CN108816250A - A kind of nanometer stick array composite material and preparation method and application - Google Patents
A kind of nanometer stick array composite material and preparation method and application Download PDFInfo
- Publication number
- CN108816250A CN108816250A CN201810573919.8A CN201810573919A CN108816250A CN 108816250 A CN108816250 A CN 108816250A CN 201810573919 A CN201810573919 A CN 201810573919A CN 108816250 A CN108816250 A CN 108816250A
- Authority
- CN
- China
- Prior art keywords
- composite material
- mos
- nanometer
- stick array
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 71
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 71
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 64
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 239000006260 foam Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000004073 vulcanization Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 31
- 239000010941 cobalt Substances 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 239000011733 molybdenum Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000005864 Sulphur Substances 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 12
- 230000001588 bifunctional effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002003 electron diffraction Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003321 amplification Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 230000005577 local transmission Effects 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [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 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005303 weighing Methods 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
Landscapes
- 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)
- Catalysts (AREA)
Abstract
The embodiment of the invention provides a kind of Co9S8/MoS2/Ni3S2/ NF nanometer stick array composite material, using nickel foam as substrate, the nickel foam partial vulcanization forms Ni3S2Nanometer rods, aligned growth is in foam nickel base；The Co9S8And MoS2The Ni is grown in the form of ultrathin nanometer piece respectively3S2In nanometer rods.Co of the present invention9S8/MoS2/Ni3S2/ NF nanometer stick array composite material can be catalyzed OER and HER reaction simultaneously, be a kind of bifunctional catalyst；Since the material is assembled by ultrathin nanometer piece, there is big specific surface area, the active site of more exposures, while introducing nickel foam with good conductivity and making substrate, there is good electric conductivity and high catalytic activity；This composite material is synthesized by one step hydro thermal method, easy to operate.
Description
Technical field
The present invention relates to nanometer stick array technical field of composite materials, more particularly to a kind of Co9S8/MoS2/Ni3S2/NF
Nanometer stick array composite material and preparation method and application.
Background technique
It is electrolysed aquatic products hydrogen and produces oxygen, electric energy is efficiently stored in chemical bond in large quantities, solve what electric energy was difficult to store
Meanwhile the Hydrogen Energy that no pollution, calorific value are high and can be recycled is also obtained, it is the efficient preparation cleaning of one kind, sustainable energy
Technology.But water-splitting reaction two half-reactions (evolving hydrogen reaction HER and oxygen evolution reaction OER) require it is larger
Activated energy barrier, need the energy barrier and overpotential of suitable the two half-reactions of catalyst degradation.
Currently, the highest evolving hydrogen reaction catalyst of activity is Pt sill, and active high oxygen evolution reaction catalysts are
RuO2And IrOxMaterial, but these precious metal materials because reserves it is few, expensive, the disadvantages of easy in inactivation, limits it and answers on a large scale
With therefore, the controlledly synthesis of base metal base nanometer electrical catalyst becomes research hotspot.In recent years, domestic and international scientist's success
The multiple materials such as transient metal sulfide, phosphide, hydroxide and phosphate have been synthesized, have produced hydrogen, production oxygen performance side in catalysis
Face obtains some progress, but electric conductivity, multifunctionality and in terms of there are still some problems.Therefore, one is found
Kind convieniently synthesized, high activity with good conductivity, multifunction catalyst are still the significant challenge in electrolysis water field.
Summary of the invention
The embodiment of the present invention is designed to provide a kind of nanometer stick array composite material, especially a kind of Co9S8/MoS2/
Ni3S2/ NF nanometer stick array composite material, using as the multifunction catalyst that can be used for HER and OER.The present invention also provides one kind
Co9S8/MoS2/Ni3S2The preparation method and application of/NF nanometer stick array composite material.Specific technical solution is as follows：
First aspect present invention provides a kind of Co9S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with nickel foam
For substrate, the nickel foam partial vulcanization forms Ni3S2Nanometer rods, aligned growth is in foam nickel base；The Co9S8And MoS2
The Ni is grown in the form of ultrathin nanometer piece respectively3S2In nanometer rods.
Herein, predicate " ultrathin nanometer piece " has the general sense of its fields, generally refers to thickness less than 10nm
Nanometer sheet.
In some embodiments of first aspect present invention, it is 200-500 μm that the nickel foam (NF), which has aperture,
Three-dimensional porous structure.The present invention uses nickel foam, on the one hand has good electric conductivity, and on the other hand, the three-dimensional of nickel foam is more
Pore structure increases the surface area of substrate for nickel sheet, is more favorable for contact and generation of the catalyst with electrolyte
The release of gas.
In some embodiments of first aspect present invention, the diameter of the nanometer rods is 300-600nm；The nanometer
The length of stick is 1.0-2.0 μm, and nanometer rods aligned growth in foam nickel base forms nanometer stick array.
In some embodiments of first aspect present invention, the ultrathin nanometer piece with a thickness of 2-4nm, it is this ultra-thin
Nanometer sheet has bigger specific surface area and more exposed active site, is more favorable for electronics transfer and generates releasing for gas
It puts, is conducive to the raising of catalyst performance.
Second aspect of the present invention provides a kind of Co as described in the first aspect of the invention9S8/MoS2/Ni3S2/ NF nanometer rods
The preparation method of array composite material, includes the following steps：
(1)：Nickel foam is pre-processed, with the oxide for the nickel surface that defoams；
(2)：Obtain the reactant aqueous solution containing cobalt source, molybdenum source, sulphur source and hydrazine hydrate；
(3)：Nickel foam is placed in the reactant aqueous solution, hydro-thermal reaction is carried out；Hydrothermal temperature is 180-220
DEG C, preferably 200 DEG C, the hydro-thermal reaction time is 18-26 hours, preferably 24 hours；
(4)：After reaction, it washs, it is dry, obtain Co9S8/MoS2/Ni3S2/ NF nanometer stick array composite material.
