CN109046371A - Efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst and preparation method thereof - Google Patents
Efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- -1 sulfate radical Chemical class 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 150000004780 naphthols Chemical class 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000000703 high-speed centrifugation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
Classifications
-
- B01J35/33—
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst, including cobaltous tungstate and nitrogen-doped graphene piece, the cobaltous tungstate is supported on the nitrogen-doped graphene on piece.It is easy to operate the invention also discloses a kind of preparation method of efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst, raw material green, at low cost, product short preparation period, and it is reproducible.
Description
Technical field
The present invention relates to a kind of efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalysts and preparation method thereof.
Background technique
Electro-catalysis is the heterocatalysis occurred in electrode and electrolyte interface, is to be related to electrochemistry, Surface Science, material supply section
The cross discipline of etc. numerous subsciences.Electro-catalysis be widely used in energy conversion and storage (fuel cell, chemical cell,
Supercapacitor, Hydrogen Energy)；Environmental protection (sewage treatment, electrochemical sensor, degradation organic waste materials, ozone generation etc.)；New object
Matter synthesis and material preparation；Electrochemical Engineering (chlorine industry, intermetallic composite coating, molding, finish etc.)；And the neck such as biology, analysis
In the electrochemical process in domain.
Electrolysis water mainly includes cathode hydrogen evolution and Oxygen anodic evolution two parts, and wherein the efficiency of electrolysis water is by complexity slow 4
Electron anode oxygen evolution reaction determines that efficient Electrochemical oxygen evolution catalysts can solve the slow process of dynamics, mention
High catalytic efficiency.
Noble metal and its oxide show good performance on electro-catalysis oxygen evolution reaction, but their prices compare
Valuableness, and metal oxide containing precious metals are easier to corrode in alkaline medium, this hinders them as analysis oxygen to a certain extent
The application of positive electrode.Therefore, various non-precious metal catalysts have developed into the substitute of noble metal and its oxide.It is usually non-expensive
Metallic catalyst mainly includes spinel oxides and Ca-Ti ore type transition metal oxide and their derivative, stratiform
Double-metal hydroxide, carbon-based non-metallic catalyst and some transition metal complexes etc..
Cobaltous tungstate belongs to divalent transition metal tungstates, and relevant result of study shows cobaltous tungstate micro-nano material in magnetism
Material, microwave dielectric ceramic, photoelectric display material, catalytic decomposition organic pollutant etc. have important role.
Graphene is the two-dimension nano materials of single layer structure, have good chemical stability, splendid electric conductivity and
The unique performance such as high surface area.Material and graphene progress is compound, and the chemical property of material can greatly enhance.But
The water solubility of graphene is bad, is hardly formed in the solution homogeneous.In comparison, graphene oxide is due to surface hydroxyl and carboxylic
The presence of the hydrophilic radicals such as base may be uniformly dispersed in aqueous solution.But graphene oxide is easy accumulation and reunites, to lead
Effective ratio area is caused to reduce.In addition, the electric conductivity of graphene oxide obviously weakens compared with graphene.Therefore graphene oxide structure is used
The chemical property for the composite material built can weaken.
Summary of the invention
The purpose of the present invention is be difficult shape in the solution to solve the water-soluble bad of the graphene in current elctro-catalyst
At homogeneous；Graphene oxide is easy accumulation and reunites, so as to cause effective ratio area reduction；Elctro-catalyst synthesis technology is cumbersome
The technical issues of.
In order to solve the above-mentioned technical problem, on the one hand, the present invention provides a kind of efficient cobaltous tungstate/nitrogen-doped graphene electricity and urges
Agent, including cobaltous tungstate and nitrogen-doped graphene piece, the cobaltous tungstate are supported on the nitrogen-doped graphene on piece.
