CN109126850A - A kind of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite and preparation - Google Patents
A kind of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite and preparation Download PDFInfo
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- CN109126850A CN109126850A CN201810899531.7A CN201810899531A CN109126850A CN 109126850 A CN109126850 A CN 109126850A CN 201810899531 A CN201810899531 A CN 201810899531A CN 109126850 A CN109126850 A CN 109126850A
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- doped carbon
- nitrogen
- cobalt nickel
- nickel coated
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 41
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract 14
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 29
- 229920000767 polyaniline Polymers 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 21
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical compound [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 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 6
- 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 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- -1 hexa-methylene four Amine Chemical compound 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000002023 wood 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of hollow cobalt nickel coated nitrogen-doped carbon nanocomposites, which is characterized in that including hollow nitrogen-doped carbon material, the hollow nitrogen-doped carbon material is coated with cobalt oxide nickel.Composite material prepared by the present invention has the pattern of hollow structure, hollow nitrogen-doped porous carbon material derived from polyaniline supports the hollow polyhedron structure of the composite material, cobalt oxide nickel is uniformly grown in the outside of hollow nitrogen-doped carbon material, the problem of cobalt oxide nickel is reunited is avoided, 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 metal oxide-carbon field of material technology, and in particular to a kind of hollow cobalt nickel coated nitrogen is mixed
Miscellaneous carbon nano-composite material and preparation method thereof.
Background technique
As a kind of sustainable, green regenerative energy sources, molecular hydrogen (H2) it is increasingly subject to extensive concern.With other fuel energy
Source is compared, H2Not many advantages, such as not generating greenhouse gases with high-energy density, after burning.Now to Hydrogen Energy wilderness demand
Under overall background, the evolution reaction (HER) of hydrogen causes the strong interest of people, can realize the function of the direct hydrogen production from water.
In order to enable HER high efficiency to carry out, it is desirable to provide a catalyst with high activity.Currently, platinum based noble metal is considered as
Most effective HER catalyst, but its is at high cost, supply is limited, it is difficult to it is extensive to implement.
In order to evade the high cost and scarcity of noble metal-based catalysts, non-precious metal catalyst is (such as: transiting metal oxidation
Object, transition metal phosphide, nitride, carbide, chalcogenide and alloy etc.) it has been increasingly becoming the expensive expensive gold of platinum base
The substitute of metal catalyst.Wherein, with nickel cobalt mine (NiCo2O4) be Typical Representative transition metal oxide because have it is inexpensive,
The advantages that high abundance, high electrons/ions conductivity, is just being widely studied and is producing in hydrogen field applied to electro-catalysis.With spinelle
The NiCo of structure2O4, it is a kind of all-hydrolytic elctro-catalyst of great potential.In order to promote NiCo as far as possible2O4Catalytic activity,
It is an effective strategy that special structure design is carried out to it.For example, hollow three-dimensional (3D) structure is introduced NiCo2O4
In material, its catalytic activity may can be substantially improved.Because the structure of inner hollow will assign material higher specific surface area
And porosity, this will provide more active sites for the absorption of electrolyte, and subsequent surface is accelerated to react, and be electrochemical energy
Source the relevant technologies bring many benefits.
Summary of the invention
The purpose of the present invention is to provide a kind of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite and its preparations
Method.
In order to achieve the above object, the present invention provides a kind of nano combined materials of hollow cobalt nickel coated nitrogen-doped carbon
Material, which is characterized in that including hollow nitrogen-doped carbon material, the hollow nitrogen-doped carbon material is coated with cobalt oxide nickel.
The present invention also provides the preparation method of above-mentioned hollow cobalt nickel coated nitrogen-doped carbon nanocomposite,
It is characterized in that, comprising: by coating polyaniline on the surface ZIF-67, obtain ZIF-67@polyaniline composite material, pass through acid etch
And carbonization treatment, hollow nitrogen-doped carbon material is obtained, through chemical codeposition and annealing, obtains hollow cobalt nickel coated N doping
Carbon nano-composite material.
