CN110075847A - A kind of graphene ribbon/cobalt hydroxide composite nano materials and preparation method thereof - Google Patents
A kind of graphene ribbon/cobalt hydroxide composite nano materials and preparation method thereof Download PDFInfo
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- CN110075847A CN110075847A CN201910199843.1A CN201910199843A CN110075847A CN 110075847 A CN110075847 A CN 110075847A CN 201910199843 A CN201910199843 A CN 201910199843A CN 110075847 A CN110075847 A CN 110075847A
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 31
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000002127 nanobelt Substances 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 9
- 230000014509 gene expression Effects 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000007248 oxidative elimination reaction Methods 0.000 claims description 11
- 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 10
- 239000000047 product Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 15
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 230000010148 water-pollination Effects 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—
-
- B01J35/61—
-
- 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
- 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 invention discloses a kind of graphene ribbon/cobalt hydroxide composite nano materials and preparation method thereof.The material is a kind of graphene nanobelt with banded structure/cobalt hydroxide composite nano materials, and chemical expression is GNRs/Co (OH)2.The material is to be synthesized using graphene nanobelt GNRs as carbon substrate by solvent thermal process.Operation of the present invention is simple, at low cost, and the requirement to equipment is low；The nano material size uniformity prepared, and material interface contact is abundant, material activity surface area is big and there is good electrochemistry to produce oxygen performance.
Description
Technical field
The present invention relates to the preparation of carbon composite/hydroxide, in particular to a kind of graphene ribbon for water oxygen/
Cobalt hydroxide composite nano materials and preparation method thereof, prepared graphene ribbon/cobalt hydroxide composite nano materials (GNRs/
Co(OH)2) there is good electro-catalysis to produce oxygen performance and sufficiently stable.
Background technique
Ever-increasing energy demand causes continuous exploration of the people to efficient, clean energy resource generation or switch technology.
Wherein, electro-catalysis water decomposition is a very potential technology.Electrolysis water process includes two half-reactions: evolving hydrogen reaction
(HER) and oxygen-absorbing reaction (OER).The latter becomes entire technology due to the factors such as its dynamic process is slow, overpotential is larger
Difficult point in implementation.Therefore, in order to push industrialize electrolysis water technology to, it is entire for developing efficient and cheap OER catalyst
The key of technology.In several potential base metal OER catalyst of tool, Co (OH)2Because its on earth rich reserves, urge
Change performance it is stable and by extensive concern.However, Co (OH)2OER catalytic activity be generally limited by its poor electric conductivity, cause
The dynamical phase of entire catalytic process is to slow.In order to solve this problem, by Co (OH)2(such as with highly conductive base material
Carbon material) be combined with each other be improve catalyst performance a very effective thinking.
Many carbon materials have superior electric conductivity, and cheap and easy to get, performance is stablized, and are used as one of conductive substrates most
Good selection.In recent years, some scholars attempt Co (OH)2It is compound with carbon material progress, to improve its electrocatalysis characteristic.Example
Such as, Yimin Jiang etc. is reported in Britain " nanoscale " makes Co (OH) by electrodeposition process2Be grown in carbon nanotube/
On Kapton (CNTs/PI), but Co (OH) in the composite nano materials of this method acquisition2With the contact of PI/CNT substrate
It is insufficient；Mustafa Aghazadeh etc. is reported in the U.S. " material science journal: electronic material " through cathode electro synthesis
Method is by carbon nanotube/cobalt hydroxide (CNTs/Co (OH)2) compound is co-deposited on Stainless steel mesh.What the method obtained
CNTs/Co(OH)2Composite nano materials pattern is irregular, size is inhomogenous, and limits it effectively because reunion is more serious
Surface area.Chemically from the point of view of synthesis technology, above-mentioned synthetic method is all based on electrochemical deposition, so that Co (OH)2And carbon
The microscopic contact of material is simultaneously insufficient.The main reason is that most of conductive carbon material surface (such as CNTs) lacks functional group,
Hydrophily is poor, can not directly anchoring surface nano particle.Also some scholars attempt under mild oxidizing condition, by right
Functionalization is with load C o (OH)2Nano particle.Although the carbon nanotube after modification has a small amount of functional group, bear
The negligible amounts of nano particle are carried, composite construction stability is not high, and the surface area in nanotube can not utilize.
