CN106984334B - The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate - Google Patents
The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate Download PDFInfo
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- CN106984334B CN106984334B CN201710146654.9A CN201710146654A CN106984334B CN 106984334 B CN106984334 B CN 106984334B CN 201710146654 A CN201710146654 A CN 201710146654A CN 106984334 B CN106984334 B CN 106984334B
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- nanobelt
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- 239000010936 titanium Substances 0.000 title claims abstract description 159
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 109
- 239000002127 nanobelt Substances 0.000 title claims abstract description 97
- 239000000758 substrate Substances 0.000 title claims abstract description 79
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000010189 synthetic method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 7
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 235000019441 ethanol Nutrition 0.000 claims description 19
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 12
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 12
- 238000005538 encapsulation Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- 238000010406 interfacial reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- 229960004756 ethanol Drugs 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000001338 self-assembly Methods 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- 108010020056 Hydrogenase Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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
-
- 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 relates to a kind of synthetic methods of cobalt disulfide nanobelt package assembly in titanium sheet substrate, preparation including cobalt disulfide nanobelt in the preparation of cobaltosic oxide nano band in the synthesis of cobalt hydroxide nanobelt in titanium substrate, titanium substrate, titanium substrate and etc., cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared.Compared with prior art, the invention is simple and feasible, reproducible, obtained cobalt disulfide nanobelt novel in shape, is evenly distributed on titanium-based bottom surface, stable structure, and with titanium substrate rigid contact, be conducive to electron-transport and interfacial reaction.This product can be widely used in electro-catalysis field directly as two-dimensional electrode material, have excellent electrolysis water H2-producing capacity.
Description
Technical field
The present invention relates to a kind of synthetic methods for producing hydrogen catalyst, receive more particularly, to cobalt disulfide in a kind of titanium sheet substrate
Synthetic method of the rice with package assembly.
Background technique
Hydrogen energy source as a kind of emerging renewable energy, development technique along with the research and development for producing hydrogen catalyst material and
It continues to develop.Therefore developing has efficient catalytic performance, at low cost, free of contamination production hydrogen electrode material, has become hydrogen energy source
The hot spot in field.Nano-electrode material produces the exhibition of hydrogen field in electro-catalysis since it is with biggish specific surface area and surface-active
Good electrochemical applications value is revealed.Currently, platinum-group noble metals material is that known most efficient electro-catalysis produces hydrogen material,
But since its reserves is limited, cost is excessively high, its application range is caused to be restricted, therefore develop base metal production hydrogen and urge
Agent, such as metal sulfide, metal selenide, metal carbides are cheap, new material easily obtained, are just increasingly subject to
The extensive concern of people.
In electrolysis aquatic products hydrogen system, producing the main function that hydrogen catalyst plays is the change for reducing free energy in reaction process
Dynamic amplitude, so that evolving hydrogen reaction be enable smoothly descent to carry out.In the first row transition metal double sulfide (FeS2、CoS2、
NiS2) in molecular structure, metallic atom is connected with the sulphur atom of surrounding with octahedral form, in this structure and biosystem
Liberation of hydrogen catalyst hydrogenase the performance similar, therefore that there is catalysis to produce hydrogen of active site, especially have metalloid conductive
Property cobalt disulfide, electrolysis aquatic products hydrogen field show excellent catalytic activity.Currently, the growth in situ in conductive substrates
Two dimension or three-diemsnional electrode material, the features such as close contact due to it without the fixation of adhesive, electrode material and substrate, from
And there is easy to operate, electronics to be easier to the advantages such as transmission, it is increasingly becoming the research hotspot for producing hydrogen electrode material.
It includes nano wire, nanometer sheet, pyrometric cone etc. that the pattern of cobalt disulfide is grown in conductive substrates, but due to pure phase
The catalysis H2-producing capacity of cobalt disulfide can not have further promotion, therefore most work are depended on and are doped to cobalt disulfide
Or synthesis bimetallic sulfide composite material, cause the process for preparing material cumbersome, controllability is not strong, and product is inhomogenous.
