Simple and convenient and efficient method is developed to be of great significance to prepare the carbon nanomaterial elctro-catalyst with high catalytic activity.
Summary of the invention
The first purpose of this invention is to provide a kind of porous class graphitic carbon nano piece of N doping, which has Platelet morphology, N doping amount abundant, big pore volume and mesoporous accounting are high, whole in high-graphitized.Meanwhile the carbon is received The rice thickness of piece, N doping amount and pore structure are controllable.
Second object of the present invention is to provide a kind of preparation method of porous class graphitic carbon nano piece of N doping, the party Method raw material is easy to get, prepares simply and cost is relatively low, it is easy to accomplish the large scale preparation of the porous class graphitic carbon nano piece of N doping.
Third object of the present invention is to provide a kind of porous class graphitic carbon nano piece of N doping and is used as efficient electro-catalysis The catalyst material of redox reactions.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of porous carbon nanosheet of high-graphitized N doping, the carbon nanosheet are using the oxide nano-slice of manganese as mould Plate, using metal-organic framework material as carbon source, the two forms a type sandwich type sandwich composite forerunner to be made.
Preferably, the widthwise size of the porous class graphitic carbon nano piece of the N doping is 0.5~2 μm, with a thickness of 2~ 20nm。
Preferably, the N doping amount of the porous class graphitic carbon nano piece of the N doping is atomic percentage content 5%~10%.
Preferably, the specific surface area of the porous class graphitic carbon nano piece of the N doping is 300-1600m2g-1, total pore volume Size is 1.2-1.8cm3g-1, mesoporous 80% or more accounting.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of the porous class graphitic carbon nano piece of N doping, includes the following steps:
1) the sandwich sandwich forerunner that the oxide nano-slice template Yu metal-organic framework material of manganese are compounded to form The preparation of material；
2) by sandwich sandwich precursor material obtained in step 1) in normal pressure, set temperature and anhydrous and oxygen-free atmosphere Lower pyrolysis, then at room temperature pickling processes 5~12 hours to remove inorganic template, obtain class graphitic carbon nano piece；
3) by class graphitic carbon nano piece obtained in step 2) and nitrogen source after evenly mixing again in set temperature and anhydrous It is annealed under oxygen-free atmosphere to get the porous class graphitic carbon nano piece of N doping is arrived.
In step 1), the preparation refers to the oxide nano-slice template surface that manganese is adsorbed on using electrostatic interactions Metal ion and organic ligand by being stirred at room temperature, mechanical lapping, hydro-thermal, solvent heat, microwave radiation, the reaction of ultrasonic treatment Approach generates metal-organic framework material in the oxide nano-slice template surface primary reconstruction of manganese.Preferably, the reaction Approach is room temperature synthesis and solvent heat.
Preferably, in step 1), the oxide nano-slice template of the manganese is MnO2。
Preferably, step 2) and 3) in, it is described pyrolysis and annealing temperature be 950 DEG C.
In preparation method of the invention, the porous structure of carbon nanosheet is that the pyrolysis and acid described in step 2) process It is generated in journey, and cavernous structure is throughout entire carbon nanosheet.It is controlled by the preparation to precursor material, nanometer sheet is adjusted Pore structure.
In preparation method of the invention, flaky inorganic template is also functioned to simultaneously in the pyrolytic process described in step 2) and is urged Change carbon nanosheet and carry out graphited effect, to obtain porous class graphitic carbon nano piece.
In preparation method of the invention, nitrogen source described in step 3) effectively can not only carry out nitrogen to carbon nanosheet and mix It is miscellaneous, it can also be obviously improved the pore volume and specific surface area of carbon nanosheet.
To reach above-mentioned third purpose, the present invention is adopted the following technical solutions:
A kind of your the non-gold of the porous class graphitic carbon nano piece of N doping as electro-catalysis redox reactions in alkaline medium Genotype catalyst applications.