The graphene nanobelt (GNRs) prepared by CNTs through oxidative cleavage has both one-dimensional CNTs and two-dimensional graphene
Common advantages can solve above the problem of being brought by CNTs as carbon substrate.Firstly, GNRs inherits the excellent conduction of CNTs
Property, and size is more regular uniform.Secondly, GNRs is also considered as the two-dimensional variation of the banded structure of graphene, stone has been had both
The black biggish surface area of alkene and enough edge active sites.Finally, because GNRs is from CNTs oxidation removing, edge exists
Many carboxylic acid groups, these groups not only have very strong water solubility, and can adsorb and be anchored metal ion.Work as metal ion
After being anchored, it may make corresponding nano particle in conductive substrates growth in situ.The composite material being achieved in that, which both ensure that, urges
Agent and conductive substrates come into full contact with, but also catalyst has more accessible active site.
Therefore, in the present invention, GNRs/Co (OH) is synthesized we have proposed a kind of low cost, simply2Composite Nano material
The method of material.Suction-operated using group on GNRs to metal ion, growth in situ Co (OH) in GNRs substrate2Nanometer
Piece.Its uniform composite construction ensure that coming into full contact with for catalyst and conduction GNRs, so that composite material is with extraordinary
Electric conductivity；Meanwhile the Co (OH) of vertical-growth2Nanometer sheet can expose more active sites, can give full play to its OER catalysis and live
Property.
Summary of the invention
The technical problem to be solved in the invention is: in order to overcome the deficiencies of the above existing technologies, providing a kind of new
It prepares GNRs/Co (OH)2The method of composite nano materials, this method are put forward for the first time using GNRs as substrate, pass through solvent thermal process
Synthesize the composite nano materials.This method simple process, easy to operate, prepared composite nano materials have uniform ruler
Very little, biggish active surface area, good electrochemistry produce oxygen performance and highly stable.
The present invention solves its technical problem, and the following technical solution is employed:
Graphene ribbon provided by the invention/cobalt hydroxide composite nano materials is a kind of graphene with banded structure
Nanobelt/cobalt hydroxide composite nano materials, chemical expression are GNRs/Co (OH)2。
Graphene ribbon provided by the invention/cobalt hydroxide composite nano materials preparation method, is with graphene nanobelt
GNRs is carbon substrate, synthesizes GNRs/Co (OH) by solvent thermal process2Composite nano materials, the material are a kind of with band-like
The graphene nanobelt of structure/cobalt hydroxide composite nano materials.
The above method the following steps are included:
A. GNRs is synthesized using oxidative cleavage CNTs method:
A. multi-walled carbon nanotube is added in the concentrated sulfuric acid and is stirred 1-2 hours, phosphoric acid solution is then added and continues to stir；
B. potassium permanganate powder is added in the solution of stirring, is first stirred at room temperature 1-2 hours, is then slowly heated
Continue to stir to 65 DEG C；Stop reaction, after being cooled to room temperature, cold deionized water and hydrogenperoxide steam generator is added, by gained
Product centrifugation；It is washed respectively three times with hydrochloric acid and ethyl alcohol again, obtains GNRs；
B. GNRs/Co (OH) is synthesized2Composite nano materials:
C. the above-mentioned GNRs being prepared is taken, is dispersed in methanol and is ultrasonically treated；
D. cabaltous nitrate hexahydrate is added in the solution to after being ultrasonically treated, and is stirred at room temperature to adsorb cobalt ions；
E. urea is added, it is polytetrafluoroethylene (PTFE) that liner is sealed in after being stirred at room temperature, and shell is the reaction of steel material
In container, solvent thermal reaction is carried out；After the reaction was completed, self-heating is cooled to room temperature, and products therefrom is centrifuged, and respectively with methanol and
Water washing twice, after 60 DEG C of vacuum ovens are dry, obtains GNRs/Co (OH)2Composite nano materials.
In above-mentioned steps A, the GNRs of the banded structure is synthesized by the method for oxidative cleavage CNTs, specifically: 65
DEG C the concentrated sulfuric acid and phosphoric acid mixed liquor in, by be added the shearing multi-walled carbon nanotube of potassium permanganate oxidation (CNTs) to prepare stone
Black alkene nanobelt (GNRs).
