CN106159287B - A kind of composite type fuel cell cathode catalyst NGPC/NCNTs and preparation method thereof - Google Patents
A kind of composite type fuel cell cathode catalyst NGPC/NCNTs and preparation method thereof Download PDFInfo
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- 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
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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 composite type fuel cell cathode catalyst NGPC/NCNTs and preparation method thereof, belong to the technical field of catalyst preparation, it is therefore intended that develop cheap and efficient non-precious metal catalyst to solve existing use platinum-base material as high cost problem existing for fuel battery cathod catalyst.Its low temperature is carbonized by NGPC/NCNTs in advance first using metal-organic framework material as carbon source, is then introduced by the substep of graphitization catalyst and nitrogen source, and is made through corresponding high-temperature heat treatment twice.Its active component is the graphitization porous carbon of N doping and the carbon nanotube of N doping, pore structure is micro- mesoporous composite, the continuous conduction skeleton on three dimensions is formed by the porous carbon particle of carbon nanotube connection dispersion in structure, thus there is good electric conductivity and faster mass transfer rate, high-efficiency catalytic activity, methanol tolerance and cyclical stability better than commercialization platinum carbon elctro-catalyst can be shown in alkaline medium.
Description
Technical field
The present invention relates to a kind of composite type fuel cell cathode catalyst NGPC/NCNTs and preparation method thereof, belong to catalysis
Technical field prepared by agent.
Background technology
Fuel cell is due to its energy conversion efficiency height, good reliability, small, the fuel range of choice of pollution big many advantages, such as
It receives significant attention, and has been successfully applied to the energy supply of motor vehicles.But since its Cathodic oxygen reduction (ORR) is relatively low
Reactivity caused by compared with large overpotential, therefore it is defeated to reach higher power density to generally require the elctro-catalyst of high carrying capacity
Go out.Currently, the main cathode elctro-catalyst that low-temperature fuel cell uses is pallium-on-carbon (Pt/C), and Pt is valuable and rare so that
Fuel cell technology is difficult to large-scale commercial applications application.Therefore, it develops and partially or completely substitutes the cheap and efficient oxygen of Pt also
Former elctro-catalyst is the emphasis of current fuel cell studies, and have become current most active and most emulative research field it
One.Currently, Pt based alloys, non-Pt alloys, non-noble metallic materials such as Me-Nx/ C and non-metal type doping carbon-based material etc. are
It can be used for the efficient catalytic of oxygen reduction reaction by wide coverage.Wherein, hetero atom (N, S, B, P, F etc.) doping carbon-based material by
In have both high catalytic activity, stability and anti-poisoning capability and as one of the Pt catalyst alternative materials of most foreground.But
Traditional efficient doping type C catalyst material such as carbon nanotube (CNT) and graphene (Graphene) etc. is mostly by chemical vapor deposition
The synthesis of the approach such as product (CVD), corona treatment and arc discharge, condition is harsh and is difficult to effectively control dopant states
System.Therefore, develop simple, efficient and controllable doping carbon-based material synthetic method and strategy and remain vast materialized scholar
The challenge faced.
Metal organic framework (Metal-Organic Frameworks, MOFs), also referred to as Porous coordination polymer
(Porous Coordination Polymers, PCPs), it is made by being coordinated by organic ligand and inorganic metal ion/cluster
With and a kind of novel organic-inorganic hybrid porous material with periodic spatial network structure for being self-assembly of.Compared to
Traditional inorganic porous material, MOFs materials have easily prepared, large specific surface area, porosity height, structure type abundant and height
The features such as adjustable and channel surfaces can be modified provides more possibility for its application in each field.However MOFs there is also
The shortcomings of mechanical strength is low, thermal stability is not high makes its application be subject to certain restrictions.But it is just based on this, in conjunction with its porous character
And the carbon content that organic component is abundant, MOFs are found to be an ideal novel precursor to be easy to be pyrolyzed at high temperature and obtain
Carbon product with porous structure.From 2008, Xu Qiang seminars of Japanese industries technical research institute and state-run material
The Yusuke Yamauchi seminars of research institute have been made that the research of a large amount of initiatives in this respect, and many MOFs materials are such as
MOF-5, ZIF-8, Al-PCP etc. in the form of presoma or template be applied to high-ratio surface porous carbon materials preparation, and
Gas storage and ultracapacitor etc. achieve good application achievements.Until 2011, U.S.'s Argonne National Laboratories
Liu Dijia of room etc. just reports the metal/nitrogen/carbon (Co-N constructed using Co bases MOFs for the first time4/ C) proximate matter material is situated between for acid
The elctro-catalyst that fuel cell oxygen reduction reacts in matter.Then, it is presoma and template, various guest molecules such as Portugal using MOFs
Grape sugar, urea, dicyandiamide, DMSO and triphenylphosphine are unit and multi-element doping type carbon prepared by the pyrolysis of hetero atom component additive
Material has been reported for the electro-catalysis of hydrogen reduction.By using rich nitrogen glyoxaline ligand and Zn2+The class of synthesis is zeolite structured
ZIF-8 is nanocrystalline while as presoma and template, and not additional additional carbon source and nitrogen source, also report has synthesized one for the first time for we
Example has the non-metal type nitrogen-doped carbon nanometer polyhedral oxygen reduction electro-catalyst of graphitization porous structure.Although using MOFs as
Presoma, which prepares doping carbon material, to be had many advantages, such as simple, efficient and controllable, however is existed respectively to MOFs and guest molecule early period
A large amount of different trials are carried out in composition, structure and type, prepared doping carbon material elctro-catalyst is in alkaline medium
Activity especially in half wave potential performance indicator, be difficult to reach the level of Pt base catalyst always.