Pretreated operation is carried out to nickel foam in step (1) to generally include：Nickel foam is immersed in a certain concentration
Acid solution in, such as hydrochloric acid, sulfuric acid, nitric acid, its object is to remove one layer of oxygen of foam nickel surface oxidation by air formation
Change nickel, be based on this purpose, other preprocess methods can also be used in those skilled in the art, and the present invention is it is not limited here.It is adopting
When being handled with acid solution, without easily controllable, HCl treatment is conventional means for sulfuric acid, nitric acid reaction excessive velocities.In the present invention
In some embodiments of second aspect, 0.8-1.5M HCl solution can be selected, preferably 1M HCl impregnates nickel foam 10-30
Minute, preferably 20 minutes；Those skilled in the art can adjust the concentration and pretreatment time of hydrochloric acid according to the actual situation, with
It is observed under scanning electron microscope, the smooth Indicator Reaction of foam nickel surface terminates.
Cobalt element, molybdenum member in some embodiments of second aspect of the present invention, in the cobalt source, molybdenum source and sulphur source
Plain, element sulphur molar ratio is 1:(0.8-1.2):(2-4), preferably 1:1:3.
In some embodiments of second aspect of the present invention, the cobalt source is selected from water soluble cobaltous salt, such as cobaltous sulfate, nitre
One of sour cobalt, cobalt chloride or combinations thereof, preferably cobaltous sulfate；The molybdenum source be selected from water-soluble molybdenum hydrochlorate, such as sodium molybdate,
One of ammonium molybdate or combinations thereof, preferably sodium molybdate；The sulphur source is selected from one of thiocarbamide, thioacetamide or its group
It closes, preferably thiocarbamide.
In some embodiments of second aspect of the present invention, the molal quantity of the cobalt element in the cobalt source and hydrazine hydrate
Mass ratio is 3：(5-20)mmol/g.In actual production, the hydrazine hydrate exists usually in the form of hydrazine hydrate aqueous solution, example
Such as the commercially available hydrazine hydrate aqueous solution that can be mass fraction 65%-85%；In the present invention, can use mass fraction for
80% hydrazine hydrate aqueous solution.
In other embodiments of second aspect of the present invention, cobalt element content is in the reactant aqueous solution
0.01-0.5mol/L；The total volume of the reactant aqueous solution be reactor volume 50%-70%, preferably 60%；It is described
Nickel foam is immersed in the reactant aqueous solution.
In some embodiments of second aspect of the present invention, step (3) after reaction, take out foam nickel material,
Obtain the precursor crude product of composite material；Then it is alternately washed with water and ethyl alcohol, obtains composite material after dry；Certainly, in addition to
Ethyl alcohol, organic solvent that can also be volatile, less toxic using acetone etc. are thick to replace the precursor of composite material obtained by ethanol washing
Product.
Cobalt source described in second aspect of the present invention, molybdenum source, sulphur source, hydrazine hydrate aqueous solution, nickel foam etc. are purchased from business
Approach, this will not be repeated here.
Third aspect present invention provides Co9S8/MoS2/Ni3S2/ NF nanometer stick array composite material is in electro-catalysis complete solution water
In application.
A kind of Co provided in an embodiment of the present invention9S8/MoS2/Ni3S2/ NF nanometer stick array composite material, can be catalyzed simultaneously
OER and HER reaction, is a kind of bifunctional catalyst, can be applied to complete solution water；Since the material has ultrathin nanometer chip architecture,
With big specific surface area, the active site of more exposures, while introducing nickel foam with good conductivity and making substrate, have good
Electric conductivity and high catalytic activity；This composite material is easy to operate by hydrothermal synthesis method one-step synthesis.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is XRD diagram corresponding to embodiment 1 and comparative example 1-3, wherein (a)-(d) is followed successively by comparative example 3, comparative example
1, comparative example 2, the XRD diagram of composite material prepared by embodiment 1.
Fig. 2 is SEM photograph corresponding to embodiment 1 and comparative example 1-3, wherein (a)-(c) is prepared by comparative example 3
Composite material Ni3S2SEM photograph of/the NF under different amplification；(d)-(f) is composite material prepared by comparative example 2
MoS2/Ni3S2SEM photograph of/the NF under different amplification；(g)-(i) is composite material Co prepared by comparative example 19S8/
Ni3S2SEM photograph of/the NF under different amplification；(j)-(l) is composite material Co prepared by embodiment 19S8/MoS2/
Ni3S2SEM photograph of/the NF under different amplification.
Fig. 3 is Co prepared by embodiment 19S8/MoS2/Ni3S2The transmission electron microscope (TEM) of/NF nanometer stick array composite material
With high-resolution-ration transmission electric-lens (HRTEM) image.(b) figure is local transmission Electronic Speculum (TEM) image of a nanorod structure；(d)
Figure is the local transmission sem image of certain nanometer of panel region；(a) figure is the HRTEM image (illustration of (b) figure lower-left encircled
(a1) it is Co9S8The selective electron diffraction figure (SAED figure) of nanometer sheet, illustration (a2) it is Ni3S2The selective electron diffraction of nanometer rods
Figure)；(c) figure be (b) figure upper right encircled HRTEM image (figure (c) in illustration be MoS2The SAED of nanometer sheet schemes).