Preferably, the specific steps in the surface ZIF-67 cladding polyaniline include: by ZIF-67 powder ultrasonic point
It dissipates in water, obtains uniform dispersion, aniline monomer is added, after keeping its evenly dispersed, ammonium persulfate aqueous solution is added, stirring is anti-
Ying Hou is centrifuged, is washed, being dried to obtain ZIF-67 polyaniline composite material.
It is highly preferred that the concentration of the ammonium persulfate aqueous solution is 0.6-2.2g/30mL, preferably 0.95g/30mL.
It is highly preferred that the time that is stirred to react is 10-12h.
It is highly preferred that the ratio of the aniline monomer and ammonium persulfate is 10-30 μ L: 0.6-2.2g.
It is highly preferred that the ratio of the ZIF-67 powder and aniline monomer be 100mg: 10-30 μ L, preferably 100mg: 20
μL。
It is highly preferred that the concentration of ZIF-67 powder is 0.5-1.5mg/mL in the uniform dispersion.
Preferably, the specific steps of the acid etch include: that ZIF-67@polyaniline composite material powder is immersed in salt
It in acid solution, is stirred to react, etches away internal ZIF-67, obtain hollow polyaniline.
It is highly preferred that the concentration of the hydrochloric acid solution is 0.5-1.5mol/L, etch period 3-9h.
It is highly preferred that the concentration of hydrochloric acid used is 1mol/L, mixing time 6h.
Preferably, the specific steps of the carbonization treatment include: that hollow polyaniline is placed in tube furnace, in indifferent gas
It is heat-treated under the atmosphere of body, obtains hollow nitrogen-doped carbon material.
It is highly preferred that the heat treatment temperature is 600-900 DEG C, time 2-5h, heating rate is 3-10 DEG C/min.
It is highly preferred that inert gas used is nitrogen, the temperature of heat treatment is 800 DEG C, heat treatment time 3h, heating
Rate is 5 DEG C/min.
Preferably, the specific steps of the chemical codeposition include: by Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and
Hexa is dissolved in ethanol/water mixed solvent, and being ultrasonically treated 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, washed and dried.
It is highly preferred that the molar ratio of the Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and hexa is 1-3
: 1-5: 8-12, preferably 1: 2: 10, the ratio of second alcohol and water is 1-2: 1-2 in ethanol/water mixed solvent.
It is highly preferred that the ratio of the second alcohol and water is 1: 1.
It is highly preferred that the sonication treatment time is 5-20min, the ultrasonic disperse time is 1-3h, preferably 2h.
It is highly preferred that the oil bath heating temperature is 60-100 DEG C, time 6-10h, preferable temperature is 80 DEG C, heating
Time is 8h.
It is highly preferred that the drying temperature is 60 DEG C, dry 10-14h.
Preferably, the annealing include the powder for obtaining chemical codeposition be placed in tube furnace in inert atmosphere into
Row annealing, obtains hollow cobalt nickel coated nitrogen-doped carbon nanocomposite.
It is highly preferred that the annealing temperature is 250-450 DEG C, time 1-3h.
It is highly preferred that the temperature of annealing process is 350 DEG C, the processing time is 2h, and inert gas used is nitrogen.
The present invention also provides above-mentioned hollow cobalt nickel coated nitrogen-doped carbon nanocomposites as HER (analysis
Hydrogen) application in catalysts.
For the present invention using ZIF-67 as template, the hollow nitrogen-doped porous carbon material as derived from polyaniline supports the composite wood
The hollow polyhedron structure of material；Cobalt oxide nickel is uniformly grown in the outside of hollow nitrogen-doped carbon material, avoids cobalt oxide nickel
The problem of reunion, has many advantages, such as that large specific surface area, good conductivity, physicochemical properties are stable, chemical property is superior.
