CN108043405A - A kind of preparation method of different valence state cobalt-carbon serial nano composite material - Google Patents
A kind of preparation method of different valence state cobalt-carbon serial nano composite material Download PDFInfo
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- CN108043405A CN108043405A CN201711144011.7A CN201711144011A CN108043405A CN 108043405 A CN108043405 A CN 108043405A CN 201711144011 A CN201711144011 A CN 201711144011A CN 108043405 A CN108043405 A CN 108043405A
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- cobalt
- carbon
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 49
- CODVACFVSVNQPY-UHFFFAOYSA-N [Co].[C] Chemical compound [Co].[C] CODVACFVSVNQPY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 zeolite imidazole metalloid Chemical class 0.000 claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 20
- 239000010457 zeolite Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910052752 metalloid Inorganic materials 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000013384 organic framework Substances 0.000 claims description 15
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- VFRXDYJVRJZXPL-UHFFFAOYSA-H [OH-].[Co+2].[C+4].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Co+2].[C+4].[OH-].[OH-].[OH-].[OH-].[OH-] VFRXDYJVRJZXPL-UHFFFAOYSA-H 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000003788 bath preparation Substances 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000009466 transformation Effects 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 235000013495 cobalt Nutrition 0.000 abstract 3
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000007039 two-step reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000001914 filtration Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- SKYGTJFKXUWZMD-UHFFFAOYSA-N ac1l2n4h Chemical compound [Co].[Co] SKYGTJFKXUWZMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/33—
-
- B01J35/398—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of preparation methods of different valence state cobalt carbon serial nano composite material, belong to technical field of composite preparation.The present invention uses same zeolite imidazole metalloid organic backbone as precursor material, provide effective cobalt source simultaneously, carbon source, one-step or two-step reaction is taken to can obtain different valence state cobalt carbon serial nano composite material, only need a kind of presoma and simple processing technology, the nanoscale that various different valence state cobalts and carbon can be realized is compound, i.e. cobalt carbon is nano combined or cobalt/cobalt oxide carbon nanocomposite, such material catalytic performance is good, available for electro-catalysis field, a variety of valence state cobalt carbon nano-composite materials, which can be realized, improves water electrolysis hydrogen production or fuel cell electrode catalyst efficiency, and its application demand is increasingly extensive.Raw material of the present invention is easy to get, and preparation process is simple, and surfactant, precipitating reagent etc. is not required, and production cost is low, is easy to mass produce.
Description
Technical field
The invention belongs to technical field of composite preparation, and in particular to a kind of different valence state cobalt-carbon serial nano is compound
Material and preparation method thereof.
Background technology
With the continuous growth to advance with world population of social economy, the mankind are to fossil fuel, such as coal and oil
Deng consumption bring unprecedented pressure and challenge to existing energy reserves and natural environment.Utilize solar energy, wind energy
A kind of clean energy resource can effectively reduce the dependence to fossil fuel.It is but efficient due to the intermittence of these clean energy resourcies
Energy carrier and energy conversion become required and vital condition for the large-scale application of this kind of clean energy resource.Hydrogen is
A kind of preferable energy carrier because it have the characteristics that it is efficient, inexpensive, sustainable and environmental-friendly, obtained extensively
Application.Fuel cell is preferable energy conversion device, has also obtained widely research and the application of part.Photocatalytic water,
Particularly electrolysis water inexpensively prepares one of important means and most effectual way of hydrogen as realization industrialization, however slowly analyses
Oxygen reaction (OER) dynamic process significantly limits the efficiency of water decomposition, adds the consumption of energy.And fuel cell is slow
Slow Cathodic oxygen reduction (ORR) dynamic process also significantly limits energy conversion efficiency.
Commercial oxygen-separating catalyst is mainly IrO at present2And RuO2Noble metals are waited, your gold business-purpose fuel cell catalyst is
Belong to Pt, their fancy prices and rare reserves constrain the development of new energy storage and conversion, therefore, find cheap
Become the hot spot of Recent study with the non-precious metal catalyst of rich reserves.
