CN107413365A - A kind of preparation method of N doping super large tube chamber carbon nano tube compound material - Google Patents
A kind of preparation method of N doping super large tube chamber carbon nano tube compound material Download PDFInfo
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- CN107413365A CN107413365A CN201710340650.4A CN201710340650A CN107413365A CN 107413365 A CN107413365 A CN 107413365A CN 201710340650 A CN201710340650 A CN 201710340650A CN 107413365 A CN107413365 A CN 107413365A
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- 239000000463 material Substances 0.000 title claims abstract description 41
- -1 carbon nano tube compound Chemical class 0.000 title claims abstract description 28
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 25
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002071 nanotube Substances 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000013110 organic ligand Substances 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000013384 organic framework Substances 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 150000004959 2-nitroimidazoles Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 229910052620 chrysotile Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- RBZVCMKUEIDTSC-UHFFFAOYSA-N formaldehyde;1h-imidazole Chemical compound O=C.C1=CNC=N1 RBZVCMKUEIDTSC-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 238000003763 carbonization Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 8
- 229910052621 halloysite Inorganic materials 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- 239000007787 solid Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000013528 metallic particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 235000019256 formaldehyde Nutrition 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- B01J35/615—
-
- B01J35/617—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention provides a kind of preparation method of N doping super large tube chamber carbon nano tube compound material, belongs to nanocomposite catalytic preparing technical field.Template procedure is removed in tubular inorganic template 1-dimention nano pipe surface Electrostatic Absorption, oriented nucleation growth, confinement carbonization and acid etching based on metal organic framework compound, obtains metal-modified nitrogen-doped carbon nanometer pipe composite.Gained composite tube chamber is big, tube wall is thin, shows the characteristic rich in electrochemical site with efficent electronic transmission.The present invention has the characteristics of easy to operate, cost is cheap, easy industrialized production, is had broad application prospects in terms of energy storage and environmental friendly catalysis.
Description
Technical field
The ultra-thin tube wall of metal-modified N doping, super large tube chamber are prepared by metal organic framework compound the present invention relates to one kind
The synthetic method of carbon nano tube compound material, belongs to new material technology field.
Background technology
In nano material, CNT is described as " super nano material ".CNT is as typical one-dimensional (1D)
Nano structural material, the physicochemical characteristics of novelty, especially high heat endurance and surface carrier mobility are shown, is made
CNT is used widely in fields such as new energy, sensor, ultracapacitors.The huge research that CNT is shown
Researcher is also result in application value to be doped CNT and compound research boom.Have at present for CNT
Various heteroatomic doping, such as the hetero atom such as boron, nitrogen phosphate and sulfur are doped, due to the knot of special electronegativity and uniqueness
Structure, these doped carbon nanometer pipe materials show special characteristic electron and surface defect, have excellent mechanics, electricity and urge
Change performance.And nitrogen-atoms radius approaches with carbon atom, it is easily accessible CNT and forms C-N keys, and the introducing meeting of nitrogen-atoms
Carbon material is increased n-type carrier concentration, the conjugated pi electron density around graphitic carbon fermi level is changed etc..At present, nitrogen is mixed
The traditional preparation methods of miscellaneous carbon nano-tube material are chemical vapor deposition and hydro-thermal method etc., such as Chinese patent
CN106450358A, CN106449183A, with pre-synthesis CNT, after macromolecule modified, again in-situ polymerization or
HTHP hydro-thermal reaction prepares carbon mano-tube composite, then obtains nitrogen-doped carbon nanometer pipe by high temperature pyrolysis.Such method
Preparation process is cumbersome, it is difficult to realizes the synchronization modulation to one-dimensional carbon nanotube chemical composition and microstructure, thus is difficult to obtain
Extensive use.
Metal-organic framework materials are a kind of novel porous materials, and wherein zeolite imidazole framework series is skeleton structure success
Model.This kind of complex is coordinated by metal ion and imidazoles or imidazole derivative and formed, and its structure is similar to zeolite
Molecular sieve.The structure of this series compound has diversity, pore size controllable, there is higher heat endurance and chemically stable
Property.Catalytic field is applied especially to, high stability can make it still keep catalytic activity in relatively harsh reaction environment, high
Specific surface area makes it to be used as catalyst carrier.In addition, form the transition metal centre ion and glyoxaline ligand of framework material
It can be widely used as preparing inorganic nano catalysis material from sacrifice template or predecessor.Such as Chinese patent
By the use of metal organic framework compound as precursor material, it is more to prepare classification by CN106410224A, CN106025239A etc.
