CN109092341A - The nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated and preparation - Google Patents
The nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated and preparation Download PDFInfo
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- CN109092341A CN109092341A CN201810895998.4A CN201810895998A CN109092341A CN 109092341 A CN109092341 A CN 109092341A CN 201810895998 A CN201810895998 A CN 201810895998A CN 109092341 A CN109092341 A CN 109092341A
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- aluminum bar
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- 238000005253 cladding Methods 0.000 title claims abstract description 69
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 62
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical compound [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 37
- 229920000767 polyaniline Polymers 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- -1 ultrasonic disperse Substances 0.000 claims description 2
- 229910000570 Cupronickel Inorganic materials 0.000 claims 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000010949 copper Substances 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000013461 design Methods 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019897 RuOx Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- JOIQWZPMQOLTHQ-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-].[Cu+2] Chemical compound [N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-].[Cu+2] JOIQWZPMQOLTHQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BBGVVPLPLBJJLS-UHFFFAOYSA-N copper ethanol dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] BBGVVPLPLBJJLS-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 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
-
- B01J35/33—
-
- B01J35/396—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated and its preparations.The nitrogen-doped carbon nanocomposite of the hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated, which is characterized in that including hollow nitrogen-doped carbon material, the hollow nitrogen-doped carbon material is coated with Copper-cladding Aluminum Bar cobalt oxide nickel.Composite material prepared by the present invention has the characteristics that structure and morphology is uniform, the hollow nitrogen-doped porous carbon material as derived from ZIF-67 and polyaniline supports the hollow polyhedron structure of the composite material, the doping of copper changes the distribution of charges of cobalt oxide nickel eigenstate, enhances its catalytic performance；The cobalt oxide nickel of Copper-cladding Aluminum Bar is uniformly grown in the outside of hollow nitrogen-doped carbon material, avoids metal oxide and is easy to the problem of reuniting, and has many advantages, such as that large specific surface area, good conductivity, physicochemical properties are stable, chemical property is superior.
Description
Technical field
The invention belongs to Heteroatom doping bimetallic oxide-carbon material technical fields, and in particular to a kind of hollow copper is mixed
The nitrogen-doped carbon nanocomposite and preparation method thereof of miscellaneous cobalt oxide nickel coated.
Background technique
Electro-catalysis hydrolysis causes great research interest as a kind of sustainable hydrogen production process.In two kinds of electrolysis waters
In half-cell reaction, anode oxygen evolution reaction (OER) is related to higher four electronic transfer process of energy requirement, significantly reduces
The efficiency of water decomposition.Therefore, the exploitation of OER effective catalyst is still one of most important challenge of water decomposition hydrogen manufacturing.Noble metal
Oxide such as IrOxAnd RuOxSo far as the highest catalyst OER of activity of elctro-catalyst, but due to its scarcity,
The reasons such as high cost and low durability and be unfavorable for its large-scale commercial applications application.
In order to evade the high cost and scarcity of noble metal-based catalysts (base metal), for example, transition metal oxide and
The catalyst such as the carbon material of Heteroatom doping have caused extensive concern, and in alkaline environment in show it is excellent
OER catalytic activity.However, the feature of unstability and the active site deficiency of non-precious metal catalyst seriously hinders it into one
The development and application of step.The improved method of existing transition metal oxide has many aspects, and the hetero atom including catalyst is mixed
Miscellaneous, defect project, structure design etc..Heteroatom doping strategy in catalyst of transition metal oxide can effectively change
Become the distribution of charges of material itself and significant raising is made to its catalytic performance.And composite material structure design be can be straight
The big factor for influencing material catalytic activity is connect, such as in catalysis reaction, hollow nanostructured catalyst can will be a large amount of
Outer surface be exposed to reactant, there is sufficient reactive surfaces site due to high specific surface area, and by will be anti-
It answers in object limitation in a limited space and allows to increase collision frequency, this can cooperate with enhancing catalytic activity, improve catalyst
Efficiency.
