CN108927177A - Graphene-supported cobalt disulfide particulate composite, preparation method and its usage - Google Patents
Graphene-supported cobalt disulfide particulate composite, preparation method and its usage Download PDFInfo
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- CN108927177A CN108927177A CN201810573912.6A CN201810573912A CN108927177A CN 108927177 A CN108927177 A CN 108927177A CN 201810573912 A CN201810573912 A CN 201810573912A CN 108927177 A CN108927177 A CN 108927177A
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- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011238 particulate composite Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 34
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 15
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 6
- 230000036571 hydration Effects 0.000 claims abstract description 5
- 238000006703 hydration reaction Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 229940011182 cobalt acetate Drugs 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- -1 cobalt sulphur compound Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/40—
-
- 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 discloses a kind of preparation method of graphene-supported cobalt disulfide particulate composite, and key step includes：Prepare the suspension that graphene uniform is dispersed in water；Four hydration cobalt acetates are added into suspension, mechanical stirring is uniform；Ethylenediamine is added into suspension, mechanical stirring is uniform；Carbon disulfide is added into suspension, mechanical stirring is uniform；The suspension being stirred is poured into the reaction kettle of polytetrafluoroethyllining lining, reaction kettle placement is subjected to hydro-thermal reaction in an oven, obtains graphene-supported cobalt disulfide particulate composite.A kind of graphene-supported cobalt disulfide particulate composite is also disclosed, by pure CoS2Object phase composition, CoS2Particle size is about 70-200nm, is uniformly distributed on graphene.The material is also disclosed to apply in catalytic electrolysis water.Equipment needed for the present invention is relatively simple and convenient to operate, condition is controllable, repeatability is high, is relatively suitble to magnanimity preparation.
Description
Technical field
The present invention relates to a kind of efficient, cheap electrolysis water nanocomposites and its preparation method and application, and in particular to
A kind of graphene-supported cobalt disulfide particulate composite, preparation method and its usage.
Background technique
In recent years, energy crisis and environmental pollution become two hang-ups of limitation human social development, and electrolysis water is as new
A generation prepares hydrogen fuel means, can not only obtain efficiently, cleaning, sustainable novel " carbon-free " energy-hydrogen, can be with
Obtain widely used high purity oxygen gas.But the disadvantages of existing overpotential is larger during being somebody's turn to do, dynamics is slow, energy consumption is big is serious
Constrain the development of electrolysis water.The addition of catalyst can not only reduce the overpotential of hydrogen, oxygen evolution, can also accelerate to react
Gas evolution rate and yield is substantially improved in dynamics.Currently, platinum-base material and metal oxide containing precious metals (IrO2,RuO2) be respectively
Two reactions of liberation of hydrogen (Hydrogen evolution reaction) and analysis oxygen (Oxygen evolution reaction) are most
Good commercial catalyst, but fancy price limits a wide range of use of precious metal material.Therefore, research and development reserves are rich
The base metal electrolysis water catalysis material rich, cheap, catalytic activity is high, stability is good has extremely important scientific meaning
And practical value.
In numerous non-precious metal catalysts, transition metal cobalt-based sulfide is low in cost, resourceful, living because having
Property the advantages such as higher, be expected to one of the alternative product as noble metal catalyst, the extensive concern by researchers.In reality
In the application process of border, in order to further increase the catalytic activity of material：On the one hand, by material micro-nano, Nano grade is formed
Structure increases the electrochemical surface area of electrode material to a certain extent, promotes the generation of reaction.But metal-is prepared at present
Sulphur alloy, common method are solid-phase thermal sulphur methods, this method generally requires experience high temperature and pressure heat treatment process, not only energy consumption compared with
Height, and Product size is generally larger, is unable to control to obtain nanometer materials；On the other hand, the electric conductivity of sulfide generally compared with
Difference, general way are to overcome the problems, such as that its native electronic conduction efficiency is low using the method for addition conductive carbon, but meeting in this way
Cause the missing of active material, while some side reactions can be caused, this is also to limit its pass as electrode material practical application
Key.
