CN106450358A - N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and preparation method thereof - Google Patents
N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and preparation method thereof Download PDFInfo
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- CN106450358A CN106450358A CN201611121230.9A CN201611121230A CN106450358A CN 106450358 A CN106450358 A CN 106450358A CN 201611121230 A CN201611121230 A CN 201611121230A CN 106450358 A CN106450358 A CN 106450358A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- 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 provides an N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and a preparation method thereof. The preparation method comprises the following steps of: adding melamine (MAM) into carbon nano-tubes (CNTs); preparing melamine modified carbon nano-tubes (CNT-MAM) according to a non-covalent bond modifying method; performing in situ polymerization on the melamine modified carbon nano-tubes, melamine and compound containing aldehyde group in dimethyl sulfoxide (DMSO) and compounding into a carbon nano-tube/poly(melamine-aldehyde) compound; and performing high-temperature pyrolysis on the compound, thereby acquiring the N-doped carbon nano-tube/carbon compound catalyst. The N-doped carbon nano-tube/carbon compound oxygen reduction catalyst provided by the invention has higher specific area and nitrogen content, excellent oxygen reduction catalytic activity, excellent methyl alcohol resistance and high stability.
Description
Technical field
The present invention relates to a kind of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst and preparation method thereof, belongs to fuel
Battery science and technology field.
Background technology
Nitrogen-doped carbon nano composite material is because of the cooperative effect between its unique structure and different materials so as to hydrogen reduction
Reaction (ORR) catalysis activity is further enhanced compared to single nitrogen-doped carbon material, is that fuel battery negative pole is preferable
Without metal (metal-free) catalyst.CNTs itself has excellent performance, and which is combined by many researcheres with polymer
To prepare the CNTs/ polymer complex of desired properties.CNTs diameter is little, and surface energy is big, it is easy to attract each other to form size
Larger aggregate, in order that CNTs can be evenly dispersed in composite, needs to modify CNTs before the polymerization.
And non-covalent modification can't be damaged to the structure of CNTs itself, CNTs can be made to keep its original excellent properties.
Although application of the nitrogen-doped carbon nanometer pipe composite in ORR has had some reports, example also compares
Few, ORR activity is strengthened by the method that innovates come synthesizing new nitrogen-doped carbon based composites remain one and lasting choose
War, and in prior art, preparation method underaction, complex operation, there is no controllability for the structure and composition for generating material,
The performance of the material for therefore obtaining is often undesirable.N is mixed CNT and other material with carbon elements (such as Graphene, carbon nano-fiber
Deng) the middle special construction for forming composite, and the cooperative effect between different materials, ORR activity can be improved further.Close
The method of nitrogen-doped carbon nano composite material is become often to have chemical vapour deposition technique (CVD), hydrothermal synthesis method, solution self-assembly method
With the nitrogenous organic precursor method of high-temperature post-treatment, wherein hydrothermal synthesis method experimental facilitiess and condition are required higher, solution from
Construction from part is the method for voluntarily assembling construction structure not against manpower, poor controllability.Although CVD can regulate and control compound well
The form of material, but reaction condition is harsher, complex operation, is unfavorable for that large-scale use the method is produced；Locate after high temperature
Manage that nitrogenous organic precursor method is the simplest, the nitrogen-doped carbon nanometer pipe composite ORR activity for obtaining is also very high, is to prepare height
A kind of good approach of effect ORR elctro-catalyst.
Analyzed based on above, we first pass through the method for non-covalent modification to improve the dispersibility of CNTs, then by itself and list
Body is polymerized to form carbon nanotube polymer composite in DMSO situ, obtains nitrogen-doped carbon nanometer pipe/carbon after pyrolysis multiple
Oxygen reduction catalyst is closed, the catalyst has excellent ORR activity, methanol tolerance and stability.
Content of the invention
In order to solve above-mentioned problems of the prior art, the present invention provides a kind of flexible design, and operating procedure is simple,
Can also control to a certain extent the structure and composition of catalyst nitrogen-doped carbon nanometer pipe/carbon composite catalytic agent preparation method and
The catalyst of its gained.
In this application, aldehyde compound has identical implication with aldehyde compound or the compound containing aldehyde radical.
According to the first embodiment of the present invention, a kind of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst is provided,
The catalyst is obtained by the preparation method for comprising the following steps：
1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：By CNT (CNTs) in organic solvent
Dispersion is mixed in (such as dehydrated alcohol), dispersion is obtained, in dispersions obtained middle interpolation tripolycyanamide (MAM) to obtain mixing
Thing, then in case of heating (in the case of preferably heating at a temperature of between 45 DEG C-organic solvent boiling point, more preferably
In the case of being heated to reflux) stirring mixture makes tripolycyanamide carbon nano-tube modified, isolates (for example by filtering or sucking filtration
Isolate) solidss it is dried, prepare CNT/tripolycyanamide complex (CNT-MAM)；
2) preparation of carbon nano-tube/poly (melamine amine-aldehyde) complex: by step 1) middle CNT/trimerization of preparing Cyanamide compound (CNT-MAM) carries out former with melamine and aldehyde compound in organic solvent (as anhydrous dimethyl sulphoxide) Position polymerization, synthesizing carbon nanotubes/poly-(melamine-aldehyde) compound; With
3) prepare nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst: by high temperature pyrolysis carbon nano-tube/poly (melamine-aldehyde) compound, prepare the agent of nitrogen-doped carbon nanometer pipe/carbon composite catalytic.
Preferably, described step 1) carry out as follows: CNT (CNTs) is placed in to organic solvent (for example absolute ethyl alcohol), utilize ultrasonic wave processing to mix dispersion, obtain dispersion, in dispersions obtained, add melamine (MAM) stirs in the situation that adding hot reflux again, after cooling, separate (for example filtering or suction filtration), washing, dry, obtain CNT/melamine compound (CNT-MAM).
Preferably, described step 2) carry out as follows: CNT/melamine compound (CNT-MAM) prepared by step 1 be dispersed in for example, in organic solvent (anhydrous dimethyl sulphoxide (DMSO) or the DMSO aqueous solution) acquisition dispersion, then dispersion exists in reactor (for example, in the reactor that is polytetrafluoroethylene (PTFE) at liner) be stirred under add successively melamine and aldehyde compound (MAM), heating allows reactant mixture react, then mixture is cooling and obtain solids, to consolidate body thing carries out fragmentation (for example pulverizing), washing (for example, with hot water and ethanol washing), dry, obtain carbon nano-tube/poly (melamine amine-aldehyde) compound.
Preferably, described step 3) carry out as follows: gained carbon nano-tube/poly (melamine-aldehyde) compound carries out thermal cracking in inert atmosphere, obtains nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
Preferably, in step 1) in, CNT (CNTs) is 1:1.2-3 with the ratio of the weight of melamine (MAM), preferably 1:1.4-2.8, is more preferably 1:1.6-2.4.
Preferably, in step 2) in, the ratio of three's weight of CNT/melamine compound (CNT-MAM), melamine and aldehyde compound is 1:1.2-3:1.3-5.5, and preferably 1:1.4-2.8:1.5-5.0, is more preferably 1:1.6-2.4:1.7-4.5.