Based on this, the present invention is prepared for the cobalt oxide nickel of Copper-cladding Aluminum Bar using the strategy of Heteroatom doping, and combines hollow receive
The design of rice structure, is prepared for the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated.Its Heteroatom doping
Design substantially increase OER catalytic activity；Meanwhile hollow structure design increases the active site of composite material and than table
Area substantially increases performance of composite material when as catalyst, shows outstanding OER catalytic activity.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of material with higher OER catalytic activity and its preparation sides
Method.
In order to solve the above-mentioned technical problems, the present invention provides following technical solutions:
A kind of nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated, which is characterized in that including hollow
Nitrogen-doped carbon material, the hollow nitrogen-doped carbon material are coated with Copper-cladding Aluminum Bar cobalt oxide nickel.
Preferably, the hollow nitrogen-doped carbon material is hollow polyhedron structure.
The present invention also provides the systems of the nitrogen-doped carbon nanocomposite of above-mentioned hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated
Preparation Method characterized by comprising a strata aniline is coated on the surface ZIF-67, obtains ZIF-67@polyaniline composite material,
Obtained ZIF-67@polyaniline composite material is obtained into hollow polyaniline by acid etch；Hollow polyaniline is subjected to high temperature again
Carbonization treatment obtains hollow nitrogen-doped carbon material；Again via chemical codeposition, the nickel cobalt layered bi-metal of cladding Copper-cladding Aluminum Bar is obtained
The hollow nitrogen-doped carbon material of hydroxide (copper-nickel cobalt LDH)；Finally hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated is obtained by annealing
Nitrogen-doped carbon nanocomposite.
Preferably, the preparation method of the ZIF-67@polyaniline composite material includes: that ZIF-67 powder is dispersed in water
In, ultrasonic disperse is uniform, obtains dispersion liquid, then aniline monomer is added in above-mentioned dispersion liquid, and it is evenly dispersed, then, incited somebody to action
Ammonium sulfate is added in above-mentioned dispersion liquid, is stirred to react, and obtained sediment is centrifuged, and is washed, dry, obtains ZIF-
67@polyaniline composite materials.
It is highly preferred that the concentration of ZIF-67 is 0.5-1.5mg/mL, more preferably 1 mg/mL in the dispersion liquid.
It is highly preferred that the mass concentration of the ammonium persulfate solution is 0.02-0.03g/mL.
It is highly preferred that the time being stirred to react is 8-14h.
It is highly preferred that the mass ratio of the ZIF-67 powder and aniline monomer, ammonium persulfate is 100: 0.01-
0.05∶750-1100。
Preferably, the acid etch includes: to immerse the powder of ZIF-67@polyaniline composite material in hydrochloric acid solution,
Stirring performs etching reaction, etches away internal ZIF-67, obtains hollow polyaniline.
It is highly preferred that the concentration of the hydrochloric acid solution is 0.5-1.5mol/L, etch period 5-7h.It is highly preferred that
The concentration of the hydrochloric acid solution is 1mol/L, etch period 6h.
Preferably, high temperature cabonization processing includes that hollow polyaniline is placed in tube furnace, in inert gas or nitrogen
Atmosphere encloses lower high-temperature process, obtains hollow nitrogen-doped carbon material.
It is highly preferred that the treatment temperature is 700-900 DEG C, time 2-5h, heating rate is 3-10 DEG C/min.
It is highly preferred that inert gas used is argon gas, the temperature of heat treatment is 800 DEG C, heat treatment time 3h, is risen
Warm rate is 5 DEG C/min.
Preferably, the specific steps of the chemical codeposition include: by Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and six
Methenamine is dissolved in the ethanol/water mixed solvent containing micro copper nitrate, and ultrasonic treatment makes it be uniformly dispersed, will be hollow
Nitrogen-doped carbon material is added in the ethanol/water mixed solution, ultrasonic disperse, oil bath heating, and it is anti-that stirring carries out chemical codeposition
It answers, the mixed-powder that reaction obtains is collected by centrifugation, wash, it is dry, obtain the nickel cobalt layered bi-metal of cladding Copper-cladding Aluminum Bar
The hollow nitrogen-doped carbon material of hydroxide (copper-nickel cobalt LDH).
It is highly preferred that the molar ratio of the Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and hexa is 1-4:
1-6:7-14.More preferably 1: 2: 10.