Fig. 4 is the reaction of OER corresponding to embodiment 1 and comparative example 1-3 and the LSV curve and Tafel slope of HER；Wherein
It (a) is the LSV curve of the OER reaction of 4 kinds of composite materials；It (b) is the Tafel slope of the OER reaction of 4 kinds of composite materials；(c) it is
The LSV curve of the HER reaction of 4 kinds of composite materials under alkaline condition；(d) anti-for the HER of 4 kinds of composite materials under alkaline condition
The Tafel slope answered；(e) the LSV curve of the HER reaction for 4 kinds of composite materials in acid condition；It (f) is 4 kinds of composite materials
The Tafel slope of HER reaction in acid condition.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
MoS2/Co9S8/Ni3S2The preparation embodiment of/NF nanometer stick array composite material
Embodiment 1
Nickel foam pretreatment：By the nickel foam of a piece of 6cm × 10cm (NF, 200-500 μm of aperture, Shenzhen day at have
Limit company) 20 minutes are dipped into 1M HCl to remove oxide on surface, water and ethanol washing are then used, dry, weighing.
Weigh 0.843g CoSO4·7H2O、0.723g Na2MoO4·2H2O and 0.685g CH4N2S (cobalt, molybdenum, sulphur mole
Than 1:1:3) it is added to 80mL reaction kettle, adds 33mL water and 12.36g hydrazine hydrate aqueous solution (mass fraction 80%, volume
15mL), NF is added after stirring 30 minutes, seals reaction kettle, reacts for 24 hours for 200 DEG C in an oven.Naturally cool to room temperature, water and
Ethyl alcohol alternately washs, and product drying in 40 DEG C of vacuum tanks for 24 hours, obtains composite material, is denoted as Co9S8/MoS2/Ni3S2/NF.Institute
State Co in composite material9S8、MoS2And Ni3S2Total load amount be 1.85mgcm-2)。
Embodiment 2
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：The nickel foam preprocessing process is:Nickel foam (NF) is dipped into 0.8M HCl 30 minutes.
Embodiment 3
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：The nickel foam preprocessing process is:Nickel foam (NF) is dipped into 1.2M HCl 10 minutes.
Embodiment 4
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：Weigh 0.843g CoSO4·7H2O、0.581g Na2MoO4·2H2O and 0.457g CH4N2S (cobalt, molybdenum,
Sulphur molar ratio 1:0.8:2) it is added to 80mL reaction kettle.
Embodiment 5
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：Weigh 0.873g Co (NO3)2·6H2O、0.582g(NH4)6Mo7O24·4H2O and 0.685g CH4N2S
(cobalt, molybdenum, sulphur molar ratio 3:3.5:9) it is added to 80mL reaction kettle.
Embodiment 6
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：Weigh 0.714g CoCl2·6H2O、0.723g Na2MoO4·2H2O and 0.902g CH3CSNH2(cobalt,
Molybdenum, sulphur molar ratio 1:1:4) it is added to 80mL reaction kettle.
Embodiment 7
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：It is added 6.59g hydrazine hydrate aqueous solution (volume 8ml).
Embodiment 8
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：It is added 16.48g hydrazine hydrate aqueous solution (volume 20ml).
Embodiment 9
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：25mL water is added.
Embodiment 10
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：41mL water is added.
Embodiment 11
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：It reacts 26 hours for 180 DEG C in an oven.
Embodiment 12
Co is prepared according to the method for embodiment 19S8/MoS2/Ni3S2/ NF nanometer stick array composite material, with embodiment 1
The difference is that：It reacts 18 hours for 220 DEG C in an oven.
Comparative example 1
Co is prepared according to the method for embodiment 19S8/Ni3S2/ NF composite material, except Na is not added2MoO4·2H2Outside O, other
Step and parameter are same as Example 1.Resulting materials are denoted as Co9S8/Ni3S2/NF(Co9S8、Ni3S2Total load amount be
1.79mg·cm-2)。
Comparative example 2
MoS is prepared according to the method for embodiment 12/Ni3S2/ NF composite material, except CoSO is not added4·7H2Outside O, other steps
It is same as Example 1 with parameter.Resulting materials are denoted as MoS2/Ni3S2/NF(MoS2、Ni3S2Total load amount be 1.81mg
cm-2)。
Comparative example 3
Ni is prepared according to the method for embodiment 13S2/ NF composite material, except CoSO is not added4·7H2O and Na2MoO4·2H2O
Outside, other steps and parameter are same as Example 1.Resulting materials are denoted as Ni3S2/NF(Ni3S2Load capacity be 0.4mgcm-2)。
MoS2/Co9S8/Ni3S2The characterization and test of/NF nanometer stick array composite material
1, XRD analysis
X-ray powder diffraction instrument (the model produced using company of Dutch Panaco company：X Pert PRO MPD) to this
The composite material prepared in inventive embodiments 1 and comparative example 1-3 carries out X-ray diffraction analysis, and analysis result is as shown in Figure 1；Point
Radioactive source during analysis is Cu-Ka, and measurement step-length is 0.017 °, and sweep time is 10 seconds/step.