Composite material prepared by the present invention has the pattern of hollow structure, using ZIF-67 as template, as derived from polyaniline
Hollow nitrogen-doped porous carbon material supports the hollow polyhedron structure of the composite material, significantly enhances its specific surface area；
Cobalt oxide nickel is uniformly grown in the outside of the hollow nitrogen-doped carbon material, avoids easy to reunite in cobalt oxide nickel synthesis process
Problem makes composite material have many advantages, such as that large specific surface area, good conductivity, physicochemical properties are stable, chemical property is superior.
The present invention will use ZIF-67 and polyaniline to be manufactured that hollow nitrogen-doped carbon nanostructure, and grow on its surface
Cobalt oxide nickel nano film has obtained hollow cobalt nickel coated nitrogen-doped carbon nanocomposite.The present invention is based on transition metal
Oxide (cobalt oxide nickel), growth in situ are prepared for a kind of hollow cobalt nickel coated in the strategy of hollow nitrogen-doped carbon material
Nitrogen-doped carbon nanocomposite, meanwhile, hollow structure design increases the specific surface area and active site of composite material, makes
It obtains the material and shows excellent HER catalytic activity.
Compared with prior art, the present invention having the following beneficial effects:
1, it is template and polyaniline as reacting precursor using ZIF-67 and has obtained hollow nitrogen-doped carbon material, both successfully
Hollow nanostructure has been arrived, and has introduced nitrogen-atoms in carbon structure Internal success.
2, cobalt oxide nickel nano film is grown in hollow nitrogen-doped carbon material surface, it is successfully that the two is compound.
3, composite material prepared by the present invention has the pattern of hollow structure, has large specific surface area, good conductivity, physics
The advantages that chemical property is stable, chemical property is superior.
4, composite material prepared by the present invention has the pattern of hollow structure, hollow N doping porous carbon derived from polyaniline
Materials for support plays the hollow polyhedron structure of the composite material, and cobalt oxide nickel is uniformly grown in the outer of hollow nitrogen-doped carbon material
Portion avoids the problem of cobalt oxide nickel is reunited, and has large specific surface area, good conductivity, physicochemical properties stabilization, electrochemistry
Can be superior the advantages that.
Detailed description of the invention
Fig. 1 is the preparation flow figure of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite of the present invention.
Fig. 2 is the XRD spectrum of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite of the present invention.
Fig. 3 is the XPS figure of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite of the present invention.
Fig. 4 is reacted hollow cobalt nickel coated nitrogen-doped carbon nanocomposite obtained in the present invention as HER
Catalyst, obtained HER performance atlas.Scheming a curve is hollow cobalt nickel coated nitrogen-doped carbon obtained in embodiment 1
The HER polarization curve of nanocomposite, 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 hollow cobalt nickel coated nitrogen-doped carbon nanocomposite, including hollow nitrogen-doped carbon material, it is described
Hollow nitrogen-doped carbon material is coated with cobalt oxide nickel, the hollow cobalt nickel coated nitrogen-doped carbon nanocomposite
The preparation method comprises the following steps:
Step 1: the synthesis of hollow nitrogen-doped carbon:
ZIF-67 powder is dispersed in the water of 100mL, 20min is ultrasonically treated, obtains uniform dispersion, ZIF-67's is dense
Degree 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.With
Afterwards, 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.The powder of ZIF-67@polyaniline composite material is soaked
Enter in the hydrochloric acid solution of 1mol/L, be stirred to react 6h, etches away internal ZIF-67, obtain hollow polyaniline.By hollow polyphenyl
Amine is placed in tube furnace, under nitrogen atmosphere 800 DEG C of processing 3h, and heating rate is 5 DEG C/min, obtains hollow N doping carbon materials
Material.