It is highly preferred that in the ethanol/water mixed solvent containing micro copper nitrate copper nitrate concentration be 0.5 ×
10-3-3×10-3Mol/L, the ratio of second alcohol and water are 1-2: 1-4.More preferably 1: 1.
It is highly preferred that the sonication treatment time is 5-20min, more preferably 10min, the ultrasonic disperse time is 1-
3h, more preferably 2h.
It is highly preferred that the oil bath heating temperature is 60-100 DEG C, time 6-12h, and more preferably 80 DEG C, when heating
Between be 8h
It is highly preferred that the washing is carried out with the mixed solution of second alcohol and water, drying temperature is 60 DEG C, time 10-
16h, more preferably 12h.
Preferably, the annealing includes the nickel cobalt layered double hydroxide (copper-nickel cobalt LDH) that will coat Copper-cladding Aluminum Bar
Hollow nitrogen-doped carbon material powder be placed in tube furnace and made annealing treatment in inert atmosphere or nitrogen, obtain hollow Copper-cladding Aluminum Bar
The nitrogen-doped carbon nanocomposite of cobalt oxide nickel coated.
It is highly preferred that the annealing temperature is 250-500 DEG C, time 1-3h.More preferable annealing temperature is 350 DEG C,
The processing time is 2h, and inert gas used is argon gas.
The present invention also provides the nitrogen-doped carbon nanocomposites of above-mentioned hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated to make
For the application of catalyst in OER.
ZIF-67 is prepared by solution stirring method in the present invention, then coats a strata aniline on the surface ZIF-67 again；
Obtained ZIF-67@polyaniline composite material is obtained into hollow polyaniline by acid etch；Hollow polyaniline is subjected to high temperature again
The treatment process of carbonization obtains hollow nitrogen-doped carbon material；The stratiform nickel cobalt bimetallic of Copper-cladding Aluminum Bar is obtained via chemical codeposition again
Hydroxide (copper-nickel cobalt LDH)；Its last preparation process by annealing obtains a kind of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated
Nitrogen-doped carbon nanocomposite.It is characterised by comprising: it is uniform to be prepared for structure and morphology by by the method for polymerisation in solution
ZIF-67, and coated a strata aniline on its surface；ZIF-67@polyaniline composite material is removed into ZIF- by acid etch
67, obtain hollow polyaniline；High temperature cabonization is carried out again, obtains hollow nitrogen-doped carbon material；Finally, using chemical coprecipitation
Product and the preparation process of annealing obtain a kind of hollow nitrogen-doped carbon nanocomposite of cobalt oxide nickel of Copper-cladding Aluminum Bar.
The present invention is prepared for the cobalt oxide nickel of Copper-cladding Aluminum Bar using the strategy of Heteroatom doping, and combines hollow nanostructures
Design, is prepared for the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated.The design of its Heteroatom doping is big
OER catalytic activity is improved greatly；Meanwhile hollow structure design increases the active site and specific surface area of composite material, greatly
Performance of composite material when as catalyst is improved greatly, shows outstanding OER catalytic activity.
Composite material prepared by the present invention has the characteristics that structure and morphology is uniform, is spread out by ZIF-67 polyaniline composite material
Raw hollow nitrogen-doped porous carbon material supports the hollow polyhedron structure of the composite material, and the doping of copper changes oxygen
The distribution of charges for changing cobalt nickel eigenstate, enhances its catalytic performance；The cobalt oxide nickel of Copper-cladding Aluminum Bar is uniformly grown in hollow nitrogen and mixes
The outside of miscellaneous carbon material avoids metal oxide and is easy to the problem of reuniting, and has large specific surface area, good conductivity, physico
Learn the advantages that property is stable, chemical property is superior.
Conventional cobalt oxide nickel material has been carried out Copper-cladding Aluminum Bar by the present invention, is manufactured that using ZIF-67 and polyaniline hollow
Nanostructure, and the two is combined to have obtained the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated.
Compared with prior art, the beneficial effects of the present invention are:
1, experimental design logicality is strong, and preparation process is rigorously mature, it is adapted to study and apply on a large scale.
2, the present invention carries out the doping of copper in conventional cobalt oxide nickel, changes the charge of cobalt oxide nickel eigenstate
It is distributed and is improved catalytic performance, is a kind of method of modifying being simple and efficient.