In general, have the characteristics that the carbon-based material of excellent hydrogen reduction electrocatalysis characteristic should have following three：(1) greatly
Specific surface area；(2) good electric conductivity；(3) evenly dispersed and highdensity active sites.And the carbon materials prepared by MOFs pyrolysis
Material generally has pore property similar with parent and chemical composition, therefore also generally shows larger specific surface area
With higher Heteroatom doping density, answered so most possibly restricting the factor that such carbon-based material catalytic activity is further promoted
It is attributed to its poor electric conductivity namely the lower degree of graphitization of its carbon skeleton.In fact, doped carbon nanometer pipe, graphene
And carbon black etc. often can also show better catalytic activity due to its preferable electric conductivity.Although MOFs passes through high temperature
(≤1200 DEG C) are heat-treated the generation that also can induce carbonization structure in carbon product, but degree is very limited, while excessively high temperature
Degree also be easy to cause pore structure cave in and the loss of hetero atom active component.And Lee of Dalian Chemiclophysics Inst., Chinese Academy of Sciences
Bright, Yang Qihua etc. and the Li Xingguo of Peking University et al. are respectively by with Fe2+、Co2+The MOFs constructed is starting material, utilizes carbon
The catalyzed graphitization effect of generated in-situ respective metal nano particle during change, but can be under lower carburizing temperature effectively
Promote the generation of carbonization structure in product.Although above-mentioned using based on Fe2+、Co2+It is given birth in situ in the MOFs carbonisations constructed
At the catalyzed graphitization of respective metal act on and assist having synthesized the carbon-based elctro-catalyst with high graphitization degree, but also lead
The lower specific surface area of its carbon product (＜ 500m are caused2g-1)；And constructed by metal ion/cluster of Fe, Co MOFs its quantity,
Type occupies the minority after all, therefore this method can not be generally applicable to give full play in the numerous MOFs of huge number, structure
Go out their potentiality.It is therefore desirable to design new synthesis strategy to promote the electric conductivity of carbon product prepared by MOFs pyrolysis, together
When be effectively retained its pore structure and active component to enhance its catalytic activity, and realize from fundamental significance and constructed by MOFs materials
The generalized method of the carbon-based elctro-catalyst of high-performance.
To overcome the shortcomings of above-mentioned background technology, realize by numerous MOFs materials to the simple of the carbon-based elctro-catalyst of high-performance
And generalization is constructed, it is expensive, rare to substitute to develop the novel carbon-based oxygen reduction electro-catalyst material of high efficiency low cost
Platinum based catalyst, the present invention propose it is a kind of it is novel construct strategy, i.e., using general metal-organic framework material as carbon source, first
Its low temperature is carbonized in advance, is then introduced by the substep of graphitization catalyst and nitrogen source, and the corresponding high-temperature heat treatment twice of warp,
Success be made it is a kind of it is novel have it is high-graphitized and with the compound of the porous carbon and carbon nanotube for enriching N doping amount
Electrocatalyst materials.Compared to the carbon-supported catalysts prepared through a step high temperature pyrolytic cracking (HTP) by MOFs in background technology, the present invention urges
The presence of the special composite nanostructure of agent especially carbon nanotube provides not only excellent electronics conduction velocity, while
The higher specific surface area of composite catalyst can be maintained to accelerate mass transfer rate, to realize in alkaline medium to commercialization
Pt/C catalyst surmounting comprehensively in the performance indicators such as take-off potential, half wave potential and Limited diffusion current density.