Preferably, described step 3) carry out as follows: gained carbon nano-tube/poly (melamine-aldehyde) compound 600～1500 DEG C, preferably 650-1200 DEG C, more preferably heat treatment at the temperature of 700-1000 DEG C, obtains nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst in inert atmosphere.
Preferably, described aldehyde compound is one or more in monoaldehyde, dialdehyde or polyaldehyde, is preferably selected from one or more in formaldehyde, benzaldehyde, methacrylaldehyde, glyoxal, citral or isocyclocitral.
In addition, according to the present invention, provide a kind of preparation method of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst, or prepare the method for above-mentioned nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst, the method comprises the following steps:
1) preparation of CNT/melamine compound (CNT-MAM): by CNT (CNTs) at organic solvent For example, in (absolute ethyl alcohol), mix dispersion, obtain dispersion, at dispersions obtained middle interpolation melamine (MAM) to obtain mixing Thing, then in heating in the situation that (preferably heating at the temperature between 45 DEG C-organic solvent boiling point, more preferably In the situation that adding hot reflux) stir the mixture (for example 15-30h, preferably 18-28h, more preferably 20-25h) allow melamine repair Decorations CNT, isolates (for example isolating by filtration or suction filtration) solids and is dried, and prepares CNT/trimerization Cyanamide compound (CNT-MAM);
2) preparation of carbon nano-tube/poly (melamine-aldehyde) compound: by step 1) middle CNT/trimerization of preparing Cyanamide compound (CNT-MAM) carries out former with melamine and aldehyde compound in organic solvent (as anhydrous dimethyl sulphoxide) Position polymerization, synthesizing carbon nanotubes/poly-(melamine-aldehyde) compound; With
3) prepare nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst: by high temperature pyrolysis carbon nano-tube/poly (melamine-aldehyde) compound, prepare the agent of nitrogen-doped carbon nanometer pipe/carbon composite catalytic.
In said method, preferably, described step 1) carry out as follows: CNT (CNTs) is placed in to organic solvent (example as absolute ethyl alcohol) in, utilize ultrasonic wave processing to mix dispersion, obtain dispersion, in dispersions obtained, add again trimerization cyanamide (MAM) stirs in the situation that adding hot reflux, after cooling, separate (for example filtering or suction filtration), washing (for example with 60-100 DEG C, preferably 70-90 DEG C, more preferably the hot water of 75-85 DEG C and ethanol washing), dry (preferably vacuum drying), obtain CNT/melamine compound (CNT-MAM).
Preferably, described step 2) carry out as follows: CNT/melamine compound (CNT-MAM) prepared by step 1 be dispersed in for example, in organic solvent (anhydrous dimethyl sulphoxide (DMSO) or the DMSO aqueous solution) acquisition dispersion, then dispersion exists in reactor (for example, in the reactor that is polytetrafluoroethylene (PTFE) at liner) be stirred under add successively melamine and aldehyde compound (MAM), heating allows reactant mixture (for example react, first at 90-150 DEG C, preferably 100-130 DEG C, more preferably constant temperature 0.5-2h at the temperature of 105-120 DEG C, preferably 0.8-1.5h, more preferably 0.9-1.2h, then, take out and stir all even, at 100-200 DEG C, preferably 120-180 DEG C, more preferably at the temperature of 150-170 DEG C, react, reaction time is 60-80h, preferably 65-75h, more preferably 68-73h), then mixture is cooling and obtain solids, solids is carried out to fragmentation (for example pulverizing), washing (for example, with hot water and ethanol washing), dry, obtain carbon nano-tube/poly (melamine-aldehyde) compound thing.
Preferably, described step 3) carry out as follows: gained carbon nano-tube/poly (melamine-aldehyde) compound carries out thermal cracking in inert atmosphere, obtains nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
Preferably, in step 1) in, CNT (CNTs) is 1:1.2-3 with the ratio of the weight of melamine (MAM), preferably 1:1.4-2.8, is more preferably 1:1.6-2.4.
Preferably, in step 2) in, the ratio of three's weight of CNT/melamine compound (CNT-MAM), melamine and aldehyde compound is 1:1.2-3:1.3-5.5, and preferably 1:1.4-2.8:1.5-5.0, is more preferably 1:1.6-2.4:1.7-4.5.
Preferably, described step 3) carry out as follows: gained carbon nano-tube/poly (melamine-aldehyde) compound 600～1500 DEG C, preferably 650-1200 DEG C, more preferably heat treatment at the temperature of 700-1000 DEG C, obtains nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst in inert atmosphere.
Preferably, described aldehyde compound is one or more in monoaldehyde, dialdehyde or polyaldehyde, is preferably selected from one or more in formaldehyde, benzaldehyde, methacrylaldehyde, glyoxal, isocyclocitral.
In this application, inert atmosphere is: Ar, He, N2In one or more.
For suction filtration, preferably, carry out suction filtration with PTFE film.
A kind of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst, makes by a kind of preparation method who comprises the following steps:
1) preparation of CNT/melamine compound (CNT-MAM): add melamine in CNT (CNTs) (MAM),, by non-covalent bond method of modifying, the CNT that melamine is modified is prepared CNT/melamine compound (CNT-MAM);
2) preparation of carbon nano-tube/poly (melamine-aldehyde) compound: by compound CNT/the melamine of preparation Thing (CNT-MAM) and melamine and aldehyde compound be in the polymerization of dimethyl sulfoxide (DMSO) (DMSO) situ, synthesizing carbon nanotubes/poly-(melamine-aldehyde) compound;
3) prepare nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst: prepare the agent of nitrogen-doped carbon nanometer pipe/carbon composite catalytic by high temperature pyrolysis carbon nano-tube/poly (melamine-aldehyde) compound.
In the present invention, non-covalent bond is modified, mainly to interact by π-π, electrostatic interaction, Van der Waals forces etc. are various noncovalent interaction makes modified additive (dispersant) melamine (MAM) absorption, be wound around, be wrapped in CNT surface or be filled in CNT in pipe, to improving CNT surface physico-chemical property, realize CNT efficiently disperses in substrate medium, and do not relate to any chemistry reaction, can not destroy conjugated system and the electronic structure thereof on CNT surface. modify and can obtain structure and remain intact by non-covalent bond functional CNT, be the CNT (CNT-MAM) that melamine is modified.