3, hollow nitrogen-doped carbon material has been obtained using ZIF-67 and polyaniline as reacting precursor, both successfully obtained
Empty nanostructure, and successfully introduce nitrogen-doped carbon.The specific surface area of product is high, and structure is uniform, and there is excellent electricity to urge
Change performance.
Detailed description of the invention
Fig. 1 is the preparation flow of the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated in the present invention
Figure.
Fig. 2 is the XPS map of the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated in the present invention.
Fig. 3 is the XRD spectrogram of the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated in the present invention.
Fig. 4 be using the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated obtained in the present invention as
The catalyst of OER, obtained OER performance atlas.Scheming a curve is hollow Copper-cladding Aluminum Bar cobalt oxide nickel packet obtained in embodiment 1
The OER polarization curve of the nitrogen-doped carbon nanocomposite covered, figure b is corresponding Tafel curve.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated, including hollow N doping carbon materials
Material, the hollow nitrogen-doped carbon material are coated with Copper-cladding Aluminum Bar cobalt oxide nickel.The hollow nitrogen-doped carbon material is hollow
Polyhedral structure.
The nitrogen-doped carbon nanocomposite of the hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated the preparation method comprises the following steps:
Step 1: coating a strata aniline on the surface ZIF-67, ZIF-67@polyaniline composite material is obtained, by what is obtained
ZIF-67@polyaniline composite material obtains hollow polyaniline by acid etch:
ZIF-67 powder is dispersed in the water of 100mL, the uniform 20min of ultrasonic disperse obtains dispersion liquid, ZIF-67's
Concentration is 1mg/mL.20 μ L aniline (Sigma-Aldrich) monomers are added in above-mentioned dispersion liquid again, it is made to be uniformly dispersed.
Then, the ammonium persulfate (Sinopharm Chemical Reagent Co., Ltd.) of 0.95g, ultrasonic treatment are dissolved in the deionized water of 30mL
It is added to after 10min in above-mentioned dispersion liquid, and is stirred to react 12h.Obtained sediment is centrifuged, then is washed with deionized
3 times, ZIF-67@polyaniline composite material is obtained within dry 12 hours in 60 DEG C.By obtained ZIF-67@polyaniline composite material
Powder immerse in the hydrochloric acid solution of 200 mL1mol/L, stirring performs etching reaction 6h, etches away internal ZIF-67, obtains
Hollow polyaniline.
Step 2: handling hollow polyaniline progress high temperature cabonization to obtain hollow nitrogen-doped carbon material again: by hollow polyaniline
It is placed in tube furnace, 800 DEG C of processing 3h under argon atmosphere, heating rate is 5 DEG C/min, obtains hollow nitrogen-doped carbon material.
Step 3: via chemical codeposition, obtaining the nickel cobalt layered double hydroxide (copper-nickel cobalt of cladding Copper-cladding Aluminum Bar
LDH hollow nitrogen-doped carbon material):
By 110mg Nickelous nitrate hexahydrate (Sinopharm Chemical Reagent Co., Ltd.), 221mg cabaltous nitrate hexahydrate (traditional Chinese medicines
Chemical reagent Co., Ltd of group), 560mg hexa (Sigma-Aldrich) is dissolved in 40mL and contains 6 × 10-5mol
Copper nitrate ethanol/water mixed solvent in (volume ratio of second alcohol and water be 1: 1), and be ultrasonically treated 10min, make its dispersion
Uniformly；The hollow nitrogen-doped carbon of 25mg is added in the ethanol/water mixed solution again, ultrasonic disperse 2h；With oil bath heating to 80
DEG C, 8h is stirred, is allowed to carry out the reaction process of chemical codeposition；And then the mixed-powder that reaction obtains is subjected to centrifugation receipts
The mixed solution of collection, the second alcohol and water for being 1: 1 with volume ratio washs, and the dry 12h at 60 DEG C, obtains the nickel of cladding Copper-cladding Aluminum Bar
The hollow nitrogen-doped carbon material of cobalt layered double hydroxide (copper-nickel cobalt LDH).
Step 4: the preparation of the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated:
Obtained mix powder is placed in tube furnace, is made annealing treatment in argon atmosphere at 350 DEG C, the time is
2h obtains the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated.