Summary of the invention
It is an object of the invention to overcome above-mentioned the shortcomings of the prior art, a kind of graphene-supported cobalt disulfide is proposed
Particulate composite, preparation method and its usage.It is proposed that preparation process it is simple, facilitate operation, repeatability is high；Graphite
The cobalt sulphur compound particle size that alkene loads in situ is about 70-200nm, and is evenly distributed, and has splendid energy catalytic applications
Prospect.
First technical solution of the invention be：The preparation method of graphene-supported cobalt disulfide particulate composite, including
Following steps：
1) suspension that graphene uniform is dispersed in water is prepared；
2) four hydration cobalt acetates are added into suspension, carry out mechanical stirring at room temperature；
3) ethylenediamine is added into suspension, carries out mechanical stirring at room temperature；
4) carbon disulfide is added into suspension, carries out mechanical stirring at room temperature；
5) it is poured into the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is placed in an oven, hydro-thermal is carried out to it
Processing；
6) washing sample three times, is collected by centrifugation product, is then freeze-dried after cooling.
The amount of graphene and deionized water is respectively 20-30mg and 35-40mL in suspension in step 1) of the present invention.
The amount of four hydration cobalt acetates is 0.1-0.2g in step 2) of the present invention；Speed of agitator is 200-800r/min, stirring
Time is 5-10min.
The amount of ethylenediamine is 0.1-0.16mL in step 3) of the present invention；Speed of agitator is 200-800r/min, mixing time
For 10-20min.
The amount of carbon disulfide is 0.16-0.24mL in step 4) of the present invention；Speed of agitator is 200-800r/min, when stirring
Between be 10-20min.
Hydro-thermal process temperature is 160-200 DEG C in step 5) of the present invention, hydrothermal conditions 9-12h.
Second technical solution of the invention be：Graphene-supported cobalt disulfide particulate composite, by pure CoS2Object phase group
At CoS2Particle size is about 70-200nm, is uniformly distributed on graphene.
Third technical solution of the present invention is：The purposes of graphene-supported cobalt disulfide particulate composite, catalytic electrolysis
Water application.
Compared with prior art, the present invention has the advantage that：
1) cobalt disulfide nano particle provided by the invention is evenly distributed on graphene, and size is about 70-200nm, solely
Special microstructure is conducive to the exposure of active site and the infiltration of electrolyte, to promote the promotion of chemical property；
2) equipment needed for preparation method proposed by the present invention is relatively simple and convenient to operate, condition is controllable, repeatability is high, than
Relatively it is suitble to magnanimity preparation；
3) graphene can provide three-dimensional conductive network channel as substrate, increase substantially conductivity.Have benefited from this
A little advantages, in alkaline solution, which shows excellent electrolysis water catalytic activity and stability, in terms of
It has broad application prospects.
Detailed description of the invention
Fig. 1 is the XRD curve of graphene-supported cobalt disulfide particulate composite produced by the present invention.
Fig. 2 is the scanning electron microscopic picture of graphene-supported cobalt disulfide particulate composite produced by the present invention.
Fig. 3 is the transmission electron microscope picture of graphene-supported cobalt disulfide particulate composite produced by the present invention.
Fig. 4 is that performance curve is precipitated in the oxygen of graphene-supported cobalt disulfide particulate composite produced by the present invention.
Fig. 5 is that performance curve is precipitated in the hydrogen of graphene-supported cobalt disulfide particulate composite produced by the present invention.
Fig. 6 is that stability curve is precipitated in the oxygen of graphene-supported cobalt disulfide particulate composite produced by the present invention.
Fig. 7 is that stability curve is precipitated in the hydrogen of graphene-supported cobalt disulfide particulate composite produced by the present invention.
Specific embodiment
Below in conjunction with specific embodiment and corresponding attached drawing, the present invention is described in detail.Following embodiment will be helpful to
Those skilled in the art further understands the present invention, but the invention is not limited in any way.It should be pointed out that ability
For the those of ordinary skill in domain, without departing from the inventive concept of the premise, various modifications and improvements can be made.These
Belong to protection scope of the present invention.