Hole carbon material.The conventional method that patent refers at present is only capable of obtaining micro-nano granules or two derived from metal organic framework compound
Carbon nanosheet material is tieed up, but because of the limitation of architectural feature, the smaller (120~170m of specific surface area of micro-nano granules material2g-1),
Ion, electron transfer rate are relatively low；The uneven thickness (2~500nm) of Two-dimensional Carbon nanometer sheet material, composition structure are difficult to regulate and control,
And there is the deficiencies of exposed catalytic active site is less in blocked up lamella.1-dimention nano is constructed based on metal organic framework compound
Carbon material, particularly construct the controllable metal-modified of composition, structure height, N doping super large tube chamber carbon nano tube compound material still
It is the huge challenge of functional material research field.
The content of the invention
To overcome above-mentioned the deficiencies in the prior art, the invention provides one kind by metal organic framework compound as forerunner
The method that body prepares metal-modified N doping super large tube chamber carbon nano tube compound material.This method is proposed with zeolite imidazole esters gold
Category organic framework compounds are structured forerunner, can assign the uniform metal of material and N doping, are easily realized to derivative nanometer
The finely regulating of carbon material microstructure.Meanwhile it is commercialized inorganic clay class material halloysite nanotubes, chrysotile nano-tubes
As stay in place form, have cheap, raw material is easy to get, and mechanical strength is higher, the first-class excellent characteristics of tubular morphology.
The invention provides one kind using different metal organic framework compounds in one-dimensional tubular inorganic template surface electrostatic
Absorption, oriented nucleation growth, confinement carbonization and acid etching go the synthetic method of removing template, are formed, the nitrogen that structure height is controllable
Adulterate super large tube chamber carbon nano tube compound material.
Present invention process is simple, can substantially reduce production cost with template using commercialization presoma, reduce cumbersome
Preparation process, it is easy to accomplish large-scale production.
Technical scheme：
A kind of preparation method of N doping super large tube chamber carbon nano tube compound material, step are as follows：
(1) by inorganic nano-tube template and transition metal salt alcoholic solution ultrasonic immersing, organic ligand is added, mixing is equal
Even, room temperature normal pressure is stood, crystallization, centrifuge washing, obtains organic framework compounds coated inorganic nanometer tube composite materials；Wherein,
The concentration of transition metal salt is 0.01-2M, and the concentration of organic ligand is 0.01-1M, organic ligand and transition metal salt mole
Than for 0.01-5.0；
(2) organic framework compounds coated inorganic nanometer tube composite materials are placed under the conditions of 400~1000 DEG C and calcined, forged
Burning process is carried out under the conditions of non-oxide protective gas, cooling, obtains the composite construction of CNT coated inorganic template；
(3) the composite construction immersion of CNT coated inorganic template is removed into inorganic nano pipe die in a solution of hydrofluoric acid
Plate, washed repeatedly with deionized water and ethanol, dry, obtain N doping super large tube chamber carbon nano tube compound material.
Described transition metal salt is more than one or both of zinc, cobalt, the nitrate of iron, acetate, chlorate mixed
Close.
The organic ligand be one or both of imidazoles, 2-methylimidazole, 2- imidazole formaldehydes or 2- nitroimidazoles with
Upper mixing.
The ultrasonic immersing time of step (1) is 0.5-4 hours.
The standing of step (1), crystallization time are 4-72 hours.
Non-oxide protective gas described in step (2) is selected from nitrogen, argon gas, helium, hydrogen, ammonia, carbon dioxide
Or one or both of ethene low-carbon hydrocarbon gas is mixed above.
The calcination time of step (2) is 1-5 hours.
The acid soak time of step (3) is 4-24 hours.
Described N doping super large tube chamber carbon nano tube compound material, its lumen diameter is 60-100nm, and specific surface area is
100-800m2g-1.Products obtained therefrom has higher specific surface area, and N doping and metal-doped composition are uniform, give full play to
The synergy of metal and carbon material, before electrochemical catalyst, energy storage have a wide range of applications with fields such as conversions
Scape.