Step 2: the preparation of the hollow nitrogen-doped carbon nanocomposite of cobalt oxide nickel:
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 (Sinopharm Chemical Reagent Co., Ltd.) be dissolved in 40mL second
In alcohol/water mixed solvent (volume ratio of second alcohol and water is 1: 1), and it is ultrasonically treated 10min, it is made to be uniformly dispersed；Again by 25mg
Hollow nitrogen-doped carbon is mixed into the ethanol/water mixed solution, and ultrasonic disperse 2h；With oil bath heating to 80 DEG C, it is stirred to react
Time is 8h, 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；Finally, the mixing that will be obtained
Object powder is placed in tube furnace, is made annealing treatment in nitrogen atmosphere at 350 DEG C, time 2h, obtains hollow cobalt nickel
Coat nitrogen-doped carbon nanocomposite.
Embodiment 2
A kind of hollow nitrogen-doped carbon nanocomposite of cobalt oxide nickel, preparation method are as follows:
Step 1: the synthesis of hollow nitrogen-doped carbon:
ZIF-67 powder is dispersed in the water of 100mL, 20min is ultrasonically treated, obtains uniform dispersion, ZIF-67's is dense
Degree is 1mg/mL.30 μ L aniline (Sigma-Aldrich) monomers are added in above-mentioned dispersion liquid again, it is made to be uniformly dispersed.With
Afterwards, 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.The powder of ZIF-67@polyaniline composite material is soaked
Enter in the hydrochloric acid solution of 1mol/L, be stirred to react 6h, etches away internal ZIF-67, obtain hollow polyaniline.By hollow polyphenyl
Amine is placed in tube furnace, under nitrogen atmosphere 800 DEG C of processing 3h, and heating rate is 5 DEG C/min, obtains hollow N doping carbon materials
Material.
Step 2: the preparation of the hollow nitrogen-doped carbon nanocomposite of cobalt oxide nickel:
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 (Sinopharm Chemical Reagent Co., Ltd.) be dissolved in 40mL second
In alcohol/water mixed solvent (volume ratio of second alcohol and water is 1: 1), and it is ultrasonically treated 10min, it is made to be uniformly dispersed；Again by 25mg
Hollow nitrogen-doped carbon is mixed into the ethanol/water mixed solution, and ultrasonic disperse 2h；With oil bath heating to 80 DEG C, it is stirred to react
Time is 8h, 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；Finally, the mixing that will be obtained
Object powder is placed in tube furnace, is made annealing treatment in nitrogen atmosphere at 350 DEG C, time 2h, obtains hollow cobalt nickel
Coat nitrogen-doped carbon nanocomposite.
This hair is characterized and tested using X-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and electrochemical workstation
The structure and performance of bright embodiment 1 hollow cobalt nickel coated nitrogen-doped carbon nanocomposite obtained, result are as follows:
(1) XRD test result shows: as shown in figure 3, hollow cobalt nickel coated nitrogen-doped carbon nanocomposite
There are apparent 6 diffraction patterns at 18.8 °, 31.3 °, 37.2 °, 44.1 °, 58.7 ° and 64.1 ° in XRD curve, respectively corresponds
(111), (220), (311), (400), (511) and (440) diffraction crystal face of cobalt oxide nickel.XRD spectrum the result shows that experiment
Obtained in during hollow cobalt nickel coated nitrogen-doped carbon nanocomposite includes hollow nitrogen-doped carbon material and is coated on
Cobalt oxide nickel outside empty nitrogen-doped carbon material, this also directly illustrates that by preparation method provided by the present invention be practicable
Referring to attached drawing 1.