Excellent place of the invention is as follows:
(1) the preparation side of macropore volume provided by the invention and the N doping class graphitic carbon nano piece rich in meso-hole structure Method, simple and convenient, cost is relatively low, can magnanimity preparation, and its pore structure, N doping amount and piece thickness are controllable.
(2) oxide nano-slice of the manganese used in the present invention acts not only as the mould of synthesis Two-dimensional Carbon material nano piece Plate can also further promote carbon nanosheet to be almost completely graphitized in pyrolytic process, make it have excellent electric conductivity.
(3) prepared by the present invention rich in pore structure and high-graphitized nitrogen-doped carbon nanometer sheet electro-catalysis oxygen also The catalytic activity better than commercialization Pt/C (20wt% containing Pt) is shown in original reaction, and there is more outstanding methanol tolerance In terms of long-time stability, higher application prospect is shown in fuel cell field, is expected to practical application popularization.
Detailed description of the invention
The present invention and its preparation and electro-catalysis application are described in further detail with reference to the accompanying drawing.
Fig. 1 shows embodiment 1 and prepares used MnO2The scanning electron microscope (SEM) photograph of nanometer sheet template.
Fig. 2 shows the scanning electron microscope (SEM) photographs of class sandwich type sandwich composite precursor material prepared by embodiment 1.
Fig. 3 shows the transmission electron microscope picture of the class sandwich type sandwich composite precursor material of the preparation of embodiment 1.
Fig. 4 shows the scanning electron microscope (SEM) photograph of the porous class graphitic carbon nano piece of N doping of the present invention.
Fig. 5 shows the transmission electron microscope picture of the porous class graphitic carbon nano piece of N doping of the present invention.
Fig. 6 shows the XRD spectrum of the porous class graphitic carbon nano piece of N doping of the present invention.
Fig. 7 shows the high-resolution C 1s x-ray photoelectron spectroscopy of the porous class graphitic carbon nano piece of N doping of the present invention.
Fig. 8 shows the high-resolution N 1s x-ray photoelectron spectroscopy of the porous class graphitic carbon nano piece of N doping of the present invention.
Fig. 9 shows the N of the porous class graphitic carbon nano piece of N doping of the present invention2Adsorption curve.
Figure 10 shows the porous class graphitic carbon nano piece of N doping of the present invention and business Pt/C when electrode revolving speed is 1600rpm Linear Circulation volt-ampere curve comparison diagram.
Figure 11 shows the porous class graphitic carbon nano piece of N doping of the present invention and business Pt/C in the case where constant voltage is 0.7V Performance current-time curvel comparison diagram steady in a long-term.
Figure 12 shows the porous class graphitic carbon nano piece of N doping of the present invention and business Pt/C in the case where constant voltage is 0.7V Methanol tolerance energy current-time curvel comparison diagram.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done furtherly below with reference to preferred implementation case and attached drawing It is bright.Similar part is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that lower mask body is retouched The content stated is illustrative rather than restrictive, should not be limited the scope of the invention with this.
Embodiment 1
A kind of porous class graphitic carbon nano piece of N doping, preparation method such as following steps:
1) 0.5g manganese acetate and 1.5g disodium EDTA are miscible in 50mL water at room temperature, then successively past The NaOH aqueous solution that concentration is 0.25M and each 50mL of persulfate aqueous solution that concentration is 0.12M are instilled in above-mentioned solution dropwise, After be warming up to 40 DEG C and stir 12 hours, product through be centrifuged and repeatedly wash, at 80 DEG C dry 12 hours, obtain MnO2It receives Rice piece template.
2) by 50mg MnO2Nanometer sheet is placed in a beaker, and 20mL methanol and ultrasound is added after 2 hours, adds 300mg nitre Sour zinc solid, and continue ultrasound, stirring.
3) mixture obtained in step 2) is poured into the 20mL methanol solution containing 500mg methylimidazole, room The lower stirring of temperature 2 hours is centrifuged after reaction, obtains class sandwich type sandwich composite precursor material washing 3 times.