In the present invention, described step 1) be: CNT (CNTs) is placed in to absolute ethyl alcohol environment, mixes dispersion, Add again melamine (MAM) to carry out return stirring, carry out suction filtration, washing after cooling, obtain CNT/melamine after dry Amine compound (CNT-MAM);
In the present invention, described step 2) be: CNT/melamine compound (CNT-MAM) of preparation is disperseed In the aqueous solution of anhydrous dimethyl sulphoxide (DMSO) or DMSO, then join in the reactor that liner is polytetrafluoroethylene (PTFE), stir Mix down add successively melamine (MAM), containing the compound of aldehyde radical, after heating, stir, then heat, cooling rear to obtaining Solid obtains carbon nano-tube/poly (melamine-aldehyde) compound after pulverizing, wash, being dried;
In the present invention, described step 3) be: the heat treatment in inert atmosphere of gained carbon nano-tube/poly (melamine-aldehyde) compound, obtains nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
In the present invention, described step 1) be specially: be that 50-200 part (is preferably 70-150 part by weight, more preferably 80-100 part) CNT (CNTs) is placed in absolute ethyl alcohol environment, the ultrasonic CNT (CNTs) that makes mixes dispersion, add again weight portion is that 100-300 part (is preferably 150-250 part, more preferably 160-200 part) melamine (MAM) reflux and stir mix 15-30h and (be preferably 18-28h, more preferably 20-25h), be cooled to after room temperature and carry out suction filtration with PTFE film, use successively 60-100 DEG C (are preferably 70-90 DEG C, more preferably 75-85 DEG C) hot water and ethanol washing, vacuum drying 5-10h (is preferably 6-9h, more preferably 7-8h) after obtain CNT/melamine compound (CNT-MAM).
In the present invention, described step 2) be specially: by the CNT/melamine compound (CNT-preparing MAM) be dispersed in the aqueous solution of anhydrous DMSO or DMSO, join again in the reactor that liner is polytetrafluoroethylene (PTFE), under stirring adding successively weight portion is that 150-1000 part (is preferably 200-800 part, more preferably 300-600 part) melamine (MAM), containing the compound of aldehyde radical, then be placed in 90-150 DEG C and (be preferably 100-130 DEG C, more preferably 105-120 DEG C) constant temperature in environment 0.5-2h (preferably 0.8-1.5h, more preferably 0.9-1.2h), taking-up stirs, put into again 100-200 DEG C and (be preferably 120-180 DEG C, more preferably 150-170 DEG C) react 60-80h (preferably 65-75h in environment, more preferably 68-73h), react cooling to room temperature, the solid obtaining pulverizes with mortar, (preferably use DMSO with organic solvent, acetone, oxolane, in carrene one or more) washing is for several times, black solid carbon nano-tube/poly (melamine-aldehyde) compound obtaining, dry under vacuum 20-30h (is preferably 22-28h, more preferably 24-26h) make and obtain carbon nano-tube/poly (melamine-aldehyde) compound.
In the present invention, described step 3) be specially: gained carbon nano-tube/poly (melamine-aldehyde) compound is in inertia Heat treatment under 600～1500 DEG C of (being preferably 650-1200 DEG C, more preferably 700-1000 DEG C) conditions in atmosphere, obtains nitrogen doping CNT/carbon compound oxygen reduction catalyst; Described inert atmosphere is: Ar, He, N2In one or more.
Preferably, the heat treatment time of described carbon nano-tube/poly (melamine-aldehyde) compound in inert atmosphere is 20-250min, is preferably 25-230min, more preferably 30-180min.
In the present invention, the described compound containing aldehyde radical is one or more in monoaldehyde, dialdehyde or polyaldehyde, as one or more in formaldehyde, benzaldehyde, methacrylaldehyde, glyoxal, isocyclocitral.
In the present invention, step 2) in what add is 1:1～5 containing the compound of aldehyde radical and the proportioning of melamine (MAM) according to containing the aldehyde radical of aldehyde compound and the amino mol ratio of melamine (MAM), be preferably 1:1.5～4, more preferably 1:2-3.
According to second embodiment provided by the invention, provide a kind of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction method for preparing catalyst the method to comprise the following steps:
1) preparation of CNT/melamine compound (CNT-MAM): CNTs is placed in to absolute ethyl alcohol environment, mixed Even dispersion, then the melamine adding (MAM) carries out return stirring, carries out suction filtration, washing after cooling, obtains carbon nanometer after dry Pipe/melamine compound (CNT-MAM);
2) preparation of carbon nano-tube/poly (melamine-aldehyde) compound: by compound CNT/the melamine obtaining Thing (CNT-MAM) is dispersed in the aqueous solution of anhydrous dimethyl sulphoxide (DMSO) or DMSO, then to join liner be polytetrafluoroethyl-ne In the reactor of alkene, under stirring, add successively melamine (MAM), containing the compound of aldehyde radical, stirring reaction after heating, then add Heat, coolingly pulverizes, washs, obtains carbon nano-tube/poly (melamine-aldehyde) compound after dry the solid obtaining afterwards;
3) obtain nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst: the heat treatment in inert atmosphere of gained carbon nano-tube/poly (melamine-aldehyde) compound, obtains nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
In the present invention, described step 1) be specially: be that 50-200 part (is preferably 70-150 part, more preferably by weight 80-100 part) CNT (CNTs) is placed in absolute ethyl alcohol environment, and the ultrasonic CNT (CNTs) that makes mixes dispersion, then adds Weight portion is that the melamine (MAM) of 100-300 part (being preferably 150-250 part, more preferably 160-200 part) refluxes and stirs Mix 15-30h (being preferably 18-28h, more preferably 20-25h), be cooled to after room temperature and carry out suction filtration, to use 60-successively with PTFE film The hot water of 100 DEG C (being preferably 70-90 DEG C, more preferably 75-85 DEG C) and ethanol washing washing for several times, vacuum drying 5-10h is (excellent Elect 6-9h as, more preferably 7-8h) after obtain CNT/melamine compound (CNT-MAM);
In the present invention, described step 2) be specially: by the CNT/melamine compound (CNT-preparing MAM) in being dispersed in the aqueous solution of anhydrous DMSO or DMSO, join again in the reactor that liner is polytetrafluoroethylene (PTFE), stir under to add successively weight portion be that 150-1000 part (is preferably 200-800 part, more preferably 300-600 part) melamine (MAM), containing the compound of aldehyde radical, then be placed in 90-150 DEG C and (be preferably 100-130 DEG C, more preferably 105-120 DEG C) environment middle constant temperature 0.5-2h (preferably 0.8-1.5h, more preferably 0.9-1.2h) take out and stir afterwards, put into again 100-200 DEG C (excellent elect 120-180 DEG C as, more preferably 150-170 DEG C) react 60-80h (preferably 65-75h in environment, more preferably 68-73h), reaction cool to room temperature, the solid obtaining pulverizes with mortar, use successively organic solvent (preferably to use DMSO, acetone, oxolane, one or more in carrene) washing is for several times, black solid carbon nano-tube/poly (melamine-aldehyde) compound obtaining, under vacuum, dry 20-30h (is preferably 22-28h, more preferably 24-26h) make and obtain carbon nano-tube/poly (melamine-aldehyde) compound.
In the present invention, described step 3) be specially: gained carbon nano-tube/poly (melamine-aldehyde) compound is in inertia Heat treatment under 600～1500 DEG C of (being preferably 650-1200 DEG C, more preferably 700-1000 DEG C) conditions in atmosphere, obtains nitrogen doping CNT/carbon compound oxygen reduction catalyst; Described inert atmosphere is: Ar, He, N2In one or more; Preferably, The heat treatment time of described carbon nano-tube/poly (melamine-aldehyde) compound in inert atmosphere is 20-250min, is preferably 25-230min, more preferably 30-180min.