(2) XPS test result shows: there are Ni and Co two in hollow cobalt nickel coated nitrogen-doped carbon nanocomposite
Kind element.As shown, being located at 2 more apparent peaks in 770-800eV, the 2p track corresponding to Co in a figure；In b figure
There is more apparent peak positioned at 850-865eV, the 2p corresponding to Ni3/2。
(3) electrochemical workstation test result shows:
In electro-chemical test, using three electrode test systems, it is with the glass-carbon electrode that prepared hybrid material is modified
Working electrode, Ag/AgCl are reference electrode, and graphite rod is to electrode, and electrolyte used is the KOH solution of 1M.Using linearly sweeping
Retouch the electro catalytic activity of hybrid material prepared in the voltammetry research present invention.HER is tested, polarization curve is recorded on
O2In the 1M KOH electrolyte of saturation, voltage range is 0 to -0.6V (relative to Ag/AgCl) to compare, and uses following equation
All current potentials are converted into RHE value: E (RHE)=E (Ag/AgCl)+0.197+0.0591pH.Above-mentioned electrochemical test method
In relevant technological parameter it is as follows: E (RHE) is potential relative to standard hydrogen electrode, and unit is volt (V)；E (Ag/AgCl) is
Relative to the potential of silver/silver chlorate (Ag/AgCl) electrode, unit is volt (V)；PH is that the hydrogen ion concentration of test environment solution refers to
Number.The pretreatment of glass-carbon electrode: glass-carbon electrode is successively polished with 1.0,0.3,0.05 microns of alumina powder, and table is ground off
The oxide layer and impurity in face.Clean after polishing with deionized water and EtOH Sonicate every time, for the last time with being dried with nitrogen after polishing
It is spare.The preparation of modified electrode: passed through prepared by the surface present invention of pretreated glass-carbon electrode using direct drop-coating
Hybrid material 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, in 70 DEG C of baking
Dry 0.5h is spare in case.
The HER polarization curve (Fig. 4 a) of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite catalyst is clearly shown
Its excellent HER activity is shown.For hollow cobalt nickel coated nitrogen-doped carbon nanocomposite, in 10mA cm-2Electric current
Under density, overpotential 164mV.The bright hollow nitrogen-doped carbon of cobalt oxide nickel of the Ta Feier chart of corresponding catalyst is received
Nano composite material catalyst has 64mV dec-1Tafel slope, this shows that hollow cobalt nickel coated nitrogen-doped carbon nanometer is multiple
Condensation material has preferable catalytic activity when as HER catalyst.
Claims (10)
1. a kind of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite, which is characterized in that including hollow N doping carbon materials
Material, the hollow nitrogen-doped carbon material are coated with cobalt oxide nickel.
2. the preparation method of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite described in claim 1, feature exist
In, comprising: by coating polyaniline on the surface ZIF-67, ZIF-67@polyaniline composite material is obtained, acid etch and carbonization are passed through
Processing, obtains hollow nitrogen-doped carbon material, through chemical codeposition and annealing, obtains hollow cobalt nickel coated nitrogen-doped carbon nanometer
Composite material.
3. the preparation method of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite as claimed in claim 2, feature
It is, the specific steps in the surface ZIF-67 cladding polyaniline include: to be dispersed in water ZIF-67 powder ultrasonic, are obtained
To uniform dispersion, aniline monomer is added, after keeping its evenly dispersed, ammonium persulfate aqueous solution is added, after being stirred to react, carry out from
The heart washs, is dried to obtain ZIF-67@polyaniline composite material.
4. the preparation method of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite as claimed in claim 2, feature
It is, the specific steps of the acid etch include: that ZIF-67@polyaniline composite material powder is immersed in hydrochloric acid solution,
It is stirred to react, etches away internal ZIF-67, obtain hollow polyaniline.
5. the preparation method of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite as claimed in claim 2, feature
It is, the specific steps of the carbonization treatment include: that hollow polyaniline is placed in tube furnace, under the atmosphere of inert gas
Heat treatment, obtains hollow nitrogen-doped carbon material.