Fig. 1 is XRD diagram corresponding to embodiment 1 and comparative example 1-3, and (a) is composite material prepared by comparative example 3 in Fig. 1
Ni3S2The XRD diagram of/NF, the Series diffractive peak that 2 θ are 21.8 °, 31.1 °, 49.7 °, 50.1 °, 55.2 ° and 55.3 ° in figure correspond to
Ni3S2(101) of (PDF card number 44-1418), (110), (113), (211), (122) and (300) crystal face, meanwhile, 2 θ are
44.5 °, 51.8 ° and 76.4 ° of peak corresponds to the diffraction of nickel foam (PDF card number 04-0850), illustrates in the water-heat process
Foam nickel surface generates Ni by partial vulcanization3S2.(b) is Co prepared by comparative example 1 in Fig. 19S8/Ni3S2/ NF composite material
XRD diagram, it can be seen that be added cobalt source and be added without molybdenum source, diffraction peak setting in 2 θ=29.8 °, 31.2 °, 47.6 °,
52.1 °, with face-centered cubic Co9S8The peak position of standard card (PDF card number is 65-6801) is consistent, illustrates life after addition cobalt source
At face-centered cubic Co9S8.(c) MoS prepared for comparative example 22/Ni3S2The XRD diagram of/NF composite material, it can be seen that molybdenum is added
Source and be added without cobalt source, corresponded respectively to positioned at 2 θ=14.5 °, 33.0 °, 34.0 °, 38.4 °, the diffraction maximums of 41.1 ° and 76.2 °
MoS2(003) of (PDF card number 17-0744), (101), (012), (104), (015) and (119) crystal face, it was demonstrated that molybdenum source is added
After generate MoS2.(d) Co synthesized for embodiment 19S8/MoS2/Ni3S2The XRD diagram of/NF, it is seen that MoS2、Co9S8、Ni3S2With
The diffraction maximum of nickel foam occurs, and thus proves, in the composite material of the method synthesis, MoS has been loaded in foam nickel base2、
Co9S8And Ni3S2。
2, scanning electron microscope analysis
It is carried out using pattern of the scanning electron microscope (SEM) to composite material prepared by embodiment 1 and comparative example 1-3
Characterization, as a result as shown in Figure 2.Wherein, (a)-(c) is Ni prepared by comparative example 33S2The SEM photograph of/NF can be seen in (a) figure
It arrives, the nickel foam through partial vulcanization still keeps the frame of nickel foam, there is 200-500 μm of diameter of three-dimensional porous structure, continues
Amplify its visible rough surface (b), and some small protrusions (c) occurs.After molybdenum source is added (comparative example 2), it is seen that many is received
Rice stick is grown in foam nickel base (e), and nanorod surfaces can be clearly apparent by, which being further amplified, grows a large amount of nanometer sheets, such as
Scheme in (f) shown in arrow.Equally, after addition cobalt source (comparative example 1), a large amount of nanometer rods (h) are also grown in foam nickel base,
But the nanometer sheet in nanometer rods is relatively fewer in SEM photograph, as shown in arrow in figure (i).Figure (j)-(l) is while molybdenum is added
The SEM photograph in source and cobalt source (embodiment 1) products therefrom, still visible to have a large amount of nanorod structures, length is about 1.0-2.0
μm, diameter is about 300-600nm (k), and nanorod surfaces have a large amount of ultrathin nanometer chip architectures (in figure (l) shown in arrow).Invention
People has found under study for action, Co9S8/MoS2/Ni3S2The tool of this ultrathin nanometer chip architecture in/NF nanometer stick array composite material
There are bigger specific surface area and more exposed active site, be more favorable for electronics transfer and generate the release of gas, is conducive to
The raising of catalyst performance；In addition, Co9S8/MoS2/Ni3S2Nanorod structure in/NF nanometer stick array composite material is directly raw
It is longer than foam nickel base, electric conductivity is good, is equally beneficial for the raising of catalyst performance.
3, transmission electron microscope analysis
Fig. 3 is Co prepared by embodiment 19S8/MoS2/Ni3S2The transmission electron microscope (TEM) of/NF nanometer stick array composite material
With high-resolution-ration transmission electric-lens (HRTEM) image.(b) figure is local transmission Electronic Speculum (TEM) figure of a nanorod structure in Fig. 3
Picture, (d) figure is the local transmission sem image of certain nanometer of panel region；(a) figure is the HRTEM image of (b) figure lower-left encircled,
(a) illustration (a in figure1) it is Co9S8The selective electron diffraction figure (SAED figure) of nanometer sheet, illustration (a2) it is Ni3S2Nanometer rods
Selective electron diffraction figure (SAED figure)；(c) figure is the HRTEM image of (b) figure upper right encircled in Fig. 3, and (c) illustration is in figure
MoS2The SAED of nanometer sheet schemes.
It can be seen that there is the spacing of lattice of 0.29nm and 0.41nm from (a) figure of Fig. 3, Ni is corresponded respectively to3S2's
(110) and (101) crystal face, illustration (a2) be monocrystalline Ni3S2Selective electron diffraction figure, illustrate nanometer rods center be monocrystalline
Ni3S2.There is the spacing of lattice of 0.28nm and 0.19nm in nanometer bar edge, corresponds respectively to Co9S8(222) and (511) it is brilliant
Face；From illustration (a1) in can also correspond to out Co9S8(311) and (511) crystal face (such as illustration (a1) in shown in arrow), explanation
There is Co in nanometer rods9S8Nanometer sheet.Scheme the spacing of lattice that can see clearly 0.27nm and 0.62nm in (c), corresponds respectively to
MoS2(100) and (002) crystal face, scheme (c) illustration in can also correspond to out MoS2(100) and (103) crystal face (in such as illustration
Shown in arrow), illustrate nanometer rods surrounding growth MoS2Nanometer sheet.From figure (d) as it can be seen that MoS of the present invention2/Co9S8/
Ni3S2The thickness about 2-4nm of nanometer sheet in/NF nanometer stick array composite material, such as 3.5nm.It is known to those skilled in the art that
MoS2And Co9S8Usually each self-forming when forming nanometer sheet, it follows that MoS of the present invention2/Co9S8/Ni3S2/ NF receives
Rice stick array composite material is the Ni by center3S2Nanometer rods and the ultra-thin Co being grown in nanometer rods9S8Nanometer sheet and MoS2It receives
Rice piece composition.