In above-mentioned steps B, the GNRs/Co (OH)2Composite nano materials are prepared using solvent-thermal method, specifically: with first
Alcohol is solvent, and the temperature of solvent thermal reaction is 120 DEG C, and the reaction time is 12 hours.
In above-mentioned steps c, using methanol as solvent, the additive amount of methanol is 15-25mL；The time of ultrasonication is 20-40
Minute, ultrasonic effect keeps GNRs fully dispersed in a solvent.
In above-mentioned steps d, cobalt source is selected from cobalt chloride hexahydrate, cabaltous nitrate hexahydrate, four hydration cobalt acetates, wherein adopting
It is best with cabaltous nitrate hexahydrate effect, and the mass ratio of cabaltous nitrate hexahydrate and GNRs are 1:1.
Compared with prior art, the present invention having the advantages that following main:
1. an experiment mainly uses solvent structure, the temperature of solvent thermal reaction is 120 DEG C, and the time is 12 hours, behaviour
Make simply, at low cost, the requirement to equipment is low.
2. the nano material size uniformity prepared, and material interface contact is abundant, material activity surface area is big.In reality
In testing, presoma production GNRs is first done using carbon pipe using the method for oxidative cleavage CNTs and is led to then using GNRs as substrate
Cross reaction in-situ preparation GNRs/Co (OH)2Composite nano materials.Because the edge GNRs has many carboxyls to be conducive to and Co2+Knot
It closes, the Co (OH) of growth in situ2It can be uniformly distributed in the edge of GNRs, therefore the composite nano materials structure prepared is steady
It is fixed.Oxygen test, which is produced, through electro-catalysis shows the GNRs/Co (OH) being prepared2The electrochemical surface area of composite nano materials
It (ECSA) is traditional CNTs/Co (OH)22.29 times of composite nano materials, it is seen that the composite Nano material that such method is prepared
Material shows good electrochemistry and produces oxygen performance.
Detailed description of the invention
Fig. 1: Co (OH)2, GNRs and GNRs/Co (OH)2The Raman spectrum of composite nano materials.
Fig. 2: Co (OH)2, GNRs and GNRs/Co (OH)2The X-ray diffractogram of composite nano materials.Co(OH)2It is corresponding
Standard card is 74-1057 (JCPDS::74-1057).
Fig. 3: GNRs/Co (OH)2Composite nano materials and CNTs/Co (OH)2The x-ray photoelectron energy of composite nano materials
Spectrum, in which: Fig. 3 (A) is the XPS map of the C 1s of two kinds of materials, and Fig. 3 (B) is the XPS map of the Co 2p of two kinds of materials.
Fig. 4: the transmission electron microscopy figure as the CNTs for preparing GNRs presoma.
Fig. 5: the transmission electron microscopy figure of the GNRs of oxidative cleavage CNTS method preparation.
Fig. 6: the product GNRs/Co (OH) of embodiment 12The transmission electron microscopy figure of composite nano materials.
Fig. 7: the product CNTs/Co (OH) of embodiment 22The transmission electron microscopy figure of composite nano materials.
Fig. 8: the product Co (OH) of embodiment 32The transmission electron microscopy figure of nano material.
Fig. 9: sample GNRs/Co (OH) prepared by embodiment 12In 0.1M O2The linear sweep voltammetry being saturated in KOH solution
Curve (a curve in figure).In figure as a comparison be CNTs/Co (OH) respectively2(the b curve in figure), Co (OH)2(in figure
C curve), GNRs (the d curve in figure).
Figure 10: sample GNRs/Co (OH) prepared by embodiment 12In 0.1M O2The Tafel slope being saturated in KOH solution
(a curve in figure).In figure as a comparison be CNTs/Co (OH) respectively2(the b curve in figure), Co (OH)2(c in figure is bent
Line), GNRs (the d curve in figure).
Figure 11: sample GNRs/Co (OH) prepared by embodiment 12In 0.1M O2The impedance diagram being saturated in KOH solution.In figure
As a comparison be CNTs/Co (OH) respectively2、Co(OH)2、GNRs。
Figure 12: the sample GNRs/Co (OH) prepared according to embodiment 12, it is the i-t curve of measuring stability.