Invention content
The invention discloses a kind of composite type fuel cell cathode elctro-catalyst NGPC/NCNTs and preparation method thereof, purposes
It is that developing cheap and efficient non-precious metal catalyst urges to solve existing use platinum-base material as fuel battery negative pole
High cost problem existing for agent.
Compound electrocatalyst NGPC/NCNTs, it is characterised in that：Active component is the graphitization porous carbon of N doping
And the carbon nanotube of N doping；Graphitization porous carbon is made of the hollow carbon of onion shape of amorphous porous carbon and spuious distribution, ruler
Very little is 0.05-1 micron；Carbon nanotube is in Bamboo-shaped, and a diameter of 20-100 nanometers, length is 0.1-3 micron；Carbon nanotube
The porous carbon particle of graphitization of connection dispersion forms a continuous conducting matrix grain on three dimensions；With micro- mesoporous composite
Pore structure.
The compound electrocatalyst NGPC/NCNTs, prepare with metal-organic framework material MOF-5, MOF-74,
The amino of ZIF-8, ZIF-9, ZIF-67, HKUST-1, MIL-53, MIL-88, MIL-101, UIO-66 and above-mentioned material, alkyl
Change modified outcome in it is one or more be carbon source, obtained through following three steps high-temperature heat treatment under inert atmosphere argon gas：
(1) be first carbonized metal-organic framework material 1 hour, pickling removing metal component in advance at 500-700 DEG C, acid
To be one or more in hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, and done after being washed to neutrality
It is dry, obtain the porous carbon dust of pre- carbonization；
(2) the porous carbon dust being carbonized in advance is added dissolved in the aqueous solution of graphitization catalyst predecessor, graphitization is urged
Agent predecessor is metallic iron, cobalt, nickel, manganese, vanadium, chromium, molybdenum, tungsten, the formates of titanium, acetate, nitrate, sulfate, phosphoric acid
One or more in salt, perchlorate and chloride, dosage is that every gram of hole carbon dust being carbonized in advance takes 3-10mmol to be graphitized
Catalyst precursors wait for the two after evenly mixing, are evaporated solvent with Rotary Evaporators, by obtained solid sample drying, grinding
It is heat-treated 1-3 hour at 1000 DEG C afterwards, products therefrom hydrochloric acid and hydrogen peroxide solution are at 120-180 DEG C at hydro-thermal
Reason is dried in vacuo after being washed to neutrality after 24 hours, obtains graphited porous carbon；
(3) above-mentioned graphitization porous carbon is placed in 34wt.% sulfuric acid solutions and is impregnated 4-12 hours, be then centrifuged for drying,
And with nitrogen source with mass ratio 1：5―1：30 ratio is uniformly mixed by medium of water, and nitrogen source is selected from urea, thiocarbamide, ammonium hydroxide, double cyanogen
Amine, melamine, polyaniline, formamide, cyanamide, acetonitrile, pyridine, pyrroles, imidazoles, pyrimidine, triazole and the above material
Solvent is evaporated by derivative with Rotary Evaporators, will be heat-treated at 800-1000 DEG C after obtained solid sample drying, grinding
1-5 hour to get to NGPC/NCNTs catalyst.
The composite catalyst NGPC/NCNTs of the present invention is applied to alkaline fuel cell cathode oxygen reduction reaction, with background
Technology is compared, and is had the following advantages：
(1) preparation method of catalyst of the present invention is simply controllable, and synthesis cost is low, while realizing by numerous MOFs materials
Generalization to the carbon-based elctro-catalyst of high-performance is constructed；
(2) there is catalyst unique graphitization porous carbon and slub type composite structure of carbon nano tube, carbon nanotube to pass through
The graphitization porous carbon of dispersion is connected to form a mutual perforative conductive network skeleton in three dimensions, is not only had
Good electric conductivity can also effectively improve specific surface area and accelerate mass transport process；
(3) catalyst is made of in active component the carbon nanotube of the graphitization porous carbon of N doping and N doping, no
Metallic components；
(4) the composite construction catalyst has the oxygen for being better than being commercialized 20wt.%Pt/C catalyst also in alkaline medium
Former electro catalytic activity, methanol tolerance and cyclical stability.