Based on the above issues, we have developed a kind of using titanium sheet as the synthetic method of the package assembly cobalt disulfide nanobelt of substrate, produce
Product novel in shape, stable structure, yield is high and is evenly distributed, and easy to operate and control, H2-producing capacity has a degree of promotion,
And better than the catalytic performance for the non-package assembly cobalt disulfide nanobelt being transformed by solution phase precursor, it is expected to be widely applied
Are produced from the fields such as oxygen in supercapacitor, lithium ion battery, full electrolysis aquatic products hydrogen.
Chinese patent CN104402065B discloses the preparation method of spherical cobalt disulfide nano-powder, will be analytically pure
CoCl2·6H2O is add to deionized water to obtain solution A；Analytically pure thiocarbamide SC (NH is added into solution A2)2, obtain molten
Liquid B；Dilute hydrochloric acid is added into solution B or sodium hydroxide solution adjusts pH and obtains solution C.The solution C of above-mentioned preparation is poured into hydro-thermal
In reaction kettle, reaction kettle is then sealed, reaction kettle is put into warm-pressing double-control microwave oven, temperature control mode is selected to carry out hydro-thermal
Then dilute hydrochloric acid is respectively adopted in reaction, carbon disulfide, deionized water, dehydrated alcohol, which washs, both obtains the spherical CoS of black2Nanometer
Powder.The reaction system of the patent needs to carry out the adjusting and calibration of pH value, and needs to carry out adequately clearly after collecting product
It washes to remove by-product.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of easy to operate, controllably
The synthetic method of cobalt disulfide nanobelt package assembly in the strong titanium sheet substrate of property.
The purpose of the present invention can be achieved through the following technical solutions:
The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate, using following steps:
(1) in titanium substrate cobalt hydroxide nanobelt synthesis: weigh cobalt salt and surfactant, be dissolved in water and N, N- diformazan
The mixed liquor of base formamide (DMF), is added dropwise hydrogenperoxide steam generator, is then transferred to reaction kettle, puts into clean naked titanium sheet, envelope
Dress, is placed under high temperature and reacts, and takes out titanium sheet, is successively rinsed well and dried with ethyl alcohol and deionized water, obtain self assembly type
Co(OH)3/Ti；
(2) in titanium substrate cobaltosic oxide nano band preparation: take Co (OH) made from step (1)3/ Ti is placed in tube furnace
In, high annealing, occurs hot dehydration decomposition reaction, obtains Co in air3O4/Ti；
(3) in titanium substrate cobalt disulfide nanobelt preparation: take Co made from step (2)3O4/ Ti is placed in tube furnace, in
Place excessive sulphur powder at the inlet end of tube furnace, under argon atmosphere protection, carry out high temperature vulcanized reaction, then dry in the air naturally to
Room temperature takes out the titanium sheet that load has cobalt disulfide nanobelt, i.e. CoS2/ Ti is successively cleaned and is dried with carbon disulfide and ethyl alcohol,
Cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared.
Surfactant described in step (1) is hexadecyltrimethylammonium chloride, and the cobalt salt is six hydrations two
Cobalt chloride, the cobalt salt of addition and the mass ratio of surfactant are 0.005~0.007:0.01~0.02.
The volume ratio of water described in step (1) and n,N-Dimethylformamide be 0.8:1~1.2:1, mixed liquor with plus
The volume ratio of the hydrogenperoxide steam generator entered is 4:1~6:1.
The mass fraction of hydrogenperoxide steam generator described in step (1) is 30wt%.
It is 140~160 DEG C that reaction temperature is controlled in reaction kettle described in step (1), and the reaction time is 1~20h.
The temperature of hot dehydration decomposition reaction is 250~350 DEG C in step (2), and the reaction time is 2~5h.
Step (3) high temperature vulcanization reaction temperature is 350~450 DEG C, and the reaction time is 2~6h, the argon gas flow velocity being passed through
For 20~60sccm.