Figure 13: the cyclic voltammetry curve of test sample electroactive area ECSA.A figure expression is prepared according to embodiment 1
GNRs/Co(OH)2；B figure indicates CNTs/Co (OH)2；C figure indicates Co (OH)2；D figure indicates to sweep the linear pass of speed and current density
System.
Specific embodiment
Below in conjunction with examples and drawings, the invention will be further described, but does not limit the present invention.
Embodiment 1:
The present invention proposes a kind of new to prepare graphene nanobelt/cobalt hydroxide composite nano materials method, chemistry
Expression formula are as follows: GNRs/Co (OH)2。
This preparation GNRs/Co (OH)2The method of composite nano materials, mainly comprises the steps that
A. GNRs is synthesized using oxidative cleavage CNTs method
A. 150mg MWCNTs is added in 98% concentrated sulfuric acid of 36mL mass fraction, is stirred 1 hour.Then again by 4mL
85% phosphoric acid solution of mass fraction is add to the above mixed solution, and continues stirring 15 minutes；
B. 750mg potassium permanganate powder is slowly added into the solution of stirring, is first stirred at room temperature 1 hour, then
It is heated slowly to 65 DEG C and continues stirring 2 hours.Stop reaction, be cooled to room temperature to above-mentioned solution, it is cold that 120mL is added into solution
Deionized water and 5mL mass fraction 30% hydrogenperoxide steam generator, by products therefrom be centrifuged (5000 turns, 6 minutes).Use matter
The hydrochloric acid and dehydrated alcohol for measuring score 37% are washed three times respectively, obtain 150mg GNRs.
B. GNRs/Co (OH) is synthesized2Composite nano materials
C. the above-mentioned GNRs being prepared of 10mg is taken, be dispersed in 20mL anhydrous methanol and is ultrasonically treated 30 minutes.
D. 10mg cabaltous nitrate hexahydrate is added into above-mentioned solution, and is stirred at room temperature 3 hours to adsorb cobalt ions.
E. and then again 13mg urea is added, being stirred at room temperature after 30min and being sealed in liner is polytetrafluoroethylene (PTFE), shell
To be reacted 12 hours in 120 DEG C in the reaction vessel of steel material.After the reaction was completed, self-heating is cooled to room temperature, by products therefrom
Be centrifuged (5000 turns, 10 minutes), and respectively with pure methanol and water washing twice after, dried in 60 DEG C of vacuum ovens 12 small
When to get arrive GNRs/Co (OH)2Composite nano materials.
Embodiment 2:
On the basis of embodiment 1, only using etc. quality CNTs substitution GNRs as substrate, other reaction conditions are constant.
Products therefrom is CNTs/Co (OH)2Composite nano materials.
Embodiment 3:
On the basis of embodiment 1, the mass ratio of GNRs/ cabaltous nitrate hexahydrate is only adjusted to 0:1, that is, the GNRs being added
For 0mg, other reaction conditions are constant.Products therefrom is Co (OH)2Nano material.
Embodiment 4:
On the basis of embodiment 1, the additive amount of anhydrous methanol is only adjusted to 15ml, other reaction conditions are constant.
Embodiment 5:
On the basis of embodiment 1, the additive amount of anhydrous methanol is only adjusted to 25ml, other reaction conditions are constant.
As can be seen from the above embodiments: the invention proposes a kind of new preparation GNRs/Co (OH)2The side of composite nano materials
Method is put forward for the first time with graphene nanobelt (GNRs) as carbon substrate, synthesizes the GNRs/Co by simple solvent thermal process
(OH)2Composite nano materials.In research before this, by Co (OH)2Carbon is generally with the carbon material of carbon material compound tense, use
Nanotube (CNTs) or graphene nanometer sheet (GO) etc., and the present invention is innovative point using GNRs.Synthesizing the method used is
Simple solvent-thermal method.Solvent-thermal method is easy to operate, at low cost, low for equipment requirements, and the GNRs/Co (OH) being prepared2
It is strong that composite nano materials pattern is uniform, active surface area is big, electro-catalysis produces oxygen performance.