In the present invention, the described compound containing aldehyde radical is one or more in monoaldehyde, dialdehyde and polyaldehyde, as one or more in formaldehyde, benzaldehyde, methacrylaldehyde, glyoxal, isocyclocitral.
In the present invention, step 2) in add containing the compound of aldehyde radical and the proportioning of melamine (MAM) according to the amino mol ratio calculating of the aldehyde radical containing aldehyde compound and melamine (MAM), described in being preferably is 1:1～5 containing the aldehyde radical of aldehyde compound and the amino mol ratio of melamine (MAM), be preferably 1:1.5～4, more preferably 1:2-3.
In the present invention, the aqueous solution of DMSO refers to the mixture of DMSO and water, and in mixture, the concentration of DMSO is not received restriction.
In the present invention, the reagent not being described and device are the conventional reagent in this area and device.
Compared with prior art, the present invention possesses and has following advantage:
1, the nitrogenous organic precursor method of non-covalent modification, in-situ polymerization and high-temperature post-treatment that the present invention combines CNT is prepared the agent of nitrogen-doped carbon nanometer pipe/carbon composite catalytic, flexible design, and operating procedure is simple.
The structure and composition controllability of the catalyst of 2, preparing is strong.
3, gained nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst has larger specific area and excellent ORR catalytic activity, stability and methanol tolerance performance.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of carbon nano-tube/poly (carbamide) compound (MCPMF) prepared of embodiment 1.
Fig. 2 is the LSV curve (while adding methyl alcohol) of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst (NCNT-m-900) of preparing of embodiment 1.
Fig. 3 is the LSV curve (adding after methyl alcohol) of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst (NCNT-m-900) of preparing of embodiment 1.
Fig. 4 is nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst (NCNT-m-900) methanol tolerance test prepared of embodiment 1 and the chronoa mperometric plot of stability test.
Fig. 5 is the infrared spectrogram of carbon nano-tube/poly (melamine-benzaldehyde) compound (MCPMB) prepared of embodiment 2.
Fig. 6 is the LSV curve of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst (NCNT-NC-900) of preparing of embodiment 2.
Detailed description of the invention
According to the first embodiment of the present invention, provide a kind of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst, make by a kind of preparation method who comprises the following steps:
1) preparation of CNT/melamine compound (CNT-MAM): add melamine in CNT (CNTs) (MAM),, by non-covalent bond method of modifying, the CNT that melamine is modified is prepared CNT/melamine compound (CNT-MAM);
2) preparation of carbon nano-tube/poly (melamine-aldehyde) compound: by compound CNT/the melamine of preparation Thing (CNT-MAM) and melamine and aldehyde compound be in the polymerization of dimethyl sulfoxide (DMSO) (DMSO) situ, synthesizing carbon nanotubes/poly-(melamine-aldehyde) compound;
3) prepare nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst: prepare the agent of nitrogen-doped carbon nanometer pipe/carbon composite catalytic by high temperature pyrolysis carbon nano-tube/poly (melamine-aldehyde) compound.
In the present invention, non-covalent bond is modified, mainly to interact by π-π, electrostatic interaction, Van der Waals forces etc. are various noncovalent interaction makes modified additive (dispersant) melamine (MAM) absorption, be wound around, be wrapped in CNT surface or be filled in CNT in pipe, to improving CNT surface physico-chemical property, realize CNT efficiently disperses in substrate medium, and do not relate to any chemistry reaction, can not destroy conjugated system and the electronic structure thereof on CNT surface. modify and can obtain structure and remain intact by non-covalent bond functional CNT, be the CNT (CNT-MAM) that melamine is modified.
In the present invention, described step 1) be: CNT (CNTs) is placed in to absolute ethyl alcohol environment, mixes dispersion, Add again melamine (MAM) to carry out return stirring, carry out suction filtration, washing after cooling, obtain CNT/melamine after dry Amine compound (CNT-MAM);
In the present invention, described step 2) be: CNT/melamine compound (CNT-MAM) of preparation is disperseed In the aqueous solution of anhydrous dimethyl sulphoxide (DMSO) or DMSO, then join in the reactor that liner is polytetrafluoroethylene (PTFE), stir Mix down add successively melamine (MAM), containing the compound of aldehyde radical, after heating, stir, then heat, cooling rear to obtaining Solid obtains carbon nano-tube/poly (melamine-aldehyde) compound after pulverizing, wash, being dried;
In the present invention, described step 3) be: the heat treatment in inert atmosphere of gained carbon nano-tube/poly (melamine-aldehyde) compound, obtains nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
In the present invention, described step 1) be specially: be that 50-200 part (is preferably 70-150 part by weight, more preferably 80-100 part) CNT (CNTs) is placed in absolute ethyl alcohol environment, the ultrasonic CNT (CNTs) that makes mixes dispersion, add again weight portion is that 100-300 part (is preferably 150-250 part, more preferably 160-200 part) melamine (MAM) reflux and stir mix 15-30h and (be preferably 18-28h, more preferably 20-25h), be cooled to after room temperature and carry out suction filtration with PTFE film, use successively 60-100 DEG C (are preferably 70-90 DEG C, more preferably 75-85 DEG C) hot water and ethanol washing, vacuum drying 5-10h (is preferably 6-9h, more preferably 7-8h) after obtain CNT/melamine compound (CNT-MAM).
In the present invention, described step 2) be specially: by the CNT/melamine compound (CNT-preparing MAM) be dispersed in the aqueous solution of anhydrous DMSO or DMSO, join again in the reactor that liner is polytetrafluoroethylene (PTFE), under stirring adding successively weight portion is that 150-1000 part (is preferably 200-800 part, more preferably 300-600 part) melamine (MAM), containing the compound of aldehyde radical, then be placed in 90-150 DEG C and (be preferably 100-130 DEG C, more preferably 105-120 DEG C) constant temperature in environment 0.5-2h (preferably 0.8-1.5h, more preferably 0.9-1.2h), taking-up stirs, put into again 100-200 DEG C and (be preferably 120-180 DEG C, more preferably 150-170 DEG C) react 60-80h (preferably 65-75h in environment, more preferably 68-73h), react cooling to room temperature, the solid obtaining pulverizes with mortar, (preferably use DMSO with organic solvent, acetone, oxolane, in carrene one or more) washing is for several times, black solid carbon nano-tube/poly (melamine-aldehyde) compound obtaining, dry under vacuum 20-30h (is preferably 22-28h, more preferably 24-26h) make and obtain carbon nano-tube/poly (melamine-aldehyde) compound.
In the present invention, described step 3) be specially: gained carbon nano-tube/poly (melamine-aldehyde) compound is in inertia Heat treatment under 600～1500 DEG C of (being preferably 650-1200 DEG C, more preferably 700-1000 DEG C) conditions in atmosphere, obtains nitrogen doping CNT/carbon compound oxygen reduction catalyst; Described inert atmosphere is: Ar, He, N2In one or more.
Preferably, the heat treatment time of described carbon nano-tube/poly (melamine-aldehyde) compound in inert atmosphere is 20-250min, is preferably 25-230min, more preferably 30-180min.