4) the class sandwich type sandwich composite precursor material solid that step 3) obtains is placed in tube furnace, nitrogen atmosphere Be warming up to 950 DEG C under enclosing with 5 DEG C of heating rates per minute and keep the temperature 2 hours, product with 0.1M hydrochloric acid solution pickling 2 hours simultaneously Repeatedly after washing centrifugation, it is dried in vacuo 12 hours in 60 DEG C.
5) black solid powder obtained in step 4) and dicyandiamide are placed on tubular type with mass ratio 1:10 mixed grinding In furnace, 950 DEG C are warming up to 5 DEG C of heating rates per minute under nitrogen atmosphere and keeps the temperature 2 hours, it is porous that N doping can be obtained Class graphitic carbon nano piece.
Fig. 1 shows the MnO that step 1) is prepared2The scanning electron microscope (SEM) photograph of nanometer sheet template shows in figure it for flake Pattern, surface are smooth.
Fig. 2 shows the scanning electron microscope (SEM) photograph for the class sandwich type sandwich composite precursor material that step 3) is prepared, figures It is the class sandwich sandwich that metal-organic framework material and sheet template are compounded to form for middle display, and metal organic frame is equal It is even to be carried on template surface, and size is more uniform.
Fig. 3 shows the transmission electron microscope picture for the class sandwich type sandwich composite precursor material that step 3) is prepared, figure It is middle to show that it is tightly packed in MnO for metal-organic framework material nano particle2Piece surface, cross section are shown as thin slice, and In sandwich.
Fig. 4 shows the scanning electron microscope (SEM) photograph for the porous class graphitic carbon nano piece of N doping that step 5) is prepared, and shows in figure Obtained material is flake, and thickness is in 20nm or so.
Fig. 5 shows the transmission electron microscope picture for the porous class graphitic carbon nano piece of N doping that step 5) is prepared, and shows in figure Obtained material is flake, and selective electron diffraction is the result shows that be pure carbon material, gained carbon nanosheet is in intimate complete stone Mo Hua.
Fig. 6 shows the XRD spectra for the porous class graphitic carbon nano piece of N doping that step 5) is prepared, can from figure It is located at 26.3 ° and 43 ° to two peaks, (002) and (100)/(101) crystal face of carbon is respectively corresponded, wherein corresponding to (002) The peak of crystal face is more sharp, shows the high-graphitized of obtained carbon nanosheet.And intensity with higher at low angle, show It is with orderly pore structure abundant.
Fig. 7 shows the x-ray photoelectron spectroscopy high score for the porous class graphitic carbon nano piece of N doping that step 5) is prepared Distinguish that C 1s is composed, which can further fit 4 peaks, including corresponding C-N/C-O and C=N/C at 286.5eV and 288.5eV The peak=O further proves that obtained is the carbon nanosheet material of N doping.
Fig. 8 shows the x-ray photoelectron spectroscopy high score for the porous class graphitic carbon nano piece of N doping that step 5) is prepared Distinguish that N 1s is composed, which can further fit 3 peaks, including corresponding pyridine nitrogen at 398.4eV, 401eV and 402.5eV, stone Black nitrogen and oxidation state nitrogen, and graphite nitrogen accounting highest further prove that obtained is high-graphitized nitrogen-doped carbon nanometer sheet Material.
Fig. 9 shows the nitrogen adsorption curve of the porous class graphitic carbon nano piece of N doping that step 5) is prepared at 77K, It may be seen that micro- mesoporous composite adsorpting type is presented in prepared carbon nanosheet, maximal absorptive capacity is more than 1000cm3g-1, and There is a biggish hysteresis loop, shows obtained for high-graphitized N doping porous carbon nanometer sheet material.
Figure 10 shows the porous class graphitic carbon nano piece of N doping that step 5) is prepared and commercialization Pt/C and is situated between in alkalinity Linear volt-ampere curve comparison diagram in matter, it may be seen that no matter prepared carbon nanosheet is in take-off potential, half wave potential and Commercialization Pt/C catalyst is superior on three key indexes of Limited diffusion current density.