Embodiment 1
It is poured into the beaker equipped with 35ml deionized water firstly, weighing 30mg graphene, ultrasonic 1h is so that it becomes uniform
Suspension；It weighs 0.1g tetra- and is hydrated cobalt acetate (Co (CH3COO)2·4H2O) pour into the suspension prepared, at room temperature with
The revolving speed of 800rpm carries out mechanical stirring 10min；It is added in suspension, is continued with the ethylenediamine (EN) that liquid-transfering gun draws 160 μ L
Mechanical stirring 20min is carried out with the revolving speed of 800rpm at room temperature；Carbon disulfide (the CS of 160 μ L is drawn with liquid-transfering gun2) be added
In suspension, continues to carry out mechanical stirring 20min at room temperature with the revolving speed of 800rpm, the liquid being stirred is poured into 50ml's
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is placed in an oven, keeps the temperature 9h at 200 DEG C.After natural cooling, washing
It three times, with sample is collected by centrifugation, is finally freeze-dried.
The XRD diagram of graphene-supported cobalt disulfide particulate composite is as shown in Figure 1, show prepared by above embodiments
Composite material is by the higher CoS of purity2Composition, it is corresponding with JCPDS standard card 41-1471.
Scanning electron microscope (SEM) photograph is as shown in Fig. 2, show that loaded cobalt disulfide particle is evenly distributed on graphene.
Transmission electron microscope is uniformly born on graphene as shown in figure 3, show that the average grain diameter of cobalt disulfide is about 70-90nm
It carries.This structure is convenient for contact and infiltration of the exposure of active site with electrolyte, is conducive to the promotion of chemical property.
By prepared graphene-supported cobalt disulfide particulate composite and isopropanol and binder (Nafion) press than
Example is made into electrode slurry, and wherein the amount of active material, isopropanol and binder is respectively 10mg, 965 μ L, 35 μ L, takes 150 μ L systems
The electrode slurry got ready constitutes three-electrode system in alkaline system as working electrode and is used for coated on the carbon paper of 1*1cm
The test of performance is precipitated in electrochemical hydrogen precipitation/oxygen, is to electrode, 1.0mol/L by reference electrode, carbon-point of saturated calomel electrode
KOH solution be electrolyte form three-electrode system.
The Electrochemical Properties of graphene-supported cobalt disulfide particulate composite：
Fig. 4 and Fig. 5 is respectively that graphene-supported cobalt disulfide particulate composite prepared by above embodiments is full in nitrogen
Oxygen in the 1.0mol/L KOH of sum is precipitated and performance map is precipitated in hydrogen.It can be seen that：It is of the present invention to be loaded on graphene
The oxygen of cobalt disulfide particulate composite is precipitated and hydrogen precipitation activity is more excellent than pure cobalt disulfide particle.
Show after 12h persistently polarizes from study on the stability oxygen being precipitated in Fig. 6 and Fig. 7 and hydrogen is precipitated, keeps
10mA cm-2Overpotential required for electric current increases only 25mV and 40mV, shows graphene-supported two sulphur prepared in the present invention
Changing cobalt granule composite material as electrolysis water catalysis material, there is excellent oxygen precipitation and hydrogen activity and stability is precipitated, in fuel
It has a good application prospect in battery, metal-air battery and electrolysis water.
Embodiment 2
It is poured into the beaker equipped with 40ml deionized water firstly, weighing 20mg graphene, ultrasonic 1h is so that it becomes uniform
Suspension；It weighs 0.1g tetra- and is hydrated cobalt acetate (Co (CH3COO)2·4H2O) pour into the suspension prepared, at room temperature with
The revolving speed of 800rpm carries out mechanical stirring 10min；It is added in suspension, is continued with the ethylenediamine (EN) that liquid-transfering gun draws 160 μ L
Mechanical stirring 20min is carried out with the revolving speed of 800rpm at room temperature；Carbon disulfide (the CS of 160 μ L is drawn with liquid-transfering gun2) be added
In suspension, continues to carry out mechanical stirring 20min at room temperature with the revolving speed of 800rpm, the liquid being stirred is poured into 50ml's
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is placed in an oven, keeps the temperature 9h at 200 DEG C.After natural cooling, washing
It three times, with sample is collected by centrifugation, is finally freeze-dried.