The embodiment of the present invention gives 13 width figures, in which:
Fig. 1 shows Co (OH)2、GNRs、GNRs/Co(OH)2Raman spectrum.Raman spectrum be identification carbon material exist and
The strong evidence of its state, graphitic carbon correspond to 1352cm-1And 1575cm-1, sp respectively in graphitic carbon2And sp3Hydridization.Raman
1570cm in figure-1The peak that left and right occurs is the graphite peaks i.e. peak G, is the characteristic peak of crystal carbon, is by graphite basal plane (i.e. carbon nanotube
Tube wall) produced by, be stronger tangential mode absorption band, graphite multi-layer sheet structure more reaches, this peak is stronger.Intact graphite linings
Piece is all by the hexagonal groups of carbon atom at can generate defect in the presence of having pentagon and heptagon or other local defects
Peak, that is, the peak D, it is located at 1352cm-1Place, by unordered or sp in carbon hexatomic ring3The C atomic vibration of hydridization generates.Pass through the peak G and the peak D
Intensity ratio R=ID/IG, can qualitatively characterize the crystallization situation of carbon nanotube.R value is smaller, shows that crystallization is more perfect.It is right
In Co (OH)2, 458cm-1It is attributed to the flexural vibrations peak of OCoO, 510cm-1Symmetric curvature corresponding to CoO (Ag) is vibrated.
Fig. 2 indicates GNRs/Co (OH)2X ray diffracting spectrum, wherein additionally providing pure Co (OH)2, pure GNRs map
As reference.In the compound carbon nanomaterial finally synthesized, the strong diffraction maximum at 11.5 ° comes from α-Co (OH)2Crystal
(003) face, furthermore two diffraction maximums at 23.4 ° and 34.3 ° are respectively from α-Co (OH)2Crystal (006) and (012) face.And
There are two weak diffraction maximums at 25.6 ° and 11.2 ° in graphene nanobelt (GNRs), corresponds respectively to it after aoxidizing unwinding
(002) crystal face and its 2D interlayer structure.Although diffraction peak intensity of the GNRs in X-ray diffraction is weaker, Co (OH)2Nanometer sheet
The diffraction maximum showed is very strong, it means that the Co (OH) of these dispersions2Nanometer sheet crystallizes on graphene nano band
Well.
That Fig. 3 is indicated is GNRs/Co (OH)2With CNTs/Co (OH)2X-ray photoelectron spectroscopy.The present invention passes through two steps
Method synthesizes GNRs/Co (OH)2Composite nano materials dissociate CNTs using oxidative cleavage CNTs method to synthesize first
GNRs.Further prove that CNTs is unlocked through peroxidization as GNRs using XPS.CNTs before unlocking has been substantially
C-C and C=C is constituted, and after unlocking, the edge of band will appear carboxylic acid group.From C 1s spectrogram it can also be seen that CNTs/Co
(OH)22 peaks of middle appearance, wherein 285.2eV corresponds to the sp of carbon3XPS characteristic peak, and 284.5eV corresponds to the sp of carbon2XPS is special
Levy peak.It compares GNRs/Co (OH)2288.47eV occur new peak it is corresponding be-COO characteristic peak.In addition, for determination
The valence state and chemical composition of cobalt have carried out the test of XPS to it.Combining at 780.9eV and 796.7eV two can corresponding peak point
It is not Co 2p3/2And Co 2p1/2Spin-orbit splitting main peak.And the combination of 780.5eV and 796.0eV can corresponding peak difference
It is Co 2p3/2And Co 2p1/2Satellite peak, about 16eV is differed between corresponding main peak and main peak, it is possible to determine that Co from
Co(OH)2In divalent cobalt.This illustrate final product really by GNRs and Co (OH)2Two phase compositions.