Description of the drawings
Fig. 1 is the SEM figures of the catalyst of the present invention.
Fig. 2 is the TEM figures of the catalyst of the present invention.
Fig. 3 is the TEM figures of the catalyst of the present invention.
Fig. 4 is compared in the rotating disk electrode (r.d.e) under 1600 revs/min of rotating speeds, in 0.1mol/L KOH solutions, this hair
The reduction kinetics of oxygen polarization curve of bright catalyst and commercialization 20wt.%Pt/C catalyst.
Fig. 5 is compared in the rotating disk electrode (r.d.e) under 1600 revs/min of rotating speeds, in 0.1mol/L KOH solutions, this hair
Bright catalyst recycles front and back reduction kinetics of oxygen polarization curve at 1000 times with commercialization 20wt.%Pt/C catalyst.
Fig. 6 is compared in the rotating disk electrode (r.d.e) under 1600 revs/min of rotating speeds, and 3mol/L methanol is added front and back
In 0.1mol/L KOH solutions, catalyst of the present invention and commercialization 20wt.%Pt/C catalyst chrono-amperometric that methanol is responded
Curve.
Specific implementation mode
The present invention is described in detail below by embodiment.
Embodiment 1
(1) first MOF-5 (Zn) is carbonized 1 hour in advance under 550 DEG C of nitrogen atmospheres, metal is removed with 1mol/L salt acid elutions
Ingredient, and the drying at 80 DEG C is washed to after neutrality, obtain the porous carbon dust of pre- carbonization；
(2) the porous carbon dust 0.1g being carbonized in advance is added dissolved in the 10mL aqueous solutions of 0.3mmol nickel formates, at room temperature
Stirring 12 hours after, moisture is evaporated at 50 DEG C with Rotary Evaporators, by after obtained solid sample drying, grinding in nitrogen gas
Lower 1000 DEG C of atmosphere is heat-treated 3 hours, and products therefrom 10mol/L hydrochloric acid and 1.25wt.% hydrogen peroxide solutions are at 160 DEG C
It after hydro-thermal process 24 hours, then is dried in vacuo at 60 DEG C after being washed to neutrality, obtains graphited porous carbon；
(3) above-mentioned graphitization porous carbon 0.1g is placed in 20mL 34wt.% sulfuric acid solutions and is impregnated 4 hours, is then centrifuged for
It is dry and miscible in 15mL water with 1g urea, after being stirred 12 hours at 60 DEG C, with Rotary Evaporators by moisture at 50 DEG C
It is evaporated, by 900 DEG C of heat treatments are urged for 3 hours to get to NGPC/NCNTs in a nitrogen atmosphere after obtained solid sample drying, grinding
Agent.
The method of the half-cell test performance of catalyst is by catalyst pulp with 100 μ g cm-2Load capacity uniformly coat
It is platinum electrode to electrode in the glass carbon disk electrode surface of rotating disk electrode (r.d.e) as working electrode, reference electrode is silver/chlorination
Silver electrode, electrolyte are the KOH solution of 0.1mol/L.Before test, first nitrogen saturation electrolyte in cyclic voltammetry into
Row multi-turn scans activated electrode, and carries out background scans test；The active testing and cyclical stability of catalyst are tested in oxygen
It is carried out in the electrolyte of saturation, using linear voltammetry, under 1600 revs/min of rotating speeds, with 5mV s-1Sweep speed ,-
0.8 records the reduction kinetics of oxygen polarization curve of catalyst between 0.1V；The methanol tolerant performance of catalyst then passes through
Chronoamperometry, under -0.4V constant pressures, the current-responsive curve before and after record methanol addition electrolyte solution on electrode.Fig. 4,
Fig. 5 and Fig. 6 has been respectively compared this catalyst (NGPC/NCNTs) and has been commercialized the catalytic activity of 20wt.%Pt/C catalyst, followed
Ring stability and methanol tolerant performance.Relative to silver/silver chloride reference electrode, in alkaline medium, its electric current under -0.4V potentials
Density is 5.06mA cm-2。
Embodiment 2
(1) first ZIF-8 (Zn) is carbonized 1 hour in advance under 500 DEG C of argon gas atmospheres, metal is removed with 1mol/L salt acid elutions
Ingredient, and the drying at 85 DEG C is washed to after neutrality, obtain the porous carbon dust of pre- carbonization；
(2) the porous carbon dust 0.1g being carbonized in advance is added dissolved in the 10mL aqueous solutions of 0.6mmol ferric trichlorides, room temperature
It is lower stirring 12 hours after, moisture is evaporated at 50 DEG C with Rotary Evaporators, by after obtained solid sample drying, grinding in argon gas
Lower 1000 DEG C of atmosphere is heat-treated 3 hours, and products therefrom 10mol/L hydrochloric acid and 1.25wt.% hydrogen peroxide solutions are at 180 DEG C
Lower hydro-thermal process is dried in vacuo after 24 hours, then after being washed to neutrality at 70 DEG C, obtains graphited porous carbon；
(3) above-mentioned graphitization porous carbon 0.1g is placed in 20mL 34wt.% sulfuric acid solutions and is impregnated 6 hours, is then centrifuged for
It is dry and miscible in 15mL water with 0.5g dicyandiamides, it, will at 50 DEG C with Rotary Evaporators after being stirred 12 hours at 60 DEG C
Moisture is evaporated, by after obtained solid sample drying, grinding under an argon atmosphere 1000 DEG C of heat treatment 3 hours to get to NGPC/
NCNTs catalyst.