Stone has been made to known to the characterization result of its structure and pattern using X-ray powder diffraction and scanning, transmission electron microscope
Black alkene loads cobalt disulfide particulate composite.The average grain diameter of cobalt disulfide is about 120-150nm, is uniformly born on graphene
It carries.
Embodiment 3
It is poured into the beaker equipped with 35ml deionized water firstly, weighing 30mg graphene, ultrasonic 1h is so that it becomes uniform
Suspension；It weighs 0.2g tetra- and is hydrated cobalt acetate (Co (CH3COO)2·4H2O) pour into the suspension prepared, at room temperature with
The revolving speed of 800rpm carries out mechanical stirring 10min；It is added in suspension, is continued with the ethylenediamine (EN) that liquid-transfering gun draws 100 μ L
Mechanical stirring 20min is carried out with the revolving speed of 800rpm at room temperature；Carbon disulfide (the CS of 240 μ L is drawn with liquid-transfering gun2) be added
In suspension, continues to carry out mechanical stirring 20min at room temperature with the revolving speed of 800rpm, the liquid being stirred is poured into 50ml's
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is placed in an oven, keeps the temperature 9h at 200 DEG C.After natural cooling, washing
It three times, with sample is collected by centrifugation, is finally freeze-dried.
Stone has been made to known to the characterization result of its structure and pattern using X-ray powder diffraction and scanning, transmission electron microscope
Black alkene loads cobalt disulfide particulate composite.The average grain diameter of cobalt disulfide is about 150-200nm, is uniformly born on graphene
It carries.
Embodiment 4
It is poured into the beaker equipped with 35ml deionized water firstly, weighing 30mg graphene, ultrasonic 1h is so that it becomes uniform
Suspension；It weighs 0.1g tetra- and is hydrated cobalt acetate (Co (CH3COO)2·4H2O) pour into the suspension prepared, at room temperature with
The revolving speed of 200rpm carries out mechanical stirring 5min；It is added in suspension, is continued with the ethylenediamine (EN) that liquid-transfering gun draws 160 μ L
Mechanical stirring 10min is carried out with the revolving speed of 200rpm at room temperature；Carbon disulfide (the CS of 160 μ L is drawn with liquid-transfering gun2) be added and hang
In turbid, continue to carry out mechanical stirring 10min at room temperature with the revolving speed of 100rpm, the liquid being stirred is poured into the poly- of 50ml
In the reaction kettle of tetrafluoroethene liner, reaction kettle is placed in an oven, keeps the temperature 9h at 200 DEG C.After natural cooling, washing three
Time, with sample is collected by centrifugation, finally it is freeze-dried.
Stone has been made to known to the characterization result of its structure and pattern using X-ray powder diffraction and scanning, transmission electron microscope
Black alkene loads cobalt disulfide particulate composite.The average grain diameter of cobalt disulfide is about 170-200nm, is uniformly born on graphene
It carries.
Embodiment 5
It is poured into the beaker equipped with 35ml deionized water firstly, weighing 30mg graphene, ultrasonic 1h is so that it becomes uniform
Suspension；It weighs 0.1g tetra- and is hydrated cobalt acetate (Co (CH3COO)2·4H2O) pour into the suspension prepared, at room temperature with
The revolving speed of 800rpm carries out mechanical stirring 10min；It is added in suspension, is continued with the ethylenediamine (EN) that liquid-transfering gun draws 160 μ L
Mechanical stirring 20min is carried out with the revolving speed of 800rpm at room temperature；Carbon disulfide (the CS of 160 μ L is drawn with liquid-transfering gun2) be added
In suspension, continues to carry out mechanical stirring 20min at room temperature with the revolving speed of 800rpm, the liquid being stirred is poured into 50ml's
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is placed in an oven, keeps the temperature 12h at 160 DEG C.After natural cooling, water
It washes three times, with sample is collected by centrifugation, is finally freeze-dried.