Figure 11 shows the porous class graphitic carbon nano piece of N doping that step 5) is prepared and commercialization Pt/C and is situated between in alkalinity Time current curve comparison figure in matter under 0.7V constant potential, it may be seen that prepared carbon nanosheet was in test 24 hours Afterwards, current density still remains with 88.9% initial current value, and Pt/C under equal conditions only remains 76.7%, shows to prepare The long-time stability of the porous class graphitic carbon nano piece of obtained N doping are better than commercialization Pt/C catalyst.
Figure 12 shows the porous class graphitic carbon nano piece of N doping that step 5) is prepared and commercialization Pt/C and is situated between in alkalinity Methanol tolerance time current curve comparison figure in matter under 0.7V constant potential, it may be seen that prepared carbon nanosheet is in first After alcohol injection, current density is kept approximately constant, and Pt/C is under equal conditions inverted in current polarizing direction, also by oxygen Primary current is changed into methanol oxidation current, shows the anti methanol toxication of the porous class graphitic carbon nano piece of the N doping being prepared Commercialization Pt/C catalyst can be significantly better than.
Embodiment 2
The porous class graphitic carbon nano piece of N doping obtained in embodiment 1 is applied in electro-catalysis redox reactions:
Preparation work electrode: it disperses carbon nanosheet 2mg in 1mL ethyl alcohol and (contains the mass fraction of 1/100 (volume ratio) For the naphthol solution of 5wt%), ultrasonic disperse 1 hour, take the 25 above-mentioned dispersant liquid drops of μ L in dried and clean and in the straight of mirror-smooth Diameter is to dry at room temperature on the glass-carbon electrode of 5mm.
The preparation of contrast sample: with the preparation method of above-mentioned working electrode, commercialization Pt/C (20wt%, Johnson is made The production of Matthey company) catalyst sample.
Electro-chemical test mainly includes cyclic voltammetry curve, linear sweep voltammetry curve.Entire test process is in electrochemistry Carry out on work station, test system is three-electrode system: drop has the glass-carbon electrode of product as working electrode, is platinum to electrode Silk, reference electrode are saturation silver-silver chloride electrode；Electrolyte solution is 0.1M KOH aqueous solution.
The resistance to tested person of methanol is the current versus time curve of the redox reactions under 0.7V voltage, at 300 seconds or so to electricity Methanol is added in electrolyte solution, observes electric current situation of change before and after methanol is added.
3~embodiment of embodiment 4
Repeat example 1, difference be only that by step 2) and 3) in methanol usage be changed to 30mL and 50mL respectively, it is acquired Precursor material structure and pattern there is no significant change, it is close with the sandwich structure in embodiment 1.
5~embodiment of embodiment 7
Example 1 is repeated, difference is only that the mixing gold that zinc nitrate in step 2) is changed to zinc nitrate and cobalt nitrate respectively Belong to salt (molar ratio is respectively 5:1,3:1 and 1:1), the structure and pattern of obtained precursor material do not have significant change, with reality The sandwich structure applied in example 1 is close.
8~embodiment of embodiment 9
The step 3) of embodiment 1 is repeated, difference is only that, methylimidazole dosage is changed to 1g and 3g respectively, is obtained Precursor material structure and pattern there is no significant change.
3- embodiment 9 is it is found that during preparing precursor material in conjunction with the embodiments, the concentration and metal salt of reactant Type and dosage and metal salt and organic ligand with the structure and pattern for comparing its precursor material without too big shadow It rings.
10~embodiment of embodiment 11
Embodiment 1 is repeated, difference is only that is changed to argon gas and ammonia for nitrogen in step 4) respectively, and other conditions are not Become, the porous class graphitic carbon nano chip architecture of obtained N doping and pattern do not have significant change.
12~embodiment of embodiment 13
Embodiment 1 is repeated, difference is only that is changed to 900 DEG C and 1000 DEG C for the pyrolysis temperature in step 4) respectively, His condition is constant, and the porous class graphitic carbon nano chip architecture of obtained N doping and pattern do not have significant change.