4, electrocatalysis characteristic is tested
The present embodiment uses traditional three-electrode system, tests composite material prepared by embodiment 1 and comparative example 1-3
It is catalyzed the performance of OER and HER.In the three-electrode system, Pt plate electrode is made to electrode, and Hg/HgO electrode makees reference electrode, real
It applies after composite material prepared by example 1 and comparative example 1-3 is cut into 1cm × 1cm respectively, directly as working electrode；OER test
It is carried out in 1.0M KOH, sweeping speed is 2mV-1.HER is tested respectively in 1.0M KOH and 0.5M H2SO4Middle completion, sweeping speed is 5mV-1。
The result of electrocatalysis characteristic test is as shown in Figure 4.(a) figure and (b) figure are respectively different composite material in Fig. 4
The polarization curve (LSV curve) and Tafel slope of OER reaction, as can be seen that Co from (a) figure9S8/MoS2/Ni3S2/ NF nanometers
Stick array composite material shows good OER catalytic activity.It is 10mAcm by electric current-2When voltage be denoted as V10, difference is again
Condensation material is catalyzed the overpotential η of OER reaction10
(mV)=(V10- 1.23) × 1000, available according to (a) figure in Fig. 3, Co9S8/MoS2/Ni3S2/ NF nanometer rods
Array composite material only needs the overpotential of 112mV that can reach 10mAcm-2Current density, overpotential be far below Co9S8/
Ni3S2/NF(η10=251mV), MoS2/Ni3S2/NF(η10=252mV) and Ni3S2/NF(η10=299mV).(b) figure is shown
The Tafel slope of several composite materials.It can be seen that Co9S8/MoS2/Ni3S2/ NF has low-down Tafel slope (58mV
dec-1), this also illustrates Co9S8/MoS2/Ni3S2/ NF has more excellent OER catalytic performance.
Existing document reports that molybdenum base material has the catalytic activity of HER in acid condition more, and rarely has under alkaline condition
The report of catalytic activity with HER reaction；Inventor is under study for action it was unexpectedly observed that Co9S8/MoS2/Ni3S2/ NF nanometer rods
Array composite material also has superior catalytic performance to HER reaction in alkaline environment.In Fig. 4 shown in (c) figure, Co9S8/
MoS2/Ni3S2/ NF has minimum take-off potential (η1=22mV)；Meanwhile Co9S8/MoS2/Ni3S2/ NF reaches 10mAcm-2
Current density overpotential η10162mV is only needed, in contrast, MoS2/Ni3S2/NF(η10=188mV), Co9S8/Ni3S2/NF
(η10=217mV), Ni3S2/NF(η10=263mV) there is higher overpotential, and under identical current potential, current density ratio
MoS2/Co9S8/Ni3S2/ NF is small.Co9S8/MoS2/Ni3S2The HER catalytic activity of/NF under alkaline environment can also can be from Tafel
Slope result is found out, as shown in (d) figure, Co9S8/MoS2/Ni3S2The Tafel slope of/NF nanometer stick array composite material is
145mV·dec-1, hence it is evident that it is lower than Co9S8/Ni3S2/NF(165mV·dec-1)、MoS2/Ni3S2/NF(176mV·dec-1) and
Ni3S2/NF(243mV·dec-1) Tafel slope, illustrate Co9S8/MoS2/Ni3S2/ NF nanometer stick array composite material is in alkali
Property environment in HER reaction have superior catalytic performance.
(e) figure is the LSV curve that different composite material is catalyzed HER reaction in acid condition in Fig. 4, it can be seen that
MoS2/Co9S8/Ni3S2The take-off potential of/NF composite material is nearly close to 0 (η1=13mV)；Simultaneously in several composite materials
In, MoS2/Co9S8/Ni3S2/ NF composite material reaches 10mAcm-2Current density overpotential η1083mV is only needed, is gathered around simultaneously
There is minimum Tafel slope (55mVdec-1)；And Co9S8/Ni3S2/NF(η10=176mV), MoS2/Ni3S2/NF(η10=
231mV)、Ni3S2/NF(η10=249mV) then possess higher overpotential and bigger Tafel slope, respectively 86,164 and
132mV·dec-1.As it can be seen that Co9S8/MoS2/Ni3S2/ NF also has good HER catalytic activity in acidic environment.
MoS provided by the present invention2/Co9S8/Ni3S2/ NF nanometer stick array composite material had not only had OER catalytic activity, but also
It is a kind of bifunctional catalyst with HER catalytic activity；Inventor is under study for action it was unexpectedly observed that Co9S8/MoS2/Ni3S2/NF
Nanometer stick array composite material ratio Co9S8/Ni3S2/NF、MoS2/Ni3S2/ NF and Ni3S2There is/NF higher OER and HER to urge
Change activity.
Moreover, the prior art is reported, when molybdenum base material is as HER catalyst, generally there is HER catalysis in acid condition
Activity；And inventor is surprisingly it has been found that Co provided by the present invention9S8/MoS2/Ni3S2/ NF nanometer stick array composite material
Also there is very high HER catalytic activity under alkaline condition.Complete solution water usually requires to carry out under neutral or basic conditions, and this hair
MoS provided by bright2/Co9S8/Ni3S2/ NF nanometer stick array composite material has urging for OER and HER simultaneously under alkaline condition
Change activity, therefore can be applied to electro-catalysis complete solution water.