Stone has been made to known to the characterization result of its structure and pattern using X-ray powder diffraction and scanning, transmission electron microscope
Black alkene loads cobalt disulfide particulate composite.The average grain diameter of cobalt disulfide is about 80-120nm, is uniformly born on graphene
It carries.
Graphene uniform load cobalt disulfide particulate composite that the present invention is disclosed and proposed and preparation method thereof and electricity
Pole application, those skilled in the art can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although of the invention
Method and technology of preparing be described by preferred embodiment, related technical personnel can obviously not depart from the present invention
Methods and techniques described herein route is modified or is reconfigured in content, spirit and scope, to realize final system
Standby technology.In particular, it should be pointed out that all similar replacements and change are apparent for a person skilled in the art
, they are considered as being included in spirit of that invention, range and content.
Claims (8)
1. the preparation method of graphene-supported cobalt disulfide particulate composite, which is characterized in that include the following steps：
1) suspension that graphene uniform is dispersed in water is prepared；
2) four hydration cobalt acetates are added into suspension, carry out mechanical stirring at room temperature；
3) ethylenediamine is added into suspension, carries out mechanical stirring at room temperature；
4) carbon disulfide is added into suspension, carries out mechanical stirring at room temperature；
5) it is poured into the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is placed in an oven, hydro-thermal process is carried out to it；
6) washing sample three times, is collected by centrifugation product, is then freeze-dried after cooling.
2. the preparation method of graphene-supported cobalt disulfide particulate composite according to claim 1, which is characterized in that
The amount of graphene and deionized water is respectively 20-30mg and 35-40mL in suspension in the step 1).
3. the preparation method of graphene-supported cobalt disulfide particulate composite according to claim 1, which is characterized in that
The amount of four hydration cobalt acetates is 0.1-0.2g in the step 2)；Speed of agitator is 200-800r/min, mixing time 5-
10min。
4. the preparation method of graphene-supported cobalt disulfide particulate composite according to claim 1, which is characterized in that
The amount of ethylenediamine is 0.1-0.16mL in the step 3)；Speed of agitator is 200-800r/min, mixing time 10-20min.
5. the preparation method of graphene-supported cobalt disulfide particulate composite according to claim 1, which is characterized in that
The amount of carbon disulfide is 0.16-0.24mL in the step 4)；Speed of agitator is 200-800r/min, mixing time 10-
20min。
6. the preparation method of graphene-supported cobalt disulfide particulate composite according to claim 1, which is characterized in that
Hydro-thermal process temperature is 160-200 DEG C in the step 5), hydrothermal conditions 9-12h.
7. graphene-supported cobalt disulfide particulate composite, using preparation method described in claim 1, it is characterised in that：
By pure CoS2Object phase composition, CoS2Particle size is about 70-200nm, is uniformly distributed on graphene.
8. the purposes of graphene-supported cobalt disulfide particulate composite according to claim 7, which is characterized in that catalysis
Electrolysis water application.
Priority Applications (1)
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| CN111111699A (en) * | 2019-09-30 | 2020-05-08 | 天津大学 | Nickel-cobalt disulfide composite material and preparation method and application thereof |
| CN111111699B (en) * | 2019-09-30 | 2022-10-21 | 赛帝迦(山东)科技有限公司 | Nickel-cobalt disulfide composite material and preparation method and application thereof |
| CN110931782A (en) * | 2019-11-15 | 2020-03-27 | 中南大学 | Preparation method and application of hollow sphere cobalt sulfide/graphene composite material |
| CN111005036A (en) * | 2019-12-13 | 2020-04-14 | 中国人民大学 | Graphene/cobalt sulfide composite electrode material and preparation method and application thereof |
| CN111005036B (en) * | 2019-12-13 | 2021-07-23 | 中国人民大学 | Graphene/cobalt sulfide composite electrode material and preparation method and application thereof |
| CN113522318A (en) * | 2021-06-23 | 2021-10-22 | 景德镇陶瓷大学 | Difunctional tungsten-cobalt bimetallic electrolytic water catalyst for hydrogen evolution and oxygen evolution and preparation method thereof |
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