Nano-complex particle catalytic performance is good, particularly in electro-catalysis field, is widely used in improving hydrolysis or fuel electricity
Pond electro-catalysis efficiency.With the development of synthetic technology, it has been found that the compound of transition metal and carbon becomes electrolysis water reaction and urges
The promising candidate material of agent, particularly cobalt-carbon composite, had both played the good electro catalytic activity of cobalt-based itself,
Metal is wrapped with the carbon of different graphitization degree degree again, the catalytic activity of compound interface is further improved, enhances catalysis
The stability of agent.As multi-functional cobalt-C catalyst, how simply and effectively to obtain different valence state cobalt-carbon composite is this
Class catalyst obtains the premise of large-scale application.And zeolite imidazole metalloid organic frame (MOFs) base novel complex carbon material is led
It is electrically good to ensure the homodisperse of active site again, and such material preparation process is simple, of low cost, the place of MOFs
Manage bar part slight changes can obtain different valence state cobalt-carbon serial nano composite material.Raw material of the present invention is easy to get, preparation process
Process is simple, and surfactant, precipitating reagent etc. is not required, and production cost is low, therefore this work is for developing cheap metal/carbon
Nanocomposite is used as the novel electro-catalytic material of analysis oxygen catalysis (OER) and hydrogen reduction catalysis (ORR), and realizes scale reality
Border application has far-reaching significance.
The content of the invention
The object of the present invention is to provide a kind of efficiently feasible, inexpensive different valence state cobalt-carbon serial nano composite materials
Preparation method, this method can realize that homogeneous raw material changes simultaneously to a variety of cobalts-carbon nano-composite material, i.e., with smaller cost
The purpose of cobalt carbon nano-composite material product diversification is realized with simple mode.
The specific technical solution that the present invention takes is：
1) synthesis material includes cobalt nitrate (or cobaltous sulfate or cobalt acetate or cobalt chloride), methylimidazole (or second butyl front three
Base imidazoles), sodium borohydride (or sodium hydrogen selenide).
2) by cobalt salt and imidazoles organic ligand (molar ratio 1 in proportion：1-1：5) (the v in ethanol water：V=1：1-1：4)
It is uniformly mixed；By mixed solution stirring at normal temperature 30 minutes, 10-24h is stored at room temperature, the product of generation has for zeolite imidazole metalloid
Machine frame frame material, the presoma unified as different valence state cobalt-carbon serial nano composite material is former after washed, filtering and drying
Material.
3) homogeneous raw material, the preparation of multiple product is using high temperature pyrolytic cracking (HTP) (heating temperature 600-900 degree keeps the temperature 2-6h), hydro-thermal
Carbonizatin method (heating temperature 120-180 degree, keep the temperature 5-15h) or two methods are used in conjunction realizations, and sodium borohydride (or selenium hydrogenates
Sodium) it can also assist in as reducing agent and play the role of adjusting different valence state cobalt constituent in cobalt-carbon nano-composite material, also
The adding proportion and addition manner of former agent be：50mg zeolite imidazole metalloid organic framework materials presomas are placed in ethanol water
In (v：V=1：1-1：4) disperse, add sodium borohydride (or sodium hydrogen selenide) aqueous solution 1mL-15mL (ice water of 1M-2M concentration
Bath prepare), stir 1-2min after it is spare.The forerunner's dispersion liquid for the addition reducing agent got ready is first positioned over hydrothermal reaction kettle carbon
Change, further according to needing further to be positioned over the carbonization of atmosphere furnace high temperature pyrolysis.
4) method realizes cobalt site after carbonization using the zeolite imidazole metalloid organic frame precursor material of the same race voluntarily synthesized
Be uniformly distributed with effective carbon coating, than same type of material use other synthetic methods more economically be applicable in.