Beneficial effects of the present invention：
1. technique is simple, raw material is cheap and easy to get；
2. under the confinement effect of tubular inorganic template, metal organic framework compound is in template surface oriented nucleation, limit
Domain growth, confinement carbonization, in the surface in situ pyrolysis generation CNT that cavity is big, tube wall is thin；
3. the nanotube of generation has flourishing pore structure, the materials such as ion, gas, electrolyte can be greatly shortened
Diffusion length, the conductive capability of the further reinforcing material of doping of nitrogen-atoms；
4. its metal and nitrogen-atoms can equably be entrained in carbon nanotube composite after metal organic framework compound carbonization
In material, assign composite good reactivity and catalytic activity.
Brief description of the drawings
Fig. 1 is the preparation flow figure of N doping super large tube chamber carbon nano tube compound material.
Fig. 2 is that the ZIF-67 metal organic framework compounds prepared by embodiment 1 derive the ultra-thin pipe wall carbon nano-tube of N doping
Pipe composite NCNT-1 transmission electron microscope photo.
Fig. 3 is that the ZIF-67 metal organic framework compounds prepared by embodiment 1 derive the ultra-thin pipe wall carbon nano-tube of N doping
The high-resolution-ration transmission electric-lens photo of pipe composite NCNT-1 tube walls.
Fig. 4 is that the ZIF-8 metal organic framework compounds prepared by embodiment 2 derive the ultra-thin tube wall CNT of N doping
Composite NCNT-2 transmission electron microscope photo.
Fig. 5 is that the Zn/Co-ZIF composition metals organic framework compounds prepared by embodiment 3 derive the ultra-thin tube wall of N doping
The NCNT-3 transmission electron microscope photos of carbon nano tube compound material.
Fig. 6 is that the ZIF-8 metal organic framework compounds derivative nitrogen that the different inorganic templates prepared by embodiment 4 add is mixed
Miscellaneous ultra-thin tube wall carbon nano tube compound material NCNT-4 transmission electron microscope photo.
Fig. 7 is the ultra-thin pipe of N doping derived from high concentration ZIF-67 metal organic framework compounds prepared by embodiment 5
Wall carbon nano-tube composite material NCNT-5 transmission electron microscope photo.
Embodiment
Below in conjunction with accompanying drawing and technical scheme, embodiment of the invention is further illustrated.
Fig. 1 is the ultra-thin tube wall carbon nano tube compound material of N doping derived from metal organic framework compound in the present invention
Preparation method schematic flow sheet, specific preparation process are as described below：
(1) tubular inorganic template is added to ultrasonic immersing in the alcoholic solution of transition metal salt, makes tubular inorganic template surface
Target metal ions in absorption, organic ligand is added, is well mixed in solvent, is stood crystallization, last ethanol centrifuge washing, obtain
To the composite of organic framework compounds coated inorganic nanotube template；Reaction temperature is room temperature；Solvent for use be methanol or
One kind in ethanol；Crystallization time is 4-72 hours；Transition metal salt, including the nitrate of zinc, cobalt, iron, chloride salt, acetic acid
It is one or more of in salt, metal salt concentrations 0.01-2M；Organic ligand includes phenylimidazole, 2-methylimidazole, 2- nitroimidazoles
Or at least one of 2- imidazole formaldehydes, organic ligand solution concentration are 0.01-1M, mole of organic imidazate and transition metal salt
Than for 0.01-5.0；
(2) by the composite of the organic framework compounds coated inorganic nanotube template obtained in step (1), in normal pressure
Under, calcined under non-oxide protective atmosphere and obtain the composite of nanotube coated inorganic template.Atmosphere used is nitrogen, argon
One kind in gas, helium, hydrogen, ammonia or carbon dioxide, calcining heat are 400-1000 DEG C, and calcination time is 1-5 hours；
(4) composite of the CNT coated inorganic template obtained in step (3) and hydrofluoric acid solution reaction are gone
Except inorganic nano-tube template, with deionized water and ethanol washed product repeatedly, the described ultra-thin tube wall of N doping is obtained after drying
Carbon nano tube compound material；Reaction temperature is room temperature, and the reaction time is 4-24 hours.