The present invention is characterized, tested using x-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), electrochemical workstation
The composed structure and performance of the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated obtained, result is such as
Under:
(1) XPS test result shows: existing in the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated
C, O, Ni, Co and Cu element.As shown in Fig. 2, four more apparent peaks being located in 800-900eV correspond respectively to the 2p of Co
The 2p track of track and Ni, and be respectively the 2p of Cu element at the peak of 900-950eV or so two labels occurred3/2Track and
2p1/2Track, this also directly illustrates the successful doping of Cu element.The peak of 500eV or so correspond to O 1s track, 400eV and
The absorption peak that 290eV or so occurs corresponds respectively to the 1s track of N and the 1s track of C, this illustrates nitrogen-doped carbon material and copper
The success of the cobalt oxide nickel of doping is compound.
(2) XRD test result shows: as shown in figure 3, the hollow nitrogen-doped carbon nanocomposite of the cobalt oxide nickel of Copper-cladding Aluminum Bar
XRD curve occur apparent 5 diffraction patterns at 31.3 °, 37.2 °, 43.9 °, 58.3 ° and 63.5 °, respectively correspond oxygen
Change (220), (311), (400), (511) and (440) diffraction crystal face of cobalt nickel.XRD spectrum the result shows that experiment obtained in
The nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated is combined by cobalt oxide nickel and nitrogen-doped carbon, this
Also directly illustrate by preparation method provided by the present invention to be practicable referring to attached drawing 1.
(3) electrochemical workstation test result shows: in electro-chemical test, using three electrode test systems, with made
The glass-carbon electrode of standby hybrid material modification is working electrode, and Ag/AgCl is reference electrode, and graphite rod is to electrode, institute's electricity consumption
Solve the KOH solution that liquid is 1M.Before testing, electrolyte is led to 30 min of oxygen in advance makes amount of oxygen in electrolyte reach saturation.
Using the electro catalytic activity of hybrid material prepared in the linear sweep voltammetry research present invention.OER is tested, polarization is bent
Line is recorded on O2In the 1M KOH electrolyte of saturation, voltage range is 0 to 0.9V (relative to Ag/AgCl) to compare, and is made
All current potentials are converted into RHE value: E (RHE)=E (Ag/AgCl)+0.197+0.0591pH with following equation.Wherein, E
It (RHE) is the potential relative to standard hydrogen electrode, unit is volt (V)；E (Ag/AgCl) is relative to silver/silver chlorate (Ag/
AgCl) the potential of electrode, unit are volt (V)；PH is the hydrogen ionexponent for testing environment solution.
The pretreatment of glass-carbon electrode: glass-carbon electrode is successively polished with 1.0,0.3,0.05 microns of alumina powder,
Grind off the oxide layer and impurity on surface.It is cleaned after polishing with deionized water and EtOH Sonicate every time, last time uses nitrogen after polishing
Air-blowing is done spare.
The preparation of modified electrode: made in the surface present invention by pretreated glass-carbon electrode using direct drop-coating
Standby hybrid material is modified.Specially 350 μ L ethyl alcohol and 50 μ L 5wt% are dispersed by hybrid material prepared by 5mg
Nafion solution forms uniform ink.Then after being ultrasonically treated 1h, take 30 μ L solution drop on platinum carbon electrode, at 70 DEG C
Dry 0.5h is spare in baking oven.
The OER polarization curve (Fig. 4) of the nitrogen-doped carbon nanocomposite catalyst of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated
Clearly demonstrate its excellent OER activity.For the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated,
In 10mAcm-2Current density under, overpotential 400mV.The bright hollow copper of Ta Feier chart of corresponding catalyst
The nitrogen-doped carbon nanocomposite catalyst for adulterating cobalt oxide nickel coated has 59mV dec-1Tafel slope, during this shows
There is the nitrogen-doped carbon nanocomposite of empty Copper-cladding Aluminum Bar cobalt oxide nickel coated preferable catalysis to live when as OER catalyst
Property.