It should be noted that, in this document, the terms "include", "comprise" or its any other variant are intended to non-row
His property includes, so that the process, method, article or equipment for including a series of elements not only includes those elements, and
And further include other elements that are not explicitly listed, or further include for this process, method, article or equipment institute it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including institute
State in the process, method, article or equipment of element that there is also other identical elements.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention
It is interior.
Claims (10)
1. a kind of Co9S8/MoS2/Ni3S2/ NF nanometer stick array composite material, which is characterized in that described using nickel foam as substrate
Nickel foam partial vulcanization forms Ni3S2Nanometer rods, aligned growth is in foam nickel base；The Co9S8And MoS2Respectively with ultra-thin
The form of nanometer sheet is grown in the Ni3S2In nanometer rods.
2. composite material as described in claim 1, it is characterised in that it is 200-500 μm of three-dimensional that the nickel foam, which has aperture,
Porous structure.
3. composite material as described in claim 1, which is characterized in that the diameter of the nanometer rods is 300-600nm；Length is
1.0-2.0μm。
4. composite material as described in claim 1, which is characterized in that the ultrathin nanometer piece with a thickness of 2-4nm.
5. a kind of such as Co of any of claims 1-49S8/MoS2/Ni3S2The system of/NF nanometer stick array composite material
Preparation Method includes the following steps：
(1)：Nickel foam is pre-processed, with the oxide for the nickel surface that defoams；
(2)：Obtain the reactant aqueous solution containing cobalt source, molybdenum source, sulphur source and hydrazine hydrate；
(3)：Nickel foam is placed in the reactant aqueous solution, hydro-thermal reaction is carried out；Hydrothermal temperature is 180-220 DEG C,
Preferably 200 DEG C, the hydro-thermal reaction time is 18-26 hours, preferably 24 hours；
(4)：After reaction, it washs, it is dry, obtain Co9S8/MoS2/Ni3S2/ NF nanometer stick array composite material.
6. method as claimed in claim 5, which is characterized in that the pretreatment in step (1) includes：
By nickel foam in 0.8-1.5M HCl solution, 10-30 minutes, preferably 20 minutes are impregnated preferably in 1M HCl solution.
7. method as claimed in claim 5, which is characterized in that cobalt element, molybdenum element in the cobalt source, molybdenum source and sulphur source,
The molar ratio of element sulphur is 1:(0.8-1.2):(2-4), preferably 1:1:3.
8. method as claimed in claim 5, which is characterized in that the cobalt source in cobaltous sulfate, cobalt nitrate, cobalt chloride one
Kind or combinations thereof；The molybdenum source is selected from one of sodium molybdate, ammonium molybdate or combinations thereof；The sulphur source is selected from thiocarbamide, thio second
One of amide or combinations thereof.
9. method as claimed in claim 5, which is characterized in that the molal quantity of the cobalt element in the cobalt source and the matter of hydrazine hydrate
Amount is than being 3：(5-20)mmol/g.
10. Co of any of claims 1-49S8/MoS2/Ni3S2/ NF nanometer stick array composite material is complete in electro-catalysis
Application in Xie Shui.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810573919.8A CN108816250B (en) | 2018-06-06 | 2018-06-06 | Nanorod array composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810573919.8A CN108816250B (en) | 2018-06-06 | 2018-06-06 | Nanorod array composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108816250A true CN108816250A (en) | 2018-11-16 |
| CN108816250B CN108816250B (en) | 2020-02-18 |
Family
ID=64144172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810573919.8A Expired - Fee Related CN108816250B (en) | 2018-06-06 | 2018-06-06 | Nanorod array composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108816250B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109686591A (en) * | 2018-12-17 | 2019-04-26 | 东南大学 | Sheet Ni3S2Coat column Ni3S2The preparation method of array electrode |
| CN110075873A (en) * | 2019-04-29 | 2019-08-02 | 苏州大学 | It is layered the Fe-MoS of self assembly2/Ni3S2/ NF composite nano materials and the preparation method and application thereof |
| CN110327942A (en) * | 2019-05-06 | 2019-10-15 | 湖北大学 | The flower-shaped MoS of lamella micron2/Ni3S2/ NiFe-LDH/NF material and its synthetic method and application |
| CN110449170A (en) * | 2019-08-12 | 2019-11-15 | 浙江师范大学 | A kind of amorphous state MoS2Modify CoS/Co0.85The preparation method of the heterogeneous nano-tube array elctro-catalyst of Se |
| CN110694646A (en) * | 2019-10-22 | 2020-01-17 | 上海交通大学 | Bimetallic sulfide composite electrocatalyst and preparation method and application thereof |
| CN110752096A (en) * | 2019-10-25 | 2020-02-04 | 青岛科技大学 | Multidimensional structure metal sulfide Ni3S2/Co3S4Preparation of (A) and its use in supercapacitors |
| CN110813323A (en) * | 2019-11-19 | 2020-02-21 | 中山大学 | High-efficiency and durable hydrogen evolution nickel-based catalyst constructed by atomic layer deposition and preparation method and application thereof |
| WO2020092188A1 (en) * | 2018-10-29 | 2020-05-07 | Northwestern University | Composite, hierarchical electrocatalytic materials for water splitting |