Description of the drawings
Fig. 1 is different valence state cobalt-carbon serial nano composite material prepared by case study on implementation 1,2,4,5,6,7 of the present invention
X-ray diffracting spectrum；
Fig. 2 is the low power scanning transmission electronic display of cobalt-carbon serial nano composite material prepared by case study on implementation of the present invention
Micro mirror picture；
Fig. 3 is the high-resolution-ration transmission electric-lens figure of cobalt-carbon serial nano composite material prepared by case study on implementation 5 of the present invention；
Fig. 4 is the x-ray photoelectron spectroscopy point of cobalt-carbon serial nano composite material prepared by case study on implementation 5 of the present invention
Analysis figure；
Fig. 5 is the electro-catalysis oxygen evolution reaction of cobalt-carbon serial nano composite material prepared by case study on implementation 1,4,5 of the present invention
(OER) LSV contrast curves；
Specific embodiment
With reference to embodiment, the invention will be further elaborated, and these embodiments be merely to illustrate the present invention without
For limiting the scope of the invention.Simultaneously after reading the content taught by the present invention those skilled in the art to institute of the present invention
Any change or modification made, all also fall within the scope of the appended claims of the present application.
Embodiment 1：
By cobalt salt and glyoxaline ligand in molar ratio 1：3.667 in methanol and alcohol mixed solvent (v：V=1：1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It will system
Standby zeolite imidazole metalloid organic framework materials are as 600 degree of high temperature pyrolysis 3h under presoma inert atmosphere, you can obtain cobalt-
Carbon nano-composite material.
Embodiment 2：
By cobalt salt and glyoxaline ligand in molar ratio 1：3.667 in methanol and alcohol mixed solvent (v：V=1：1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It will system
Standby zeolite imidazole metalloid organic framework materials are decomposed as 140 degree of hydro-thermal 9h of presoma, you can obtain cobaltosic oxide-carbon
Nanocomposite.
Embodiment 3：
By cobalt salt and glyoxaline ligand in molar ratio 1：3.667 in methanol and alcohol mixed solvent (v：V=1：1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 3mL of 1M is stirred 5 minutes, then is positioned over 150 degree of reaction 7h of hydrothermal reaction kettle, can obtain hydroxide
Cobalt-carbon nano-composite material.
Embodiment 4：
By cobalt salt and glyoxaline ligand in molar ratio 1：3.667 in methanol and alcohol mixed solvent (v：V=1：1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 3mL of 1M is stirred 5 minutes, then is positioned over 150 degree of reaction 7h of hydrothermal reaction kettle, can obtain hydroxide
Cobalt-carbon nano-composite material.Again through tube furnace or box atmosphere furnace under protective atmosphere, the pyrolytic 2h at 700 DEG C, you can
Obtain cobalt protoxide-carbon nano-composite material.
Embodiment 5：
By cobalt salt and glyoxaline ligand in molar ratio 1：3.667 in methanol and alcohol mixed solvent (v：V=1：1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 6mL of 2M is stirred 5 minutes, then is positioned over 140 degree of reaction 9h of hydrothermal reaction kettle, can obtain cobalt-hydroxide
Sub- cobalt-carbon nano-composite material.Again through tube furnace or box atmosphere furnace under protective atmosphere, the pyrolytic 5h at 600 DEG C, i.e.,
It can obtain using cobalt as cobalt-cobalt protoxide-carbon nanometer heterogeneous composite material of main phase.
Embodiment 6：
By cobalt salt and glyoxaline ligand in molar ratio 1：3.667 in methanol and alcohol mixed solvent (v：V=1：1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 6mL of 1M is stirred 5 minutes, then is positioned over 160 degree of reaction 5h of hydrothermal reaction kettle, can obtain hydroxide
Cobalt-cobalt-carbon nano-composite material.Again through tube furnace or box atmosphere furnace under protective atmosphere, the pyrolytic 6h at 700 DEG C,
It is i.e. available using cobalt protoxide as cobalt protoxide-cobalt-carbon nanometer heterogeneous composite material of main phase.
Embodiment 7：
By cobalt salt and glyoxaline ligand in molar ratio 1：3.667 in methanol and alcohol mixed solvent (v：V=1：1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 1mL of 1M is stirred 5 minutes, then is positioned over 170 degree of reaction 5h of hydrothermal reaction kettle, can obtain four oxidations three
Cobalt-hydroxide cobalt-carbon nano-composite material.Again through tube furnace or box atmosphere furnace under protective atmosphere, the high temperature at 600 DEG C
Decompose 3h, you can obtain cobaltosic oxide-cobalt protoxide-carbon nanometer heterogeneous composite material.