Below will the invention will be further described by several specific embodiments
Embodiment 1
0.78g halloysite nanotubes are scattered in 80mL cobalt nitrates ethanol solution (0.125M), after first stirring 30 minutes
Ultrasound 30 minutes, 80mL methylimidazoles methanol solution (0.5M) is added, stirring is stored at room temperature 24 hours after 30 minutes, is reacted
Terminate, with ethanol by product centrifuge washing 3 times, 60 DEG C of drying obtain ZIF-67 cladding halloysite composite materials.By composite
800 DEG C are heated in nitrogen stream, it is 5 DEG C of min to control heating rate-1, calcine 2 hours, obtain black solid powder.Finally
Material is soaked in hydrofluoric acid, reaction is separated by filtration after 12 hours, is washed with deionized 3 times, is obtained after 60 DEG C of drying
ZIF-67 metal organic framework compounds derive the ultra-thin tube wall CNT (being designated as NCNT-1) of cobalt/N doping, its specific surface area
Up to 541m2g-1, cobalt content is about 26.2wt.%.Fig. 2 is NCNT-1 transmission electron microscope (TEM) photo, can from figure
To find out that CNT outer surface is connected with ultra-thin carbon nanosheet, tube wall surface it is dispersed cobalt metallic particles, cobalt nanometer
Grain average-size about 10nm, official jargon diameter is about 100nm.It can be seen that from Fig. 3 NCNT-1 high resolution electron microscope photos
Nanotube pipe thickness about 5nm.The composite is than other nano carbon tube materials, its larger-diameter tube chamber and ultra-thin pipe
Wall is beneficial to the more active sites of exposure, beneficial to electrolyte and ion, the transmission of proton.
Embodiment 2
0.78g halloysite nanotubes are scattered in 80mL zinc nitrates (0.125M) ethanol solution, after first stirring 30 minutes
Ultrasound 30 minutes, adds 80mL methylimidazoles methanol solution (0.5M), and stirring is stored at room temperature 24 hours after 30 minutes；Reaction
After end, with ethanol by product centrifuge washing 3 times, 60 DEG C of drying obtain ZIF-8 cladding galapectite powder body materials.By powder body material
800 DEG C are heated in nitrogen stream, is calcined 2 hours, it is 5 DEG C of min to control heating rate-1, obtain black solid powder.Finally
Powder is soaked in excessive hydrofluoric acid, reaction is separated by filtration after 12 hours, is washed with deionized 3 times, after 60 DEG C of drying
Obtain ZIF-8 metal organic framework compounds and derive the ultra-thin tube wall CNT (being designated as NCNT-2) of N doping.Fig. 4 is shown
NCNT-2 TEM photos.It can be seen that the CNT obtained by the use of zinc nitrate as precursor salt is compared to embodiment 1
Obtained sample, NCNT-2 surface do not have obvious metallic particles to assemble.
Embodiment 3
1.56g halloysite nanotubes are scattered in 80mL zinc nitrates (0.0625M) and cobalt nitrate (0.0625M) mixed ethanol
In solution, stirring 30 minutes, ultrasound 1 hour after add 80mL methylimidazoles methanol solution (0.5M), stir 30 minutes rear chambers
Temperature stands 24 hours；After reaction terminates, product is centrifuged and washed 3 times with ethanol, 60 DEG C of drying obtain Zn/Co-ZIF bags
The halloysite composite material covered.Material is heated to 800 DEG C in nitrogen stream, calcined 2 hours, it is 5 DEG C to control heating rate
min-1.Finally the black solid powder after carbonization is soaked in hydrofluoric acid, reaction is separated by filtration after 12 hours, uses deionized water
Washing 3 times, obtain Zn/Co-ZIF metal organic framework compounds after 60 DEG C of drying and derive the ultra-thin pipe wall carbon nano-tube of cobalt/N doping
Manage (being designated as NCNT-3).Fig. 5 is NCNT-3 TEM image, it is seen then that the metal organic framework compound constructed through compound precursor salt
Derivative CNT, maintain the characters and appearances of CNT.
Embodiment 4
1.56g chrysotile nano-tubes are scattered in 80mL zinc nitrate solutions (0.25M), stir 30 minutes, ultrasound 30
80mL methylimidazoles methanol solution (1.0M) is added after minute, it is small that mixed dispersion liquid is stored at room temperature 12 by stirring after 30 minutes
When；After reaction terminates, product is centrifuged and washed 3 times with ethanol, the choysotile that 60 DEG C of drying obtain ZIF-8 claddings is answered
Condensation material.Composite is heated to 650 DEG C in argon gas stream again, it is 5 DEG C of min to control heating rate-1, calcine 2 hours.Instead
After should terminating, black solid powder will be obtained and be soaked in hydrofluoric acid, reaction is separated by filtration after 12 hours, is washed with deionized
3 times, the ZIF-8 metal organic framework compounds derivative ultra-thin tube wall CNT of cobalt/N doping is obtained after 60 DEG C of drying and (is designated as
NCNT-4), its specific surface area reaches 361m2g-1.Fig. 6 is NCNT-4 TEM photos, as seen from the figure, in relatively low carbonization temperature
Under degree (650 DEG C), the CNT that is grown in the embodiment still maintains tubular morphology, but CNT is short and small, unordered, pipe
Wall is thicker.