In the present invention, the described compound containing aldehyde radical is one or more in monoaldehyde, dialdehyde or polyaldehyde, as one or more in formaldehyde, benzaldehyde, methacrylaldehyde, glyoxal, isocyclocitral.
In the present invention, step 2) in what add is 1:1～5 containing the compound of aldehyde radical and the proportioning of melamine (MAM) according to containing the aldehyde radical of aldehyde compound and the amino mol ratio of melamine (MAM), be preferably 1:1.5～4, more preferably 1:2-3.
According to second embodiment provided by the invention, provide a kind of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction method for preparing catalyst the method to comprise the following steps:
1) preparation of CNT/melamine compound (CNT-MAM): CNTs is placed in to absolute ethyl alcohol environment, mixed Even dispersion, then the melamine adding (MAM) carries out return stirring, carries out suction filtration, washing after cooling, obtains carbon nanometer after dry Pipe/melamine compound (CNT-MAM);
2) preparation of carbon nano-tube/poly (melamine-aldehyde) compound: by compound CNT/the melamine obtaining Thing (CNT-MAM) is dispersed in the aqueous solution of anhydrous dimethyl sulphoxide (DMSO) or DMSO, then to join liner be polytetrafluoroethyl-ne In the reactor of alkene, under stirring, add successively melamine (MAM), containing the compound of aldehyde radical, stirring reaction after heating, then add Heat, coolingly pulverizes, washs, obtains carbon nano-tube/poly (melamine-aldehyde) compound after dry the solid obtaining afterwards;
3) obtain nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst: the heat treatment in inert atmosphere of gained carbon nano-tube/poly (melamine-aldehyde) compound, obtains nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
In the present invention, described step 1) be specially: be that 50-200 part (is preferably 70-150 part, more preferably by weight 80-100 part) CNT (CNTs) is placed in absolute ethyl alcohol environment, and the ultrasonic CNT (CNTs) that makes mixes dispersion, then adds Weight portion is that the melamine (MAM) of 100-300 part (being preferably 150-250 part, more preferably 160-200 part) refluxes and stirs Mix 15-30h (being preferably 18-28h, more preferably 20-25h), be cooled to after room temperature and carry out suction filtration, to use 60-successively with PTFE film The hot water of 100 DEG C (being preferably 70-90 DEG C, more preferably 75-85 DEG C) and ethanol washing washing for several times, vacuum drying 5-10h is (excellent Elect 6-9h as, more preferably 7-8h) after obtain CNT/melamine compound (CNT-MAM);
In the present invention, described step 2) be specially: by the CNT/melamine compound (CNT-preparing MAM) in being dispersed in the aqueous solution of anhydrous DMSO or DMSO, join again in the reactor that liner is polytetrafluoroethylene (PTFE), stir under to add successively weight portion be that 150-1000 part (is preferably 200-800 part, more preferably 300-600 part) melamine (MAM), containing the compound of aldehyde radical, then be placed in 90-150 DEG C and (be preferably 100-130 DEG C, more preferably 105-120 DEG C) environment middle constant temperature 0.5-2h (preferably 0.8-1.5h, more preferably 0.9-1.2h) take out and stir afterwards, put into again 100-200 DEG C (excellent elect 120-180 DEG C as, more preferably 150-170 DEG C) react 60-80h (preferably 65-75h in environment, more preferably 68-73h), reaction cool to room temperature, the solid obtaining pulverizes with mortar, use successively organic solvent (preferably to use DMSO, acetone, oxolane, one or more in carrene) washing is for several times, black solid carbon nano-tube/poly (melamine-aldehyde) compound obtaining, under vacuum, dry 20-30h (is preferably 22-28h, more preferably 24-26h) make and obtain carbon nano-tube/poly (melamine-aldehyde) compound.
In the present invention, described step 3) be specially: gained carbon nano-tube/poly (melamine-aldehyde) compound is in inertia Heat treatment under 600～1500 DEG C of (being preferably 650-1200 DEG C, more preferably 700-1000 DEG C) conditions in atmosphere, obtains nitrogen doping CNT/carbon compound oxygen reduction catalyst; Described inert atmosphere is: Ar, He, N2In one or more; Preferably, The heat treatment time of described carbon nano-tube/poly (melamine-aldehyde) compound in inert atmosphere is 20-250min, is preferably 25-230min, more preferably 30-180min.
In the present invention, the described compound containing aldehyde radical is one or more in monoaldehyde, dialdehyde and polyaldehyde, as one or more in formaldehyde, benzaldehyde, methacrylaldehyde, glyoxal, isocyclocitral.
In the present invention, step 2) in add containing the compound of aldehyde radical and the proportioning of melamine (MAM) according to the amino mol ratio calculating of the aldehyde radical containing aldehyde compound and melamine (MAM), described in being preferably is 1:1～5 containing the aldehyde radical of aldehyde compound and the amino mol ratio of melamine (MAM), be preferably 1:1.5～4, more preferably 1:2-3.
The present invention taking Ag/AgCl as reference electrode, Pt silk is as electrode, the diameter that is coated with catalyst are formed to three electrode test systems as the glass-carbon electrode of 3mm as working electrode, with O2Saturated 0.1mol/L KOH solution is that electrolyte carries out a series of electro-chemical tests, adopts rotating disk electrode (r.d.e) and linear volt-ampere scanning method, electrochemical AC impedance method, chronoamperometry to investigate this catalyst hydrogen reduction catalytic activity under alkali condition.
Embodiment 1
A preparation for nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst, comprises the steps:
(1) preparation of CNT/melamine compound (CNT-MAM): 1000mg CNTs and 200mL absolute ethyl alcohol are placed in to 500mL round-bottomed flask, then in ultrasonic wave, ultrasonic 30min makes CNTs fully scattered, add again 2000mg tri-Poly cyanamid (MAM), is refluxed 24h. is cooled to room temperature, with PTFE film suction filtration, product washs 3 times with hot water and the ethanol of 80 DEG C successively, finally dry 8h. in vacuum drying chamber
(2) preparation of carbon nano-tube/poly (carbamide) complex:The CNT that step (1) is prepared/ Tripolycyanamide (CNT-MAM) is is dispersed in the anhydrous DMSO of 33.6mL (2.5g), is then added to reaction of the liner for politef in still, under stirring, add successively MAM (3.78g, 30mmol), formaldehyde (1.62g, 54mmol), then be placed in 120 DEG C of baking ovens permanent Warm 1h takes out and stirs into uniform solution, places into reaction 72h in 170 DEG C of baking ovens.Reaction is cooled to room temperature, and the solid for obtaining is with grinding alms bowl pulverizes, use successively DMSO, acetone, oxolane, washed with dichloromethane 3 times, dry 24h under vacuum, obtain carbon nano-tube/poly (carbamide) complex (MCPMF), its infrared spectrum is as shown in Figure 1.