14~embodiment of embodiment 15
Embodiment 1 is repeated, difference is only that is changed to sulfuric acid and nitric acid for the hydrochloric acid in step 4) respectively, and other conditions are not Become, the porous class graphitic carbon nano chip architecture of obtained N doping and pattern do not have significant change.
16~embodiment of embodiment 17
Embodiment 1 is repeated, difference is only that is changed to urea and thiocarbamide, other conditions for the dicyandiamide in step 5) respectively Constant, the porous class graphitic carbon nano chip architecture of obtained N doping and pattern do not have significant change.
18~embodiment of embodiment 19
Embodiment 1 is repeated, difference, which is only that, distinguishes the mass ratio of black solid powder and dicyandiamide in step 5) It is changed to 1:5 and 1:20, other conditions are constant, and the porous class graphitic carbon nano chip architecture of obtained N doping and pattern obviously do not become Change.
Embodiment 20
Embodiment 1 is repeated, difference, which is only that, is changed to 800 DEG C for the annealing temperature in step 5), and other conditions are constant, obtain To the porous class graphitic carbon nano chip architecture of N doping and pattern there is no significant change.
Obviously, above-mentioned case study on implementation of the invention just for the sake of illustrating examples made by the present invention with clearing, and is not It is the restriction to embodiments of the present invention, for those of ordinary skill in the art, on the basis of the above description Other various forms of variations or variation can also be made, all embodiments can not be exhaustive here, it is all to belong to Technical solution of the present invention changes and variations that derived from are still in the scope of protection of the present invention.

Claims (12)

1. a kind of porous class graphitic carbon nano piece of N doping, which is characterized in that the carbon nanosheet is the oxidate nano with manganese Piece is template, metal-organic framework material is that carbon source is made；The nitrogen-doped carbon nanometer sheet is platelet morphology, pore volume it is big and It is whole in high-graphitized rich in mesoporous.
2. the porous class graphitic carbon nano piece of N doping according to claim 1, which is characterized in that the carbon nanosheet is lateral Size is 0.5~2 μm, with a thickness of 2~20nm.
3. the N doping amount of carbon nanosheet is atomic percentage content 5%~10% according to claim 1；The carbon nanosheet Specific surface area be 300~1600m2g-1, total pore volume size is 1.2~1.8cm3g-1, mesoporous 80% or more accounting.
4. the preparation method of the porous class graphitic carbon nano piece of N doping as claimed in any one of claims 1 to 3, feature exist In including the following steps:
1) the sandwich sandwich precursor material that the oxide nano-slice template Yu metal-organic framework material of manganese are compounded to form Preparation；
2) sandwich sandwich precursor material obtained in step 1) is hot under normal pressure, set temperature and anhydrous and oxygen-free atmosphere Solution, then at room temperature pickling processes 5~12 hours to remove inorganic template, obtain class graphitic carbon nano piece；
3) by class graphitic carbon nano piece obtained in step 2) and nitrogen source after evenly mixing again in set temperature and anhydrous and oxygen-free It is annealed under atmosphere to get the porous class graphitic carbon nano piece of N doping is arrived.
5. the preparation method according to claim 4, which is characterized in that in step 1), the oxide of the manganese includes MnO, MnO2, Mn2O3And Mn3O4；Preferably, the oxide nano-slice template of the manganese is MnO2。
6. the preparation method according to claim 4, which is characterized in that in step 1), the metal-organic framework material Structure type includes ZIF-8, ZIF-9, ZIF-67, ZIF-68, ZIF-69, ZIF-70, MOF-5, MOF-74, HKUST-1, UiO- The hydroxyl of 66, UiO-67, MIL-53, MIL-88, MIL-100, MIL-101, MIL-125 and above structure, amino, aldehyde radical, carboxylic Base, methyl, sulfydryl and sulfonic functional derivative structure.