| CN111524714A (en) * | 2020-04-06 | 2020-08-11 | 电子科技大学 | Preparation method of self-supporting nano array with secondary structure |
| CN111686764A (en) * | 2020-05-06 | 2020-09-22 | 东莞理工学院 | Fe-Ni (OH)2/Ni3S2@ NF heterostructure and preparation method and application thereof |
| CN112023942A (en) * | 2020-09-03 | 2020-12-04 | 广州大学 | NiMoO3S/foam nickel composite material and preparation method and application thereof |
| CN112133886A (en) * | 2020-08-12 | 2020-12-25 | 南昌航空大学 | Preparation method and application of in-situ integrated electrode for alkali ion battery |
| CN112169824A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Co9S8Preparation method of/N-CCA composite electrode |
| CN112473697A (en) * | 2020-12-04 | 2021-03-12 | 福州大学 | Nickel-cobalt-tungsten multi-sulfide bifunctional catalyst with core-shell spherical structure and preparation method and application thereof |
| CN113713833A (en) * | 2021-09-15 | 2021-11-30 | 北京师范大学 | Molybdenum oxysulfide/nickel sulfide/foamed nickel complex and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105332003A (en) * | 2015-11-30 | 2016-02-17 | 天津理工大学 | Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies |
| CN105428081A (en) * | 2015-12-28 | 2016-03-23 | 吉林大学 | Ni3S2 coated MMoO4 composite material grown in-site on metal substrate and application of composite material |
| CN105664977A (en) * | 2016-02-03 | 2016-06-15 | 中国科学院化学研究所 | Molybdenum disulfide-cadmium sulfide nanometer composite material and preparing method and application thereof |
| CN106521460A (en) * | 2016-10-31 | 2017-03-22 | 华南理工大学 | A preparing method for a hydrogen production composite catalytic electrode |
| CN107010670A (en) * | 2016-07-27 | 2017-08-04 | 北京大学 | A kind of MoSxOy/ carbon nano-composite material, its preparation method and its application |
| CN107051550A (en) * | 2017-04-24 | 2017-08-18 | 山东大学 | A kind of electro-catalysis water decomposition MoSe2/Co0.85Se composites and preparation method and application |
| CN107968208A (en) * | 2017-12-01 | 2018-04-27 | 吉林大学 | A kind of nano-lamellar structure of three nickel of curing/molybdenum disulfide composite material and preparation method thereof |
-
2018
- 2018-06-06 CN CN201810573919.8A patent/CN108816250B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105332003A (en) * | 2015-11-30 | 2016-02-17 | 天津理工大学 | Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies |
| CN105428081A (en) * | 2015-12-28 | 2016-03-23 | 吉林大学 | Ni3S2 coated MMoO4 composite material grown in-site on metal substrate and application of composite material |
| CN105664977A (en) * | 2016-02-03 | 2016-06-15 | 中国科学院化学研究所 | Molybdenum disulfide-cadmium sulfide nanometer composite material and preparing method and application thereof |
| CN107010670A (en) * | 2016-07-27 | 2017-08-04 | 北京大学 | A kind of MoSxOy/ carbon nano-composite material, its preparation method and its application |
| CN106521460A (en) * | 2016-10-31 | 2017-03-22 | 华南理工大学 | A preparing method for a hydrogen production composite catalytic electrode |
| CN107051550A (en) * | 2017-04-24 | 2017-08-18 | 山东大学 | A kind of electro-catalysis water decomposition MoSe2/Co0.85Se composites and preparation method and application |
| CN107968208A (en) * | 2017-12-01 | 2018-04-27 | 吉林大学 | A kind of nano-lamellar structure of three nickel of curing/molybdenum disulfide composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YAQING YANG，等: "MoS2-Ni3S2 Heteronanorods as Efficient and Stable Bifunctional Electrocatalysts for Overall Water Splitting", 《ACS CATAL.》 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020092188A1 (en) * | 2018-10-29 | 2020-05-07 | Northwestern University | Composite, hierarchical electrocatalytic materials for water splitting |
| US11932952B2 (en) | 2018-10-29 | 2024-03-19 | Northwestern University | Composite, hierarchical electrocatalytic materials for water splitting |
| CN109686591A (en) * | 2018-12-17 | 2019-04-26 | 东南大学 | Sheet Ni3S2Coat column Ni3S2The preparation method of array electrode |
| CN110075873A (en) * | 2019-04-29 | 2019-08-02 | 苏州大学 | It is layered the Fe-MoS of self assembly2/Ni3S2/ NF composite nano materials and the preparation method and application thereof |
| CN110075873B (en) * | 2019-04-29 | 2021-11-23 | 苏州大学 | Layered self-assembled Fe-MoS2/Ni3S2/NF composite nano material and preparation method and application thereof |
| CN110327942A (en) * | 2019-05-06 | 2019-10-15 | 湖北大学 | The flower-shaped MoS of lamella micron2/Ni3S2/ NiFe-LDH/NF material and its synthetic method and application |
| CN110327942B (en) * | 2019-05-06 | 2022-03-18 | 湖北大学 | Lamellar micro flower-shaped MoS2/Ni3S2NiFe-LDH/NF material and synthetic method and application thereof |
| CN110449170A (en) * | 2019-08-12 | 2019-11-15 | 浙江师范大学 | A kind of amorphous state MoS2Modify CoS/Co0.85The preparation method of the heterogeneous nano-tube array elctro-catalyst of Se |
| CN110449170B (en) * | 2019-08-12 | 2022-02-18 | 浙江师范大学 | Amorphous MoS2Modified CoS/Co0.85Preparation method of Se heterogeneous nanotube array electrocatalyst |
| CN110694646A (en) * | 2019-10-22 | 2020-01-17 | 上海交通大学 | Bimetallic sulfide composite electrocatalyst and preparation method and application thereof |
| CN110752096A (en) * | 2019-10-25 | 2020-02-04 | 青岛科技大学 | Multidimensional structure metal sulfide Ni3S2/Co3S4Preparation of (A) and its use in supercapacitors |