The half-cell performance test of catalyst is identical with the method in examples detailed above 1 in the present embodiment, unlike
Used catalyst is the catalyst in the present embodiment.Relative to silver/silver chloride reference electrode, in alkaline medium ,-
Its current density is 4.79mA cm under 0.4V potentials-2。
Embodiment 3
(1) first HKUST-1 (Cu) is carbonized 1 hour in advance under 600 DEG C of argon gas atmospheres, gold is removed with 1mol/L salt acid elutions
Belong to ingredient, and be washed to after neutrality the drying at 65 DEG C, obtains the porous carbon dust of pre- carbonization；
(2) the porous carbon dust 0.1g being carbonized in advance is added dissolved in the 10mL aqueous solutions of 0.9mmol cobalt nitrates, at room temperature
Stirring 12 hours after, moisture is evaporated at 50 DEG C with Rotary Evaporators, by after obtained solid sample drying, grinding in argon gas gas
Lower 1000 DEG C of atmosphere is heat-treated 1 hour, and products therefrom 10mol/L hydrochloric acid and 1.25wt.% hydrogen peroxide solutions are at 120 DEG C
It after hydro-thermal process 24 hours, then is dried in vacuo at 60 DEG C after being washed to neutrality, obtains graphited porous carbon；
(3) above-mentioned graphitization porous carbon 0.1g is placed in 25mL 34wt.% sulfuric acid solutions and is impregnated 8 hours, is then centrifuged for
It is dry and miscible in 15mL water with 3g ammonium hydroxide, after being stirred 12 hours at 60 DEG C, with Rotary Evaporators by moisture at 50 DEG C
It is evaporated, by 800 DEG C of heat treatments are urged for 5 hours to get to NGPC/NCNTs under an argon atmosphere after obtained solid sample drying, grinding
Agent.
The half-cell performance test of catalyst is identical with the method in examples detailed above 1 in the present embodiment, unlike
Used catalyst is the catalyst in the present embodiment.Relative to silver/silver chloride reference electrode, in alkaline medium ,-
Its current density is 4.75mA cm under 0.4V potentials-2。
Embodiment 4
(1) first MOF-74 (Mg) is carbonized 1 hour in advance under 700 DEG C of nitrogen atmospheres, gold is removed with 1mol/L salt acid elutions
Belong to ingredient, and be washed to after neutrality the drying at 60 DEG C, obtains the porous carbon dust of pre- carbonization；
(2) the porous carbon dust 0.1g being carbonized in advance is added dissolved in the 10mL aqueous solutions of 0.5mmol manganese acetates, at room temperature
Stirring 12 hours after, moisture is evaporated at 50 DEG C with Rotary Evaporators, by after obtained solid sample drying, grinding in nitrogen gas
Lower 1000 DEG C of atmosphere is heat-treated 3 hours, and products therefrom 10mol/L hydrochloric acid and 1.25wt.% hydrogen peroxide solutions are at 150 DEG C
It after hydro-thermal process 24 hours, then is dried in vacuo at 60 DEG C after being washed to neutrality, obtains graphited porous carbon；
(3) above-mentioned graphitization porous carbon 0.1g is placed in 25mL 34wt.% sulfuric acid solutions and is impregnated 5 hours, is then centrifuged for
It is dry and miscible in 15mL water with 3g polypyrroles, after being stirred 12 hours at 60 DEG C, with Rotary Evaporators by water at 50 DEG C
Point be evaporated, by after obtained solid sample drying, grinding in a nitrogen atmosphere 900 DEG C of heat treatment 1 hour to get to NGPC/NCNTs
Catalyst.