7. the preparation method according to claim 4, which is characterized in that in step 1), the preparation, which refers to, utilizes electrostatic phase The metal ion and organic ligand that interreaction force is adsorbed on Mn oxide nanometer sheet template surface are by being stirred at room temperature, mechanical grinding The reaction path of mill, hydro-thermal, solvent heat, microwave radiation, ultrasonic treatment is in situ from group in the oxide nano-slice template surface of manganese Dress generates metal-organic framework material, and reaction temperature is 30~200 DEG C, and the reaction time is 0.5~24 hour；Preferably, described Reaction path is room temperature synthesis and solvent heat.
8. preparation method according to claim 7, which is characterized in that the oxide nano-slice template of the manganese and metal from The materials mass ratio of son is 1:1~1:10；The materials mole ratio of the organic ligand and metal ion is 2:1~48:1.
9. the preparation method according to claim 4, which is characterized in that in step 2), the acid includes sulfuric acid, nitric acid, salt Acid, phosphoric acid, boric acid, perchloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid and the above-mentioned two or more of mixed acid of acid.
10. the preparation method according to claim 4, which is characterized in that step 2) and 3) in, it is described pyrolysis and annealing in nothing Carried out in water oxygen-free atmosphere, including nitrogen, argon gas, ammonia, hydrogen, methane, ethylene, two kinds of hydrogen sulfide atmosphere and above-mentioned gas or A variety of mixed atmospheres；The pyrolysis and annealing temperature are 600~1200 DEG C；Preferably, the pyrolysis and annealing temperature are 950 ℃。
11. preparation method according to claim 4, which is characterized in that in step 3), the nitrogen source includes ammonium hydroxide, urine Element, biuret, thiocarbamide, acetonitrile, formamide, ethylenediamine, triethylamine, ethylenediamine tetra-acetic acid, hexa, carbonitride are single Cyanamide, dicyandiamide, melamine, pyridine, pyrimidine, pyrazine, triazine, pyrroles, imidazoles, triazole, aniline, dopamine, amino acid And the derivative and homologue of above-mentioned substance；The materials mass ratio of the nitrogen source and class graphitic carbon nano piece is 5:1~20:1.
12. the porous class graphitic carbon nano piece of N doping according to claims 1 to 3 is as electro-catalysis redox reactions Purposes without metal mold elctro-catalyst.
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CN112201785A (en) * 2019-07-08 2021-01-08 中国科学院上海硅酸盐研究所 Lithium-philic and sulfur-philic co-doped two-dimensional layered graphitized porous carbon material and preparation method and application thereof
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CN113659137A (en) * 2021-08-17 2021-11-16 广东工业大学 Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof
CN113830762A (en) * 2021-09-29 2021-12-24 中钢集团鞍山热能研究院有限公司 Nitrogen-doped porous carbon material with microstructure easy to regulate and control, and preparation method and application thereof
CN115784228A (en) * 2022-12-21 2023-03-14 陕西科技大学 Bimetal modified nitrogen-doped porous carbon nanosheet and preparation method and application thereof
CN116396249A (en) * 2023-04-11 2023-07-07 中国科学院山西煤炭化学研究所 Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran

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CN110124736A (en) * 2019-05-16 2019-08-16 上海应用技术大学 The preparation method of composite visible light catalyst ZIF-8@S-g- carbonitride
CN110026225A (en) * 2019-05-16 2019-07-19 苏州大学 There is one kind visible light to urge active In-NH2/g-C3N4Composite material and its application
CN112201785A (en) * 2019-07-08 2021-01-08 中国科学院上海硅酸盐研究所 Lithium-philic and sulfur-philic co-doped two-dimensional layered graphitized porous carbon material and preparation method and application thereof