Fig. 4-8 indicates the sample in the sample that embodiment 1 synthesizes and synthesis process in transmission electron microscope (abbreviation
TEM resulting data are characterized under).What Fig. 4 was indicated is the transmission electron microscopy figure as the CNTs for preparing GNRs presoma, and is schemed
5 expressions are using the GNRs of oxidative cleavage CNTs method synthesis, and two width figures of comparison are can be found that: the GNRs after oxidation unwinding is put down
Equal diameter is 50nm, and 2~3 times bigger than the average diameter of CNTs, this shows to be into CNTs unwinding by oxidative cleavage CNTs method
Function and high yield.Fig. 6 is the resulting sample TEM phenogram of embodiment 1, from the figure, it can be seen that the Co (OH) of lamella2Uniformly divide
Cloth is at the edge of GNRs；Fig. 7 is the resulting sample TEM phenogram of embodiment 2, and Cong Tuzhong sees, is synthesized Co (OH)2Nanometer sheet heap
Folded serious and CNTs is also wound mutually, and the two is not combined together well.Fig. 6, Fig. 7 compare it follows that with GNRs
For substrate, conductive matrix is provided not only, and also acts as and makes Co (OH)2The effect of nanometer sheet dispersion.Fig. 8 is embodiment 3
Resulting sample TEM phenogram, from the figure, it can be seen that without using GNRs as substrate and the identical situation of other conditions
Under, only obtain a small amount of Co (OH)2Nano flower, this result confirm GNRs as substrate in the Co (OH) for generating dispersion2It receives
Key effect is played during rice structure.
Fig. 9 indicates the sample prepared according to embodiment 1 in 0.1M O2The linear sweep voltammetry curve being saturated in KOH solution
(a curve in figure).In figure as a comparison be CNTs/Co (OH) respectively2(the b curve in figure), Co (OH)2(c in figure is bent
Line), GNRs (the d curve in figure).Scanning linearity voltammogram can weight for product analysis oxygen performance.By comparison, it was found that
In these four samples, GNRs/Co (OH)2Catalyst shows optimal catalytic activity.GNRs/Co(OH)2Analyse the starting electricity of oxygen
Position is in 1.46V, and CNTs/Co (OH)2The take-off potential of oxygen is analysed in 1.50V, is respectively 280mV and 320mV when applying overvoltage
When current density just reach 10mA/cm2, from the GNRs/Co (OH) of this result alternatively bright synthesis2Since band-like 2D is tied
Structure and with Co (OH)2It orderly closely combines and improves performance, and because of CNTs and Co (OH)2Binding force is weaker, and the two cannot play
The effect of collaboration, therefore, chemical property is poor.
Figure 10 indicates the sample prepared according to embodiment 1 in 0.1M O2The Tafel slope in KOH solution is saturated (in figure
A curve).In figure as a comparison be CNTs/Co (OH) respectively2(the b curve in figure), Co (OH)2(the c curve in figure),
GNRs (the d curve in figure).From Tafel slope figure it can also be seen that GNRs/Co (OH)2Tafel slope be 66mV/
Dec is much smaller than CNTs/Co (OH)2(81mV/dec) and Co (OH)2(109mV/dec) illustrates GNRs/Co (OH)2In electro-catalysis
The overpotential for reaching required when identical current density during analysis oxygen is low, shows GNRs/Co (OH)2Have in catalysis reaction
Faster reaction rate.
Figure 11 indicates the sample GNRs/Co (OH) prepared according to embodiment 12In 0.1M O2The impedance being saturated in KOH solution
Figure.In figure as a comparison be CNTs/Co (OH) respectively2、Co(OH)2,GNRs.Impedance diagram can characterize the electric conductivity of sample,
Rct is diameter corresponding to electronics transfer resistance i.e. semicircle in electrochemical reaction, and the smaller i.e. electric conductivity of semicircle is better.Pass through
Measurement show that the Rct of three kinds of materials is respectively GNRs/Co (OH)2(Rct=24 Ω), CNTs/Co (OH)2(Rct=122 Ω), Co
(OH)2(Rct=124 Ω), it can be seen that the two-dimentional banded structure of GNRs is conducive to the conduction of electronics.
Figure 12 indicates the sample GNRs/Co (OH) prepared according to embodiment 12, for the i-t curve for testing its stability.It is bent
Line expression, the best sample GNRs/Co (OH) of performance2In current density 10mA/cm2Lower reaction 12h, there is no bright for current density
Aobvious variation illustrates GNRs/Co (OH)2Stability is good in electrochemical reaction.