On the other hand, the present invention provides a kind of preparation method of efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst, including
Following steps:
(1) natural graphite powder and sodium nitrate are added in the cold concentrated sulfuric acid, then in the ice-water bath being stirred continuously slowly
KMnO is added4, the temperature of this process holding mixture is lower than 20 DEG C；
(2) after the mixture of step (1) being stirred 30min at 35 DEG C, being slowly added to deionized water makes temperature rise to 95
DEG C, and keep this temperature 1h；
(3) H is added in the mixed solution of step (2)2O2While deionized water is added, after solid product filters while hot
With HCl solution, into filtrate, there is no until sulfate radical for rinse repeatedly；
(4) by the high speed of 6000rpm after the mixed solution of step (3) being used deionized water supersound washing 3-4 times again
Centrifuge is centrifuged 10min and removes residue；It collects and retains graphene oxide solution, finally disperse in aqueous solution, to form 5mg/mL
Graphene oxide solution, for use；
(5) under agitation, cobalt chloride hexahydrate and Disodium tungstate (Na2WO4) dihydrate are dissolved in water respectively, ammonia is then added
Water is separately added into a certain amount of step (4) resulting graphene oxide solution after stirring；
(6) mixed solution obtained in step (5) is transferred in the reaction kettle of polytetrafluoroethyllining lining, after sealing in
12h is reacted in 180 DEG C of air dry ovens；Gained powder is centrifugated after reacting and being cooled to room temperature, with deionized water and nothing
Alternately washing three times, is placed in 60 DEG C of vacuum ovens dry 4h to water-ethanol；
(7) solid product 5mg obtained in step (6) is weighed to be dissolved in the solution of 1mL (V isopropanol: V water=2:1),
Ultrasonic 30min；Then the naphthols of 40 μ L is added, continues ultrasound 30min；The amount of 5 μ L is pipetted in the glass carbon prepared with liquid-transfering gun
On electrode, chemical property is measured overnight.
Catalyst good water solubility prepared by the present invention, it is easy to form homogeneous in the solution, it is not easy to accumulation and reunion, significantly
Improve effective ratio area；The synthesis technology of this catalyst is simple, raw material green, at low cost, product short preparation period, and again
Renaturation is good.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of graphene oxide prepared by preparation method of the present invention.
Fig. 2 is the X-ray diffractogram of graphene oxide prepared by preparation method of the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of cobaltous tungstate/nitrogen-doped graphene prepared by preparation method of the present invention.
Fig. 4 is that the electrochemistry line of cobaltous tungstate/nitrogen-doped graphene prepared by preparation method of the present invention sweeps curve.
Specific embodiment
Presently in connection with embodiment, the present invention is described in further detail, and application of the invention is not limited to following
Embodiment, the accommodation in any form done to the present invention fall within protection scope of the present invention.
Embodiment
In the present embodiment, graphene oxide synthesis process is as follows:
Graphene oxide is prepared using natural graphite powder as raw material using improved Hummers method.Specific preparation method:
10g natural graphite powder and 5g sodium nitrate are added in the 230mL cold concentrated sulfuric acid, is then slowly added in the ice-water bath being stirred continuously
30g KMnO4, the temperature of this process holding mixture is lower than 20 DEG C.After mixture is stirred 30min at 35 DEG C, it is slowly added to
460mL deionized water makes temperature rise to 95 DEG C, and keeps this temperature 1h.Then 80mL 30%H is being added2O2While be added
720mL deionized water.Solid product uses 1M HCl solution after filtering while hot into filtrate, there is no until sulfate radical for rinse repeatedly.
Residue is removed by supercentrifuge (6000rpm) centrifugation 10min later with deionized water supersound washing 3-4 times again.It collects and protects
Graphene oxide solution is stayed, (5mgmL in aqueous solution is finally dispersed-1), for use.
Surface of graphene oxide is more smooth as seen from Figure 1, and there are electric discharge phenomena, electric conductivity is bad.It can by Fig. 2
Know, graphene oxide diffraction maximum occurs at 2 θ=11.6 °, and the peak is very sharp, and intensity is stronger.It is calculated through bragg's formula
It learns, graphene oxide layer spacing is d=0.78nm.
It is cleaning and 5mgml is added in dry autoclave (V=50mL)-1Graphene oxide 0.5mL, then
The ultrapure water of 35mL, ultrasonic disperse 1h is added.1mmol CoCl is added later2·6H2O is added after being uniformly mixed
The Na of 1mmol2WO4·2H2O continues stirring 15 minutes；Then the ammonium hydroxide of 0.5mL is added into reaction kettle again, continues to stir
Magneton is taken out after 15min.By reaction kettle screwing hermetic it is good after be put into electric heating constant-temperature blowing drying box, react 12 at 180 DEG C
Hour.Cooled to room temperature after reaction takes out product.It is washed for several times with high purity water and dehydrated alcohol respectively, it will be from
It is dry that the product of heart wash clean is placed in vacuum oven.Load graphene 0.5mL product is named as Sample1.Fig. 3 is
The scanning electron microscope (SEM) photograph of Sample1, it can be seen from the figure that rodlike cobaltous tungstate uniform load is on the graphene film of N doping.