(3) preparation of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst: Weigh 200mg carbon nano-tube/poly (trimerizationCyanogen amine-for-aldehyde) complex is put into porcelain crucible and is placed in tube furnace, under nitrogen atmosphere, from room temperature with 4 DEG C of min-1Intensification speed leads and is raised to 900 DEG C, after constant temperature 1h, then with 4 DEG C of min-1Rate of temperature fall cool to room temperature, gained nitrogen-doped carbon nanometer pipe/carbon is multiple Close oxygen reduction catalyst to be labeled as:NCNT-m-900.Its chemical property is investigated with linear voltammetric scan method, such as Fig. 2, Shown in Fig. 3; Its methanol tolerance and stability are as shown in Figure 4.
Embodiment 2
A kind of preparation of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst, comprises the steps：
(1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：Weigh 1000mg CNTs and 200mL is anhydrous
Ethanol is in 500mL round-bottomed flask, and then in ultrasound wave, ultrasound 30min makes CNTs fully dispersed good, adds 2000mg tri-
Poly cyanamid (MAM), is refluxed 24h.Room temperature is cooled to, PTFE film sucking filtration is used, product is washed with 80 DEG C of hot water and ethanol successively
Wash 3 times, most in vacuum drying oven, dry 8h.
(2) preparation of carbon nano-tube/poly (tripolycyanamide-benzaldehyde) complex：The CNT-MAM that step (1) is prepared
It is placed in 500mL round-bottomed flask with tripolycyanamide (6.3g, 50mmol), benzaldehyde (7.95g, 75mmol), adds 200mL anhydrous
DMSO, in ultrasound wave, ultrasound 10min (40kHz) makes CNT-MAM be well dispersed in reaction dissolvent, drum argon deoxygenation after good seal
30min, moves into the lower reaction 72h of argon protection in 170 DEG C of oil bath pans.Be cooled to room temperature, sucking filtration, product successively with water, acetone, two
Chloromethanes are washed, and dry 24h, obtain final product carbon nano-tube/poly (tripolycyanamide-benzaldehyde) complex (MCPMB) under vacuum, and which is infrared
Spectrum is as shown in Figure 5.
(3) preparation of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst：Weigh 200mg carbon nano-tube/poly (trimerization
Cyanamide-benzaldehyde) complex is put into porcelain crucible and is placed in tube furnace, under nitrogen atmosphere, from room temperature with 4 DEG C of min-1Intensification
Speed is raised to 900 DEG C, after constant temperature 1h, then with 4 DEG C of min-1Rate of temperature fall be cooled to room temperature.Gained nitrogen-doped carbon nanometer pipe/carbon
Compound oxygen reduction catalyst is labeled as：NCNT-NC-900.Its chemical property is investigated with linear voltammetric scan method, such as
Shown in Fig. 6.
Embodiment 3
(1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：Weigh weight to be placed in for 500mgCNTs
In 200mL dehydrated alcohol environment, ultrasonic 20min makes CNTs mix dispersion, adds tripolycyanamide (MAM) of the weight for 1500mg
Carrying out 18h is refluxed, sucking filtration is carried out after being cooled to room temperature with PTFE film, is washed with 60 DEG C of hot water and washing with alcohol for several times successively
Wash, after vacuum drying 5h, obtain CNT/tripolycyanamide complex (CNT-MAM).
(2) preparation of carbon nano-tube/poly (tripolycyanamide-benzaldehyde) complex：The CNT-MAM for preparing is dispersed in no
In water DMSO, be then added to liner for, in the reactor of politef, mol ratio 1 being sequentially added under stirring：The MAM of 3 proportionings
(6.3g, 50mmol), formaldehyde (15.9g, 150mmol), is subsequently placed in take out after constant temperature 0.5h in 90 DEG C of environment and stirs, then
Be put in 100 DEG C of environment reaction 60h, reaction is cooled to room temperature, and the solid for obtaining is pulverized with mortar, successively with DMSO, acetone, four
Hydrogen furan, dichloromethane are washed 5 times, the black solid carbon nano-tube/poly for obtaining (melamine amine-aldehyde) complex, are done under vacuum
Dry 20h obtains carbon nano-tube/poly (melamine amine-aldehyde) complex.
3) nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst is obtained：Gained carbon nano-tube/poly (melamine amine-aldehyde)
Complex 600 DEG C in He atmosphere under the conditions of heat treatment 20min, obtain final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
Embodiment 4
(1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：Weigh weight to be placed in for 700mgCNTs
In 300ml dehydrated alcohol environment, ultrasonic 40min makes CNTs mix dispersion, adds tripolycyanamide (MAM) of the weight for 1600mg
Carrying out 30h is refluxed, sucking filtration is carried out after being cooled to room temperature with PTFE film, successively with 75 DEG C of hot water and washing with alcohol 6 times, very
Sky obtains CNT/tripolycyanamide complex (CNT-MAM) after drying 10h.
(2) preparation of carbon nano-tube/poly (tripolycyanamide-benzaldehyde) complex：The CNT-MAM for preparing is dispersed in
In the anhydrous DMSO of 200ml, be then added to liner for mol ratio in the reactor of politef, being sequentially added under stirring for 1：
2.5 MAM (6.3g, 50mmol), formaldehyde (13.25g, 125mmol), are subsequently placed in constant temperature 02h in 150 DEG C of environment and (take out afterwards
Stir, reaction 80h in 200 DEG C of environment is placed into, reaction is cooled to room temperature, and the solid for obtaining is pulverized with mortar, is used successively
DMSO, acetone, tetrahydrofuran, dichloromethane are washed 4 times, and the black solid carbon nano-tube/poly for obtaining (melamine amine-aldehyde) is combined
Thing, dries 30h and obtains carbon nano-tube/poly (melamine amine-aldehyde) complex under vacuum.
3) nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst is obtained：Gained carbon nano-tube/poly (melamine amine-aldehyde)
Complex 1500 DEG C in Ar inert atmosphere under the conditions of heat treatment 250min, obtain final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction
Catalyst.
Embodiment 5
(1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：Weigh weight be placed in for 800mgCNTs anhydrous
In alcoholic environment, ultrasound makes CNTs mix dispersion, and the tripolycyanamide (MAM) for adding weight portion for 1800mg is refluxed
18h, carries out sucking filtration, successively with 90 DEG C of hot water and washing with alcohol 5 times with PTFE film after being cooled to room temperature, after vacuum drying 6h
To CNT/tripolycyanamide complex (CNT-MAM).
(2) preparation of carbon nano-tube/poly (tripolycyanamide-benzaldehyde) complex：The CNT-MAM for preparing is dispersed in
In the anhydrous DMSO of 300ml, be then added to liner for mol ratio in the reactor of politef, being sequentially added under stirring for 1：2
MAM (6.3g, 50mmol), formaldehyde (10.6g, 100mmol), be subsequently placed in 100 DEG C of environment after constant temperature 1.5h take out stirring
Uniformly, place in 120 DEG C of environment reaction 75h, reaction is cooled to room temperature, and the solid for obtaining is pulverized with mortar, successively with DMSO,
Acetone, tetrahydrofuran, dichloromethane are washed 3 times, the black solid carbon nano-tube/poly for obtaining (melamine amine-aldehyde) complex, very
22h is dry under sky obtains carbon nano-tube/poly (melamine amine-aldehyde) complex.
3) nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst is obtained：Gained carbon nano-tube/poly (melamine amine-aldehyde)
Complex 1200 DEG C in nitrogen inert atmosphere under the conditions of heat treatment 25min, obtain final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction
Catalyst.
Embodiment 6
(1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：Weigh weight to be placed in for 1000mgCNTs
In 200ml dehydrated alcohol environment, ultrasonic 35min makes CNTs mix dispersion, adds tripolycyanamide of the weight portion for 1500mg
(MAM) carrying out 28h is refluxed, sucking filtration is carried out after being cooled to room temperature with PTFE film, successively with 75 DEG C of hot water and washing with alcohol 7
Secondary, CNT/tripolycyanamide complex (CNT-MAM) is obtained after vacuum drying 9h.
(2) preparation of carbon nano-tube/poly (tripolycyanamide-benzaldehyde) complex：The CNT-MAM for preparing is dispersed in no
In water DMSO, be then added to liner for, in the reactor of politef, mol ratio 1 being sequentially added under stirring：1 MAM
(6.3g, 50mmol), formaldehyde (5.3g, 50mmol), is subsequently placed in take out after constant temperature 0.9h in 130 DEG C of environment and stirs, then
Be put in 150 DEG C of environment reaction 68h, reaction is cooled to room temperature, and the solid for obtaining is pulverized with mortar, successively with DMSO, acetone, four
Hydrogen furan, dichloromethane are washed 5 times, the black solid carbon nano-tube/poly for obtaining (melamine amine-aldehyde) complex, are done under vacuum
Dry 24h obtains carbon nano-tube/poly (melamine amine-aldehyde) complex.
3) nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst is obtained：Gained carbon nano-tube/poly (melamine amine-aldehyde)
Complex 700 DEG C in He inert atmosphere under the conditions of heat treatment 230min, obtain final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction and urge
Agent.
Embodiment 7
(1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：Weigh weight to be placed in for 800mg CNTs
In 250ml dehydrated alcohol environment, ultrasonic 25min makes CNTs mix dispersion, and the tripolycyanamide (MAM) for adding weight 1600mg enters
Row is refluxed 20h, carries out sucking filtration with PTFE film, successively with 85 DEG C of hot water and washing with alcohol 8 times, vacuum after being cooled to room temperature
CNT/tripolycyanamide complex (CNT-MAM) is obtained after drying 7h.
(2) preparation of carbon nano-tube/poly (tripolycyanamide-benzaldehyde) complex：The CNT-MAM for preparing is dispersed in
In the anhydrous DMSO of 200ml, be then added to liner for, in the reactor of politef, 1 being sequentially added under stirring：1 MAM
(6.3g, 50mmol), formaldehyde (5.3g, 50mmol), is subsequently placed in take out after constant temperature 1.2h in 105 DEG C of environment and stirs, then
Be put in 170 DEG C of environment reaction 73h, reaction is cooled to room temperature, and the solid for obtaining is pulverized with mortar, successively with DMSO, acetone, four
Hydrogen furan, dichloromethane are washed for several times, black solid carbon nano-tube/poly (melamine amine-aldehyde) complex for obtaining, and are done under vacuum
Dry 26h obtains carbon nano-tube/poly (melamine amine-aldehyde) complex.
3) nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst is obtained：Gained carbon nano-tube/poly (melamine amine-aldehyde)
Complex 1000 DEG C in nitrogen inert atmosphere under the conditions of heat treatment 30min, obtain final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction
Catalyst.
Embodiment 8
Repeat embodiment 1, simply benzaldehyde replaces formaldehyde as aldehyde compound.
Embodiment 9
Repeat embodiment 1, simply acrylic aldehyde replaces formaldehyde as aldehyde compound.
Embodiment 10
Repeat embodiment 1, simply Biformyl replaces formaldehyde as aldehyde compound.
Embodiment 11
Repeat embodiment 3, simply carbon nano-tube/poly (melamine amine-aldehyde) complex heat treatment time in an inert atmosphere
For 180min.
Embodiment 12
Repeat embodiment 3, simply carbon nano-tube/poly (melamine amine-aldehyde) complex heat treatment time in an inert atmosphere
For 150min.
Claims (10)
1. a kind of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst, it is characterised in that：The catalyst is by including following step
Rapid preparation method is obtained：
1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：By CNT (CNTs) in organic solvent (for example
Dehydrated alcohol) middle mixing dispersion, dispersion is obtained, in dispersions obtained middle interpolation tripolycyanamide (MAM) so that mixture is obtained, so
(in the case of preferably heating at a temperature of between 45 DEG C-organic solvent boiling point, more preferably adding afterwards in case of heating
In the case of hot reflux) stirring mixture makes tripolycyanamide carbon nano-tube modified, isolates (for example by filtering or sucking filtration is separated
Go out) solidss it is dried, prepare CNT/tripolycyanamide complex (CNT-MAM)；
2) preparation of carbon nano-tube/poly (melamine amine-aldehyde) complex：By step 1) the middle CNT/tripolycyanamide for preparing
Complex (CNT-MAM) carries out in situ gathering with tripolycyanamide and aldehyde compound in organic solvent (as anhydrous dimethyl sulphoxide)
Close, synthesizing carbon nanotubes/poly- (melamine amine-aldehyde) complex；With
3) nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst is prepared：By high temperature pyrolysis carbon nano-tube/poly (tripolycyanamide-
Aldehyde) complex, prepare nitrogen-doped carbon nanometer pipe/carbon composite catalytic agent.
2. catalyst according to claim 1, it is characterised in that：The step 1) it is carried out as follows：By CNT
(CNTs) being placed in organic solvent (such as dehydrated alcohol), mixing dispersion is carried out using ultrasonic Treatment, obtains dispersion, in institute
Add tripolycyanamide (MAM) in resulting dispersion again to be stirred in the case of being heated to reflux, carry out after cooling separating (such as mistake
Filter or sucking filtration), washing, dry, obtain CNT/tripolycyanamide complex (CNT-MAM)；Or
The step 2) it is carried out as follows：CNT prepared by step 1/tripolycyanamide complex (CNT-MAM) has been dispersed in
Dispersion is obtained in machine solvent (such as anhydrous dimethyl sulphoxide (DMSO) or DMSO aqueous solution), and then dispersion is in the reactor
(for example in reactor of the liner for politef) be stirred in the case of under add tripolycyanamide (MAM) and aldehydes successively
Compound, heating allows reactant mixture to be reacted, and then cools down mixture and obtains solidss, solidss are crushed
(for example pulverizing), wash (for example with hot water and washing with alcohol), dry, obtaining carbon nano-tube/poly (melamine amine-aldehyde) and be combined
Thing；Or
The step 3) it is carried out as follows：Gained carbon nano-tube/poly (melamine amine-aldehyde) complex carries out hot tearing in an inert atmosphere
Solution, obtains final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
3. catalyst according to claim 1 and 2, it is characterised in that：In step 1) in, CNT (CNTs) and trimerization
The weight ratio of cyanamide (MAM) is 1:1.2-3, preferably 1:1.4-2.8, more preferably 1:1.6-2.4；And/or
In step 2) in, three's weight of CNT/tripolycyanamide complex (CNT-MAM), tripolycyanamide and aldehyde compound
The ratio of amount is 1:1.2-3:1.3-5.5, preferably 1:1.4-2.8:1.5-5.0, more preferably 1:1.6-2.4:1.7-4.5.