The half-cell performance test of catalyst is identical with the method in examples detailed above 1 in the present embodiment, unlike
Used catalyst is the catalyst in the present embodiment.Relative to silver/silver chloride reference electrode, in alkaline medium ,-
Its current density is 4.63mA cm under 0.4V potentials-2。
Claims (10)
1. a kind of composite type fuel cell cathode base metal type elctro-catalyst NGPC/NCNTs, it is characterised in that：Active component
For the graphitization porous carbon of N doping and the carbon nanotube of N doping；Porous carbon is graphitized by amorphous porous carbon and spuious distribution
Onion shape hollow carbon composition, size is 0.05-1 micron；Carbon nanotube be in Bamboo-shaped, a diameter of 20-100 nanometers, length
It is 0.1-3 micron；The porous carbon particle of graphitization of carbon nanotube connection dispersion forms a continuous conduction on three dimensions
Skeleton；With micro- mesoporous composite pore structure.
2. the preparation side of composite type fuel cell cathode base metal type elctro-catalyst NGPC/NCNTs described in claim 1
Method, which is characterized in that using metal-organic framework material as carbon source, obtained under an inert atmosphere through following three steps high-temperature heat treatment：
(1) be first carbonized metal-organic framework material 1 hour, pickling removing metal component in advance under carburizing temperature, and is washed to
It is dry after neutrality, obtain the porous carbon dust of pre- carbonization；
(2) the porous carbon dust being carbonized in advance is added dissolved in the aqueous solution of graphitization catalyst predecessor, after evenly mixing, is used
Solvent is evaporated by Rotary Evaporators, will be heat-treated 1-3 hour at 1000 DEG C after obtained solid sample drying, grinding, gained production
Object hydrochloric acid and the hydrogen peroxide solution hydro-thermal process at 120-180 DEG C are dried in vacuo after 24 hours after being washed to neutrality,
Obtain graphited porous carbon；
(3) above-mentioned graphitization porous carbon is placed in 34wt.% sulfuric acid solutions and is impregnated 4-12 hours, be then centrifuged for drying, and with
Nitrogen source with water be uniformly mixed, solvent is evaporated with Rotary Evaporators, by after obtained solid sample drying, grinding 800-1000
1-5 hour is heat-treated at DEG C to get to NGPC/NCNTs catalyst.
3. preparation method according to claim 2, which is characterized in that the metal-organic framework material be selected from MOF-5,
The ammonia of MOF-74, ZIF-8, ZIF-9, ZIF-67, HKUST-1, MIL-53, MIL-88, MIL-101, UIO-66 and the above material
Base, alkylation modified outcome.
4. preparation method according to claim 2, which is characterized in that the inert atmosphere is argon gas.
5. preparation method according to claim 2, which is characterized in that the carburizing temperature described in step (1) is 500-
700℃。
6. preparation method according to claim 2, which is characterized in that acid described in step (1) be selected from hydrochloric acid, sulfuric acid,
Nitric acid, hydrofluoric acid, perchloric acid, phosphoric acid, formic acid, acetic acid.
7. preparation method according to claim 2, which is characterized in that the graphitization catalyst forerunner described in step (2)
The dosage of object is that every gram of porous carbon dust being carbonized in advance takes 3-10mmol graphitization catalyst predecessors.
8. preparation method according to claim 2, which is characterized in that the graphitization catalyst forerunner described in step (2)
Object is selected from metallic iron, cobalt, nickel, manganese, vanadium, chromium, molybdenum, tungsten, the formates of titanium, acetate, nitrate, sulfate, phosphate, high chlorine
Hydrochlorate and chloride.
9. preparation method according to claim 2, which is characterized in that the graphitization porous carbon described in step (3) and nitrogen
The mass ratio in source is 1：5―1：30.
10. preparation method according to claim 2, which is characterized in that nitrogen source described in step (3) be selected from urea, thiocarbamide,
Ammonium hydroxide, dicyandiamide, melamine, polyaniline, formamide, cyanamide, acetonitrile, pyridine, pyrroles, imidazoles, pyrimidine, triazole and with
The derivative of upper material.
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