CN112201785B (en) * 2019-07-08 2021-12-07 中国科学院上海硅酸盐研究所 Lithium-philic and sulfur-philic co-doped two-dimensional layered graphitized porous carbon material and preparation method and application thereof
CN110550612A (en) * 2019-09-29 2019-12-10 福州大学 Porous graphite phase carbon nitride nanosheet and preparation method and application thereof
CN110661008B (en) * 2019-10-11 2022-08-16 南京航空航天大学 Double-metal-activity monatomic catalyst for metal-air battery, preparation method of monatomic catalyst and metal-air battery
CN110661008A (en) * 2019-10-11 2020-01-07 南京航空航天大学 Double-metal-activity monatomic catalyst for metal-air battery, preparation method of monatomic catalyst and metal-air battery
CN112768712A (en) * 2019-10-21 2021-05-07 中国科学院福建物质结构研究所 Composite, preparation method thereof, catalyst containing composite and electrochemical neutralization energy battery
CN112768712B (en) * 2019-10-21 2022-04-19 中国科学院福建物质结构研究所 Composite, preparation method thereof, catalyst containing composite and electrochemical neutralization energy battery
CN111268668B (en) * 2020-02-17 2021-11-19 西安交通大学 Nitrogen-doped porous nano carbon material, preparation method and application of nitrogen-doped porous nano carbon material as negative electrode material of lithium ion battery
CN111268668A (en) * 2020-02-17 2020-06-12 西安交通大学 Nitrogen-doped porous nano carbon material, preparation method and application of nitrogen-doped porous nano carbon material as negative electrode material of lithium ion battery
CN111204761B (en) * 2020-03-31 2021-06-25 郑州中科新兴产业技术研究院 Method for electrochemically reducing carbon dioxide by combining ionic liquid and nitrogen-doped porous carbon material
CN111204761A (en) * 2020-03-31 2020-05-29 郑州中科新兴产业技术研究院 Method for electrochemically reducing carbon dioxide by combining ionic liquid and nitrogen-doped porous carbon material
CN111495411A (en) * 2020-04-30 2020-08-07 浙江师范大学 Catalyst for decomposing ozone and preparation method thereof
CN111495411B (en) * 2020-04-30 2023-06-16 浙江师范大学 Catalyst for decomposing ozone and preparation method thereof
KR102282388B1 (en) * 2020-05-12 2021-07-26 성균관대학교산학협력단 Hollow type carbon nanostructure and manufacturing method of the same
CN112246266A (en) * 2020-09-30 2021-01-22 宁夏大学 Two-dimensional carbon nanosheet with accurately controllable thickness and preparation method thereof
CN112246266B (en) * 2020-09-30 2022-07-15 宁夏大学 Two-dimensional carbon nanosheet with accurately controllable thickness and preparation method thereof
CN112349915B (en) * 2020-10-28 2021-11-12 贝特瑞新材料集团股份有限公司 Graphite composite material, preparation method and application thereof
CN112349915A (en) * 2020-10-28 2021-02-09 贝特瑞新材料集团股份有限公司 Graphite composite material, preparation method and application thereof
CN112885895A (en) * 2021-01-25 2021-06-01 北海惠科光电技术有限公司 Preparation method of graphene conductive film, thin film transistor and display device
CN112885895B (en) * 2021-01-25 2023-06-27 北海惠科光电技术有限公司 Preparation method of graphene conductive film, thin film transistor and display device
CN113659137A (en) * 2021-08-17 2021-11-16 广东工业大学 Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof
CN113830762A (en) * 2021-09-29 2021-12-24 中钢集团鞍山热能研究院有限公司 Nitrogen-doped porous carbon material with microstructure easy to regulate and control, and preparation method and application thereof
CN113830762B (en) * 2021-09-29 2023-09-12 中钢集团鞍山热能研究院有限公司 Nitrogen-doped porous carbon material with microstructure easy to regulate and control, and preparation method and application thereof
CN115784228A (en) * 2022-12-21 2023-03-14 陕西科技大学 Bimetal modified nitrogen-doped porous carbon nanosheet and preparation method and application thereof
CN116396249A (en) * 2023-04-11 2023-07-07 中国科学院山西煤炭化学研究所 Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran
CN116396249B (en) * 2023-04-11 2023-11-21 中国科学院山西煤炭化学研究所 Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran

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