Electro-catalysis is carried out with the catalyst prepared in embodiment 2 and produces oxygen experiment, and reaction condition is as follows:
The catalytic performance of elctro-catalyst is tested using Linear Circulation volt-ampere (LSV).The test of chemical property exists
It is carried out on the CHI660D electrochemical workstation of Beijing China Tech Pu Tian scientific & technical corporation, is done with platinum filament to electrode, joined with being saturated calomel and doing
Compare electrode.Weigh 5mg composite catalyst to be dissolved in the solution of 1mL (V isopropanol: V water=2:1), ultrasonic 30min, then plus
Enter the naphthols of 40 μ L, continues ultrasound 30min.The amount for pipetting 5 μ L with liquid-transfering gun measures electricity on the glass-carbon electrode prepared overnight
Chemical property.The electrolyte of test system is the KOH of 0.5M, and the speed of sweeping of LSV is 10mV/s.As shown in Figure 4,1.95V (vs
Current density can achieve 61.7mAcm when RHE)-2。
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (2)
1. efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst, which is characterized in that including cobaltous tungstate and nitrogen-doped graphene piece,
The cobaltous tungstate is supported on the nitrogen-doped graphene on piece.
2. efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst preparation method, which comprises the following steps:
(1) natural graphite powder and sodium nitrate are added in the cold concentrated sulfuric acid, is then slowly added in the ice-water bath being stirred continuously
KMnO4, the temperature of this process holding mixture is lower than 20 DEG C；
(2) after the mixture of step (1) being stirred 30min at 35 DEG C, being slowly added to deionized water makes temperature rise to 95 DEG C, and
Keep this temperature 1h；
(3) H is added in the mixed solution of step (2)2O2While deionized water is added, solid product uses HCl after filtering while hot
Into filtrate, there is no until sulfate radical for rinse repeatedly for solution；
(4) by the high speed centrifugation of 6000rpm after the mixed solution of step (3) being used deionized water supersound washing 3-4 times again
Machine is centrifuged 10min and removes residue；It collects and retains graphene oxide solution, finally disperse the oxygen for forming 5mg/mL in aqueous solution
Graphite alkene solution, for use；
(5) under agitation, cobalt chloride hexahydrate and Disodium tungstate (Na2WO4) dihydrate are dissolved in water respectively, ammonium hydroxide are then added,
A certain amount of step (4) resulting graphene oxide solution is separately added into after stirring；
(6) mixed solution obtained in step (5) is transferred in the reaction kettle of polytetrafluoroethyllining lining, in 180 DEG C after sealing
12h is reacted in air dry oven；Gained powder is centrifugated after reacting and being cooled to room temperature, with deionized water and dehydrated alcohol
Alternately washing three times, is placed in 60 DEG C of vacuum ovens dry 4h；
(7) it weighs solid product 5mg obtained in step (6) to be dissolved in the solution of 1mL (V isopropanol: V water=2:1), ultrasound
30min；Then the naphthols of 40 μ L is added, continues ultrasound 30min；The amount of 5 μ L is pipetted in the glass-carbon electrode prepared with liquid-transfering gun
On, chemical property is measured overnight.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772411A (en) * | 2019-02-22 | 2019-05-21 | 山西大学 | A kind of base metal diatomic elctro-catalyst and its preparation method and application |
| CN113604831A (en) * | 2021-08-06 | 2021-11-05 | 广西师范大学 | Co4S3-WS2Preparation method of oxygen evolution hydrogen evolution electrocatalyst |
| CN113774403A (en) * | 2021-09-22 | 2021-12-10 | 辽宁师范大学 | Water decomposition electrocatalyst Ag8W4O16/CoWO4Preparation method of (1) |
-
2018
- 2018-08-15 CN CN201810926954.3A patent/CN109046371A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772411A (en) * | 2019-02-22 | 2019-05-21 | 山西大学 | A kind of base metal diatomic elctro-catalyst and its preparation method and application |
| CN113604831A (en) * | 2021-08-06 | 2021-11-05 | 广西师范大学 | Co4S3-WS2Preparation method of oxygen evolution hydrogen evolution electrocatalyst |
| CN113604831B (en) * | 2021-08-06 | 2022-12-13 | 广西师范大学 | Co 4 S 3 -WS 2 Preparation method of oxygen evolution hydrogen evolution electrocatalyst |
| CN113774403A (en) * | 2021-09-22 | 2021-12-10 | 辽宁师范大学 | Water decomposition electrocatalyst Ag8W4O16/CoWO4Preparation method of (1) |
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