4. according to arbitrary described catalyst in claim 2-4, it is characterised in that：The step 3) it is carried out as follows：Gained carbon
Nanotube/poly- (melamine amine-aldehyde) complex in an inert atmosphere 600～1500 DEG C, preferred 650-1200 DEG C, more preferably
Heat treatment at a temperature of 700-1000 DEG C, obtains final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
5. according to arbitrary described catalyst in claim 1-4, it is characterised in that：Described aldehyde compound be monoaldehyde,
One or more in dialdehyde or polyaldehyde, is preferably selected from formaldehyde, benzaldehyde, acrylic aldehyde, Biformyl, citral or different
One or more in cyclocitral.
6. a kind of preparation method of nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst or prepare claim 1-5 in any
The method of the nitrogen-doped carbon nanometer pipe described in/carbon compound oxygen reduction catalyst, the method is comprised the following steps：
1) preparation of CNT/tripolycyanamide complex (CNT-MAM)：By CNT (CNTs) in organic solvent (for example
Dehydrated alcohol) middle mixing dispersion, dispersion is obtained, in dispersions obtained middle interpolation tripolycyanamide (MAM) so that mixture is obtained, so
(in the case of preferably heating at a temperature of between 45 DEG C-organic solvent boiling point, more preferably adding afterwards in case of heating
In the case of hot reflux) stirring mixture makes tripolycyanamide carbon nano-tube modified, isolates (for example by filtering or sucking filtration is separated
Go out) solidss it is dried, prepare CNT/tripolycyanamide complex (CNT-MAM)；
2) preparation of carbon nano-tube/poly (melamine amine-aldehyde) complex：By step 1) the middle CNT/tripolycyanamide for preparing
Complex (CNT-MAM) carries out in situ gathering with tripolycyanamide and aldehyde compound in organic solvent (as anhydrous dimethyl sulphoxide)
Close, synthesizing carbon nanotubes/poly- (melamine amine-aldehyde) complex；With
3) nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst is prepared：By high temperature pyrolysis carbon nano-tube/poly (tripolycyanamide-
Aldehyde) complex, prepare nitrogen-doped carbon nanometer pipe/carbon composite catalytic agent.
7. method according to claim 6, it is characterised in that：The step 1) it is carried out as follows：By CNT (CNTs)
Being placed in organic solvent (such as dehydrated alcohol), mixing dispersion is carried out using ultrasonic Treatment, obtain dispersion, disperses in gained
Adding tripolycyanamide (MAM) in body again to be stirred in the case of being heated to reflux, separation is carried out after cooling and (is for example filtered or take out
Filter), washing, dry, obtain CNT/tripolycyanamide complex (CNT-MAM)；Or
The step 2) it is carried out as follows：CNT prepared by step 1/tripolycyanamide complex (CNT-MAM) has been dispersed in
Dispersion is obtained in machine solvent (such as anhydrous dimethyl sulphoxide (DMSO) or DMSO aqueous solution), and then dispersion is in the reactor
(for example in reactor of the liner for politef) be stirred in the case of under add tripolycyanamide (MAM) and aldehydes successively
Compound, heating allows reactant mixture to be reacted, and then cools down mixture and obtains solidss, solidss are crushed
(for example pulverizing), wash (for example with hot water and washing with alcohol), dry, obtaining carbon nano-tube/poly (melamine amine-aldehyde) and be combined
Thing；Or
The step 3) it is carried out as follows：Gained carbon nano-tube/poly (melamine amine-aldehyde) complex carries out hot tearing in an inert atmosphere
Solution, obtains final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
8. the method according to claim 6 or 7, it is characterised in that：In step 1) in, CNT (CNTs) and melamine
The weight ratio of amine (MAM) is 1:1.2-3, preferably 1:1.4-2.8, more preferably 1:1.6-2.4；And/or
In step 2) in, three's weight of CNT/tripolycyanamide complex (CNT-MAM), tripolycyanamide and aldehyde compound
The ratio of amount is 1:1.2-3:1.3-5.5, preferably 1:1.4-2.8:1.5-5.0, more preferably 1:1.6-2.4:1.7-4.5.
9. according to arbitrary described method in claim 6-8, it is characterised in that：The step 3) it is carried out as follows：Gained carbon is received
Mitron/poly- (melamine amine-aldehyde) complex is in an inert atmosphere at 600～1500 DEG C, preferred 650-1200 DEG C, more preferably 700-
Heat treatment at a temperature of 1000 DEG C, obtains final product nitrogen-doped carbon nanometer pipe/carbon compound oxygen reduction catalyst.
10. according to arbitrary described method in claim 6-8, it is characterised in that：Described aldehyde compound be monoaldehyde, two
One or more in first aldehyde or polyaldehyde, is preferably selected from formaldehyde, benzaldehyde, acrylic aldehyde, Biformyl, isocyclocitral
One or more.
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| CN108946734A (en) * | 2017-05-25 | 2018-12-07 | 中国科学院大连化学物理研究所 | A kind of SiC ceramic matrix composite material and preparation method thereof of N doping multi-walled carbon nanotube modification |
| CN108470916A (en) * | 2018-02-07 | 2018-08-31 | 深圳大学 | It is a kind of using three-dimensional porous carbon material as the fuel cell oxygen reduction catalyst of raw material and preparation method |
| CN108470916B (en) * | 2018-02-07 | 2020-09-01 | 深圳大学 | Fuel cell oxygen reduction catalyst taking three-dimensional porous carbon material as raw material and preparation method thereof |
| CN109473684A (en) * | 2018-09-29 | 2019-03-15 | 中国科学院山西煤炭化学研究所 | The elctro-catalyst and preparation method of a kind of sulphur-nitrogen-carbon-based oxygen reduction of transition metal codope and application |
| CN109507240A (en) * | 2018-10-22 | 2019-03-22 | 武汉理工大学 | The method for assessing fuel-cell catalyst oxygen reduction activity under specified potential |
| CN110544774A (en) * | 2019-09-09 | 2019-12-06 | 长春理工大学 | Transition metal nanocrystalline-nitrogen-doped carbon nanotube composite bifunctional catalyst and preparation method and application thereof |
| CN110544774B (en) * | 2019-09-09 | 2020-11-10 | 长春理工大学 | Transition metal nanocrystalline-nitrogen-doped carbon nanotube composite bifunctional catalyst and preparation method and application thereof |
| CN112701265A (en) * | 2020-12-30 | 2021-04-23 | 桐乡市融杭科技合伙企业(有限合伙) | Mesoporous carbon coated SnO2Nano flower lithium ion battery cathode material and preparation method thereof |
| CN114975906A (en) * | 2022-07-27 | 2022-08-30 | 湘潭大学 | Preparation method of nitrogen-doped fluorinated modified graphene negative electrode material and battery |
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