| CN110813323A (en) * | 2019-11-19 | 2020-02-21 | 中山大学 | High-efficiency and durable hydrogen evolution nickel-based catalyst constructed by atomic layer deposition and preparation method and application thereof |
| CN111524714A (en) * | 2020-04-06 | 2020-08-11 | 电子科技大学 | Preparation method of self-supporting nano array with secondary structure |
| CN111524714B (en) * | 2020-04-06 | 2022-07-29 | 电子科技大学 | Preparation method of self-supporting nano array with secondary structure |
| CN111686764A (en) * | 2020-05-06 | 2020-09-22 | 东莞理工学院 | Fe-Ni (OH)2/Ni3S2@ NF heterostructure and preparation method and application thereof |
| CN111686764B (en) * | 2020-05-06 | 2022-09-30 | 东莞理工学院 | Fe-Ni (OH) 2 /Ni 3 S 2 @ NF heterostructure and preparation method and application thereof |
| CN112133886A (en) * | 2020-08-12 | 2020-12-25 | 南昌航空大学 | Preparation method and application of in-situ integrated electrode for alkali ion battery |
| CN112133886B (en) * | 2020-08-12 | 2022-09-30 | 南昌航空大学 | Preparation method and application of in-situ integrated electrode for alkali ion battery |
| CN112023942A (en) * | 2020-09-03 | 2020-12-04 | 广州大学 | NiMoO3S/foam nickel composite material and preparation method and application thereof |
| CN112169824B (en) * | 2020-11-08 | 2023-06-23 | 杭州长氢新材料有限公司 | Preparation method of composite electrode |
| CN112169824A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Co9S8Preparation method of/N-CCA composite electrode |
| CN112473697A (en) * | 2020-12-04 | 2021-03-12 | 福州大学 | Nickel-cobalt-tungsten multi-sulfide bifunctional catalyst with core-shell spherical structure and preparation method and application thereof |
| CN113713833A (en) * | 2021-09-15 | 2021-11-30 | 北京师范大学 | Molybdenum oxysulfide/nickel sulfide/foamed nickel complex and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108816250B (en) | 2020-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108816250A (en) | A kind of nanometer stick array composite material and preparation method and application | |
| Chandrasekaran et al. | Developments and perspectives on robust nano‐and microstructured binder‐free electrodes for bifunctional water electrolysis and beyond | |
| Cai et al. | Amorphous versus crystalline in water oxidation catalysis: A case study of NiFe alloy | |
| Doan et al. | Hierarchical three-dimensional framework interface assembled from oxygen-doped cobalt phosphide layer-shelled metal nanowires for efficient electrocatalytic water splitting | |
| Liu et al. | Engineering Ni2P-NiSe2 heterostructure interface for highly efficient alkaline hydrogen evolution | |
| Wang et al. | A critical review: 1D/2D nanostructured self-supported electrodes for electrochemical water splitting | |
| Li et al. | Hierarchical porous Co9S8/nitrogen-doped carbon@ MoS2 polyhedrons as pH universal electrocatalysts for highly efficient hydrogen evolution reaction | |
| Su et al. | CoO-Mo2N hollow heterostructure for high-efficiency electrocatalytic hydrogen evolution reaction | |
| Xu et al. | Engineering Ni (OH) 2 nanosheet on CoMoO4 nanoplate array as efficient electrocatalyst for oxygen evolution reaction | |
| Huang et al. | 3D ordered mesoporous cobalt ferrite phosphides for overall water splitting | |
| Hao et al. | Nickel incorporated Co9S8 nanosheet arrays on carbon cloth boosting overall urea electrolysis | |
| Yang et al. | An efficient bifunctional electrocatalyst for water splitting based on cobalt phosphide | |
| Wang et al. | Metal-organic-framework template-derived hierarchical porous CoP arrays for energy-saving overall water splitting | |
| Paygozar et al. | Recent progress in non-noble metal-based electrocatalysts for urea-assisted electrochemical hydrogen production | |
| Singh et al. | Interface engineering induced electrocatalytic behavior in core-shelled CNTs@ NiP2/NbP heterostructure for highly efficient overall water splitting | |
| Zhou et al. | In situ hydrothermal growth of metallic Co9S8-Ni3S2 nanoarrays on nickel foam as bifunctional electrocatalysts for hydrogen and oxygen evolution reactions | |
| US20230220570A1 (en) | Fast Ambient-Temperature Synthesis of OER Catalysts for Water Electrolysis | |
| CN108396329B (en) | Iron-doped two-phase nickel sulfide nano array material, preparation method and application thereof | |
| Maslana et al. | High catalytic performance of tungsten disulphide rodes in oxygen evolution reactions in alkaline solutions | |
| Ao et al. | Fe-doped Co9S8 nanosheets on carbon fiber cloth as pH-universal freestanding electrocatalysts for efficient hydrogen evolution | |
| KR102065680B1 (en) | Hierarchical Nanostructure of Transition Metal Sulfides, Hydrogen Evolution Reaction Catalysts, and the Fabrication Method Thereof | |
| CN110075873B (en) | Layered self-assembled Fe-MoS2/Ni3S2/NF composite nano material and preparation method and application thereof | |
| Flores et al. | Electrocatalytic oxygen evolution reaction of hierarchical micro/nanostructured mixed transition cobalt oxide in alkaline medium | |
| Sheng et al. | Rational design of Co-SP nanosheet arrays as bifunctional electrocatalysts for both ethanol oxidation reaction and hydrogen evolution reaction | |
| Yang et al. | Construction of Co3O4/Fe2O3 nanosheets on nickel foam as efficient electrocatalyst for the oxygen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200218 |