Embodiment 2
Similar to the nitrogen-doped carbon nanocomposite of the hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated of embodiment 1, difference is:
Annealing temperature described in step 5 in embodiment 1 is changed to 450 DEG C, obtained Product Labeling is hollow Copper-cladding Aluminum Bar cobalt oxide nickel
The nitrogen-doped carbon nanocomposite -1 of cladding.
Embodiment 3
Similar to the nitrogen-doped carbon nanocomposite of the hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated of embodiment 1, difference is:
The heat treatment temperature of argon atmosphere described in step 3 in embodiment 1 is changed to 700 DEG C, obtained Product Labeling is hollow copper
Adulterate the nitrogen-doped carbon nanocomposite -2 of cobalt oxide nickel coated.
Claims (9)
1. a kind of nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated, which is characterized in that including hollow nitrogen
Carbon material is adulterated, the hollow nitrogen-doped carbon material is coated with Copper-cladding Aluminum Bar cobalt oxide nickel.
2. the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated as described in claim 1, feature exist
In the hollow nitrogen-doped carbon material is hollow polyhedron structure.
3. the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated of any of claims 1 or 2, feature exist
In, comprising: a strata aniline is coated on the surface ZIF-67, obtains ZIF-67@polyaniline composite material, the ZIF-67@that will be obtained
Polyaniline composite material obtains hollow polyaniline by acid etch；Again hollow polyaniline progress high temperature cabonization is handled to obtain hollow
Nitrogen-doped carbon material；Again via chemical codeposition, the hollow nitrogen of the nickel cobalt layered double hydroxide of cladding Copper-cladding Aluminum Bar is obtained
Adulterate carbon material；Finally the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated is obtained by annealing.
4. the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated as claimed in claim 3, feature exist
In the preparation method of the ZIF-67@polyaniline composite material includes: to be dispersed in water ZIF-67 powder, ultrasonic disperse
Uniformly, obtain dispersion liquid, then aniline monomer be added in above-mentioned dispersion liquid, it is evenly dispersed, then, by ammonium persulfate solution plus
Enter into above-mentioned dispersion liquid, be stirred to react, obtained sediment is centrifuged, washs, it is dry, it is multiple to obtain ZIF-67@polyaniline
Condensation material.
5. the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated as claimed in claim 3, feature exist
In the acid etch includes: to immerse the powder of ZIF167@polyaniline composite material in hydrochloric acid solution, and stirring performs etching
Reaction etches away internal ZIF-67, obtains hollow polyaniline.
6. the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated as claimed in claim 3, feature exist
In the high temperature cabonization processing includes that hollow polyaniline is placed in tube furnace, the high temperature under inert gas or nitrogen atmosphere
Processing, obtains hollow nitrogen-doped carbon material.
7. the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated as claimed in claim 3, feature exist
In the specific steps of the chemical codeposition include: that Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and hexa is molten
Xie Yu contains in the ethanol/water mixed solvent of micro copper nitrate, and ultrasonic treatment makes it be uniformly dispersed, by hollow nitrogen-doped carbon material
It is added in the ethanol/water mixed solution, ultrasonic disperse, oil bath heating, stirring carries out chemical codeposition reaction, and reaction is obtained
Mixed-powder be collected by centrifugation, wash, it is dry, obtain the nickel cobalt layered double hydroxide (copper-nickel of cladding Copper-cladding Aluminum Bar
Cobalt LDH) hollow nitrogen-doped carbon material.
8. the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated as claimed in claim 3, feature exist
In the annealing includes the hollow N doping that will coat the nickel cobalt layered double hydroxide (copper-nickel cobalt LDH) of Copper-cladding Aluminum Bar
Carbon material powder is placed in tube furnace and is made annealing treatment in inert atmosphere or nitrogen, obtains hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated
Nitrogen-doped carbon nanocomposite.
9. the nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated of any of claims 1 or 2 is as OER
The application of middle catalyst.
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| CN111686752A (en) * | 2020-07-20 | 2020-09-22 | 浙江大学 | Taraxacum-shaped load type amorphous alloy catalyst and preparation method and application thereof |
| CN112642457A (en) * | 2020-12-21 | 2021-04-13 | 安徽师范大学 | Hollow iron-based metal organic framework material, iron-doped carbon-nitrogen nano material and preparation method |
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