Embodiment 5
3.9g halloysite nanotubes are scattered in 80mL cobalt nitrate solutions (2.5M), stirring 30 minutes, ultrasound 30 minutes
The ethanol solution (10M) of 80mL diimidazole formaldehyde is added afterwards, and mixed liquor is stored at room temperature 24 hours by stirring after 30 minutes；Reaction knot
Shu Hou, product is centrifuged and washed 3 times with ethanol, 60 DEG C of drying obtain the halloysite composite material of ZIF-67 claddings.With
ZIF-67 cladding galapectite powders are heated to 950 DEG C in argon gas stream again afterwards, it is 5 DEG C of min to control heating rate-1, calcining 4
Hour.After reaction terminates, obtained black solid powder is soaked in hydrofluoric acid 6 hours, is then separated by filtration, uses deionization
Water washing 3 times, obtain ZIF-67 metal organic framework compounds after 60 DEG C of drying and derive the ultra-thin tube wall CNT of cobalt/N doping
(being designated as NCNT-5), its specific surface area are up to 615m2g-1.Fig. 7 is NCNT-5 TEM) image, as seen from the figure, by amplifying gold
Belong to the dose ratio of organic compound and galapectite, and the nitrogen-doped carbon that further raising temperature, extension carbonization time obtain is received
Mitron, metal cobalt granule showed increased, and metallic particles reunion is more serious at high temperature.
Claims (10)
1. a kind of preparation method of N doping super large tube chamber carbon nano tube compound material, it is characterised in that step is as follows：
(1) by inorganic nano-tube template and transition metal salt alcoholic solution ultrasonic immersing, organic ligand is added, is well mixed, room
Normal temperature and pressure is stood, crystallization, centrifuge washing, obtains organic framework compounds coated inorganic nanometer tube composite materials；Wherein, transition gold
The concentration of category salt is 0.01-2M, and the concentration of organic ligand is 0.01-1M, and the mol ratio of organic ligand and transition metal salt is
0.01-5.0；
(2) organic framework compounds coated inorganic nanometer tube composite materials are placed under the conditions of 400~1000 DEG C and calcined, it is calcined
Journey is carried out under the conditions of non-oxide protective gas, cooling, obtains the composite construction of CNT coated inorganic template；
(3) the composite construction immersion of CNT coated inorganic template is removed into inorganic nano-tube template in a solution of hydrofluoric acid,
Washed repeatedly with deionized water and ethanol, dry, obtain N doping super large tube chamber carbon nano tube compound material.
2. preparation method according to claim 1, it is characterised in that described inorganic nano-tube template is galapectite nanometer
Pipe or chrysotile nano-tubes.
3. preparation method according to claim 1 or 2, it is characterised in that described transition metal salt is zinc, cobalt, iron
One or both of nitrate, acetate, chlorate are mixed above.
4. preparation method according to claim 3, it is characterised in that the organic ligand is imidazoles, 2-methylimidazole, 2-
One or both of imidazole formaldehyde or 2- nitroimidazoles are mixed above.
5. according to the preparation method described in claim 1,2 or 4, it is characterised in that the ultrasonic immersing time of step (1) is 0.5-
4 hours；The standing of step (1), crystallization time are 4-72 hours.
6. preparation method according to claim 5, it is characterised in that the non-oxide protective gas described in step (2)
It is mixed above selected from one or both of nitrogen, argon gas, helium, hydrogen, ammonia, carbon dioxide, ethene low-carbon hydrocarbon gas.
7. preparation method according to claim 6, it is characterised in that the calcination time of step (2) is 1-5 hours.
8. preparation method according to claim 7, it is characterised in that the acid soak time of step (3) is 4-24 hours.
9. according to the preparation method described in claim 1,2,4,6,7 or 8, it is characterised in that described N doping super large tube chamber
Carbon nano tube compound material, its lumen diameter are 60-100nm, specific surface area 100-800m2g-1。
10. preparation method according to claim 5, it is characterised in that described N doping super large tube chamber CNT is answered
Condensation material, its lumen diameter are 60-100nm, specific surface area 100-800m2g-1。
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