Figure 13 indicates the sample GNRs/Co (OH) prepared according to embodiment 12, to test following for its electroactive area ECSA
Ring volt-ampere curve.A, B, C figure respectively indicate GNRs/Co (OH)2、CNTs/Co(OH)2、Co(OH)2It is arrived in rate for 50mV/s
The cyclic voltammetry curve of 800mV/s, scanning potential region between -0.05V to 0.05V.Cyclic voltammetry (CV) calculates double electricity
Layer capacitance (Cdl) it is a kind of important method electric double layer capacitance (C for studying active surface areadl) value is proportional to effective active surface
Product.CdlValue is respectively GNRs/Co (OH)2(0.353mF/cm2)、CNTs/Co(OH)2(0.151mF/cm2)、Co(OH)2
(0.136mF/cm2) by calculation formula ESCA=Cdl/CS, wherein ic is that the current value v- under open-circuit voltage sweeps speed, CdlIndicate light
Its value of the electric double layer capacitance of sliding electrode surface is usually Cs=0.03mF/cm2.Be calculated ECSA be respectively 11.7,5.1,
4.5.It can thus be seen that GNRs not only increases the electric conductivity of material, and to lamella Co (OH)2Also play the work of dispersion
With increasing electrochemical surface area.
Claims (8)
1. a kind of graphene ribbon/cobalt hydroxide composite nano materials, it is characterized in that a kind of graphene nano with banded structure
Band/cobalt hydroxide composite nano materials, chemical expression are GNRs/Co (OH)2。
2. a kind of graphene ribbon/cobalt hydroxide composite nano materials preparation method, it is characterized in that with graphene nanobelt GNRs
For carbon substrate, GNRs/Co (OH) is synthesized by solvent thermal process2Composite nano materials, the material are a kind of with banded structure
Graphene nanobelt/cobalt hydroxide composite nano materials.
3. graphene ribbon according to claim 2/cobalt hydroxide composite nano materials preparation method, it is characterized in that including
Following steps:
A. GNRs is synthesized using oxidative cleavage CNTs method:
A. multi-walled carbon nanotube is added in the concentrated sulfuric acid and is stirred 1-2 hours, phosphoric acid solution is then added and continues to stir；
B. potassium permanganate powder is added in the solution of stirring, is first stirred at room temperature 1-2 hours, is then slowly heated to 65
DEG C continue to stir；Stop reaction, after being cooled to room temperature, cold deionized water and hydrogenperoxide steam generator is added, by products therefrom
Centrifugation；It is washed respectively three times with hydrochloric acid and ethyl alcohol again, obtains GNRs；
B. GNRs/Co (OH) is synthesized2Composite nano materials:
C. the above-mentioned GNRs being prepared is taken, is dispersed in methanol and is ultrasonically treated；
D. cabaltous nitrate hexahydrate is added in the solution to after being ultrasonically treated, and is stirred at room temperature to adsorb cobalt ions；
E. urea is added, it is polytetrafluoroethylene (PTFE) that liner is sealed in after being stirred at room temperature, and shell is the reaction vessel of steel material
In, carry out solvent thermal reaction；After the reaction was completed, self-heating is cooled to room temperature, and products therefrom is centrifuged, and uses methanol and washing respectively
It washs twice, after 60 DEG C of vacuum ovens are dry, obtains GNRs/Co (OH)2Composite nano materials.
4. graphene ribbon according to claim 2/cobalt hydroxide composite nano materials preparation method, it is characterised in that step
In rapid A, the GNRs of the banded structure is synthesized by the method for oxidative cleavage CNTs.
5. graphene ribbon according to claim 2/cobalt hydroxide composite nano materials preparation method, it is characterised in that step
In rapid B, the GNRs/Co (OH)2Composite nano materials are prepared using solvent-thermal method.
6. graphene ribbon according to claim 2/cobalt hydroxide composite nano materials preparation method, it is characterised in that step
In rapid e, the temperature of solvent thermal reaction is 120 DEG C, and the reaction time is 12 hours.
7. graphene ribbon according to claim 2/cobalt hydroxide composite nano materials preparation method, it is characterised in that step
In rapid c, using methanol as solvent, the additive amount of methanol is 15-25mL；The time of ultrasonication is 20-40 minutes, ultrasonic effect
Keep GNRs fully dispersed in a solvent.
8. graphene ribbon according to claim 2/cobalt hydroxide composite nano materials preparation method, it is characterised in that step
In rapid d, cobalt source is selected from cobalt chloride hexahydrate, cabaltous nitrate hexahydrate, four hydration cobalt acetates, wherein using cabaltous nitrate hexahydrate
Effect is best, and the mass ratio of cabaltous nitrate hexahydrate and GNRs are 1:1.
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