6. the preparation method of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite as claimed in claim 2, feature
It is, the specific steps of the chemical codeposition include: by Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and hexa-methylene four
Amine is dissolved in ethanol/water mixed solvent, and being ultrasonically treated makes it be uniformly dispersed, and hollow nitrogen-doped carbon material is added to the second
In alcohol/water mixed solution, ultrasonic disperse, oil bath heating, stirring progress chemical codeposition reaction, the mixed-powder that reaction is obtained
It is collected by centrifugation, washed and dried.
7. the preparation method of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite as claimed in claim 6, feature
It is, the molar ratio of the Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and hexa is 1-3: 1-5: 8-12.
8. the preparation method of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite as claimed in claim 2, feature
It is, the annealing includes that the powder for obtaining chemical codeposition is placed in tube furnace and carries out at annealing in inert atmosphere
Reason, obtains hollow cobalt nickel coated nitrogen-doped carbon nanocomposite.
9. the preparation method of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite as claimed in claim 8, feature
It is, the annealing temperature is 250-450 DEG C, time 1-3h.
10. hollow cobalt nickel coated nitrogen-doped carbon nanocomposite described in claim 1 is as HER catalysts
In application.
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| CN110415986A (en) * | 2019-07-12 | 2019-11-05 | 江苏理工学院 | A kind of Ni doping CoO/C composite material and preparation method |
| CN110639591A (en) * | 2019-10-12 | 2020-01-03 | 苏州大学 | Indium zinc sulfide loaded on nitrogen-doped carbon hollow sphere, preparation method thereof and application thereof in wastewater treatment |
| CN112509817A (en) * | 2020-12-02 | 2021-03-16 | 桐乡市吉曼尔信息技术有限公司 | Honeycomb nano NiCo2O4Preparation method and application of nitrogen-loaded doped mesoporous carbon |
| CN113621986A (en) * | 2021-07-13 | 2021-11-09 | 齐齐哈尔大学 | Preparation method of defective nickel cobaltate/porous carbon |
| CN113621177A (en) * | 2021-07-20 | 2021-11-09 | 山东科技大学 | Preparation method of DOPO/ZIF 67/polyaniline nano-composite flame retardant |
| CN113725449A (en) * | 2020-05-25 | 2021-11-30 | 深圳清华大学研究院 | Fuel cell catalyst, preparation method and application thereof |
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| CN110415986A (en) * | 2019-07-12 | 2019-11-05 | 江苏理工学院 | A kind of Ni doping CoO/C composite material and preparation method |
| CN110415986B (en) * | 2019-07-12 | 2021-05-18 | 江苏理工学院 | Ni-doped CoO/C composite material and preparation method thereof |
| CN110639591A (en) * | 2019-10-12 | 2020-01-03 | 苏州大学 | Indium zinc sulfide loaded on nitrogen-doped carbon hollow sphere, preparation method thereof and application thereof in wastewater treatment |
| CN110639591B (en) * | 2019-10-12 | 2022-07-19 | 苏州大学 | Indium zinc sulfide loaded on nitrogen-doped carbon hollow sphere, preparation method thereof and application thereof in wastewater treatment |
| CN113725449A (en) * | 2020-05-25 | 2021-11-30 | 深圳清华大学研究院 | Fuel cell catalyst, preparation method and application thereof |
| CN112509817A (en) * | 2020-12-02 | 2021-03-16 | 桐乡市吉曼尔信息技术有限公司 | Honeycomb nano NiCo2O4Preparation method and application of nitrogen-loaded doped mesoporous carbon |
| CN113621986A (en) * | 2021-07-13 | 2021-11-09 | 齐齐哈尔大学 | Preparation method of defective nickel cobaltate/porous carbon |
| CN113621177A (en) * | 2021-07-20 | 2021-11-09 | 山东科技大学 | Preparation method of DOPO/ZIF 67/polyaniline nano-composite flame retardant |
| CN113621177B (en) * | 2021-07-20 | 2022-06-28 | 山东科技大学 | Preparation method of DOPO/ZIF 67/polyaniline nano-composite flame retardant |
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