Claims (11)
1. a kind of preparation method of different valence state cobalt-carbon serial nano composite material, it is characterised in that：Choose same zeolite miaow
Azole metal-organic framework material is presoma, is used in conjunction through the carbonization of atmosphere furnace high temperature pyrolysis, hydrothermal carbonization or two kinds of synthetic methods,
And it is aided with sodium borohydride (or sodium hydrogen selenide) and makees reducing agent, you can realizes the system of different valence state cobalt-carbon serial nano composite material
It is standby；Wherein different valence state cobalt-based particle forms nanocomposite, the nano combined material of preparation with single-phase or heterogeneous form and carbon
Expect that species reaches 5-15 kinds.
2. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature exist
In including the following steps：
1) by cobalt salt and glyoxaline ligand (molar ratio 1 in proportion：1-1：5) it is uniformly mixed in ethanol water；It will mix molten
Liquid stirs 30 minutes, is stored at room temperature 10-24h, and the product of generation is zeolite imidazole metalloid organic framework materials, washed, mistake
Filter and drying for standby；
2) tube furnace or box atmosphere furnace are placed in using the zeolite imidazole metalloid organic framework materials of preparation as presoma, protected
It protects under atmosphere and roasts 2-6h pyrolytics in 600-900 DEG C, you can obtain cobalt-carbon nano-composite material；
3) using the zeolite imidazole metalloid organic framework materials of preparation as presoma hydrothermal decomposition, by being positioned over hydro-thermal reaction
120-180 DEG C of reaction 5-15h in kettle, you can obtain cobaltosic oxide-carbon nano-composite material；
4) the zeolite imidazole metalloid organic framework materials 50mg of preparation is placed in as presoma in ethanol water and disperseed, root
According to sodium borohydride (or sodium hydrogen selenide) the aqueous solution 1mL-15mL (ice-water bath preparation) for needing to add in 1M-2M concentration, then it is positioned over
120-180 DEG C of reaction 5-15h, obtains cobaltosic oxide or hydroxide cobalt or cobalt-carbon nano-composite material in hydrothermal reaction kettle,
Wherein cobalt valence state is the one or more in cobaltosic oxide, hydroxide cobalt and cobalt phase, and phase composition can be carried out according to reducing agent
Further adjust；
5) cobalt-carbon nano-composite material of hydrogeneous cobalt protoxide phase is further arranged in the tube furnace of logical protective atmosphere or box atmosphere
In stove, 2-6h pyrolytics are roasted in 600-900 DEG C, you can hydroxide cobalt is changed into cobalt protoxide, is obtained sub- containing oxidation
Single-phase or multiphase cobalt-carbon nano-composite material of cobalt phase.
3. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature exist
In the different valence state cobalt-carbon serial nano composite material precursor is zeolite imidazole metalloid organic framework materials series
One kind, and be same forerunner.
4. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature exist
Synthesized in, composite material precursor zeolite imidazole metalloid organic framework materials in room temperature, and can provide simultaneously carbon source and
Cobalt source.
5. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature exist
In soluble cobalt needed for the presoma of synthetic composite material is at least one in cobalt nitrate, cobaltous sulfate, cobalt acetate or cobalt chloride
Kind.
6. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature exist
In the protective atmosphere needed for synthetic composite material refers at least one of argon gas, helium, carbon dioxide or nitrogen.
7. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature exist
In the different valence state of cobalt relies on the change of mode of heating or sodium borohydride (or sodium hydrogen selenide) reducing agent addition amount in composite material
Change realize.
8. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature exist
In zeolite imidazole metalloid organic framework materials can directly prepare cobalt-carbon of zeroth order cobalt valence state by atmosphere furnace high temperature pyrolysis
Nanocomposite, and Direct Hydrothermal reaction can prepare cobaltosic oxide-carbon nanometer of positive two and positive trivalent mixing cobalt valence state
Composite material.
9. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature exist
In, only by hydro-thermal reaction and reducing agent adjusting can prepare it is a variety of containing hydroxide cobalt or without hydroxide cobalt not
With valence state cobalt-carbon serial nano composite material.
10. a kind of preparation method of different valence state cobalt-carbon serial nano composite material according to claim 1, feature
It is, the different valence state cobalt containing hydroxide cobalt-carbon serial nano composite material can realize it again through atmosphere furnace high temperature pyrolysis
The transformation of the middle opposite cobalt protoxide phase of hydroxide cobalt, and the valence state of cobalt is constant in the phase.
11. a kind of application of different valence state cobalt-carbon serial nano composite material according to claim 1, it is characterised in that：
Different valence state cobalt-carbon serial nano composite material can be used in electrolysis water reaction and fuel cell catalyst reaction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| CN109647477A (en) * | 2018-11-26 | 2019-04-19 | 大连理工大学 | A kind of fast preparation method and application of the derivative catalyst of high yield MOF |
| CN110931798A (en) * | 2019-12-12 | 2020-03-27 | 哈尔滨理工大学 | Preparation method of 3DPC/Co/CoO lithium battery negative electrode material |
| CN111346642A (en) * | 2020-02-05 | 2020-06-30 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN113151841A (en) * | 2020-11-10 | 2021-07-23 | 南京大学 | Preparation method of CoO @ carbon nanotube film with HER/OER (HER/OER) dual-functional catalytic activity |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564875A (en) * | 2016-11-09 | 2017-04-19 | 江苏理工学院 | Preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles |
| CN107176598A (en) * | 2016-03-08 | 2017-09-19 | 中国科学院青岛生物能源与过程研究所 | A kind of N doping mesoporous carbon-loaded cobalt-oxidation cobalt nanocomposites and its preparation method and application |
| CN107557811A (en) * | 2017-09-05 | 2018-01-09 | 济南大学 | A kind of preparation method and application of porous carbon@cobaltosic oxide nano composite materials |
-
2017
- 2017-11-17 CN CN201711144011.7A patent/CN108043405B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107176598A (en) * | 2016-03-08 | 2017-09-19 | 中国科学院青岛生物能源与过程研究所 | A kind of N doping mesoporous carbon-loaded cobalt-oxidation cobalt nanocomposites and its preparation method and application |
| CN106564875A (en) * | 2016-11-09 | 2017-04-19 | 江苏理工学院 | Preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles |
| CN107557811A (en) * | 2017-09-05 | 2018-01-09 | 济南大学 | A kind of preparation method and application of porous carbon@cobaltosic oxide nano composite materials |
Non-Patent Citations (1)
| Title |
|---|
| BINLING CHEN等: "Metal-organic-frameworks derived cobalt embedded in various carbon structures as bifunctional electrocatalysts for oxygen reduction and evolution reactions", 《SCIENTIFIC REPORTS》 * |
Cited By (8)
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|---|---|---|---|---|
| CN109647477A (en) * | 2018-11-26 | 2019-04-19 | 大连理工大学 | A kind of fast preparation method and application of the derivative catalyst of high yield MOF |
| CN109647477B (en) * | 2018-11-26 | 2021-10-22 | 大连理工大学 | Rapid preparation method and application of high-yield MOF (Metal organic framework) derivative catalyst |
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| CN110931798A (en) * | 2019-12-12 | 2020-03-27 | 哈尔滨理工大学 | Preparation method of 3DPC/Co/CoO lithium battery negative electrode material |
| CN111346642A (en) * | 2020-02-05 | 2020-06-30 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN111346642B (en) * | 2020-02-05 | 2023-02-28 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN113151841A (en) * | 2020-11-10 | 2021-07-23 | 南京大学 | Preparation method of CoO @ carbon nanotube film with HER/OER (HER/OER) dual-functional catalytic activity |
| CN113151841B (en) * | 2020-11-10 | 2022-03-18 | 南京大学 | Preparation method of CoO @ carbon nanotube film with HER/OER (HER/OER) dual-functional catalytic activity |
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