The sulphur powder and Co being added in step (3)3O4The proportionate relationship of/Ti is 1~2g/1~3cm2。
Cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared, is nano strip of the homoepitaxial in titanium sheet
Cobalt disulfide, the width of nanobelt are 3~5 μm, and length is 10~20 μm, and thickness average value is 130~170nm.
Compared with prior art, the cobalt disulfide nanometer of the titanium substrate over-assemble structure for the method synthesis that the present invention uses
Band, novel in shape, crystallinity is high, stable structure, is in close contact and is evenly distributed with titanium substrate, to ensure that the smooth of electronics
Transmission and the adequately reaction of production hydrogen, easy to operate, controllability is strong.Electrolysis aquatic products hydrogen test is carried out to product, and and by solution phase
The cobalt disulfide nanobelt that presoma converts compares, the experimental results showed that in the curing of titanium substrate over-assemble structure
Cobalt nanobelt H2-producing capacity is more preferable, and electric conductivity is stronger, therefore the material can be widely applied to electro-catalysis and produce hydrogen field.
In above-mentioned preparation technology parameter, what the material proportional quantity and gas-phase presulfiding for synthesizing presoma cobalt hydroxide reacted
Temperature, time have decisive impact the pattern of final product, structural stability and performance.Material proportional quantity is to hydrogen-oxygen
The stability of the pattern and structure of changing cobalt nanobelt has conclusive effect, if proportional quantity exceeds suitable range, material
A degree of variation can occur for the pattern of material, also can phase strain differential in the structural stability of growth in situ in substrate；Gas phase sulfur
The temperature and time for changing reaction, can have an impact to the performance and structural stability of final product cobalt disulfide nanobelt, temperature mistake
The low and time is too short, will lead to product vulcanization it is insufficient, object is mutually impure, thus degradation, the excessively high meeting of temperature is so that product knot
Structure bad stability, again such that performance is affected.
Reaction system of the invention is uniformly distributed independent of accurate pH value, product in substrate surface, stabilized structure, only
The titanium sheet for loading product need to be carried out to simple infiltration cleaning, and gas phase reaction is simple, by-product is few, success rate
It is high.Simultaneously when carrying out electrolysis aquatic products hydrogen test, product of the present invention can carry out production hydrogen directly as working electrode, not need to carry out
The processing such as drop coating, adhesive fixation, have the advantages such as easy to operate, active area is big.And material closely connects with conductive substrates
Touching peomotes electric charge transfer, reaction barrier is reduced, to facilitate the promotion of the electrocatalysis characteristic of material.
Detailed description of the invention
Fig. 1 is Co (OH) in the corresponding titanium substrate of different the hydro-thermal reaction times (1,5,10,20h) of embodiment 1-4 preparation3
The electron scanning micrograph of nanobelt；
Fig. 2 is the CoS in titanium substrate over-assemble structure prepared by embodiment 52The scanning electron microscope of nanobelt and thoroughly
Penetrate electron micrograph；
Fig. 3 is the CoS in titanium substrate over-assemble structure prepared by embodiment 52The Raman spectrum and X-ray diffraction of nanobelt
Map；
Fig. 4 is solution phase Co (OH) prepared by embodiment 63The non-package assembly CoS that nanobelt and conversion obtain2Nanobelt
Electron micrograph；
Fig. 5 is the CoS in titanium substrate over-assemble structure prepared by embodiment 72Nanobelt is in acid and alkaline electrolyte
Linear volt-ampere curve；
Fig. 6 is the CoS in titanium substrate over-assemble structure prepared by embodiment 72Impedance of the nanobelt in alkaline electrolyte
Spectrogram.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.Following embodiment will be helpful to this field
Technical staff further understand the present invention, but the invention is not limited in any way.It should be pointed out that the general of this field
For logical technical staff, without departing from the inventive concept of the premise, various modifications and improvements can be made.These are belonged to
Protection scope of the present invention.
Embodiment 1
Co (OH) in titanium sheet substrate3The synthesis of nanobelt
It weighs 0.0065g six and is hydrated cobaltous dichloride and 0.0125g hexadecyltrimethylammonium chloride (CTAC), be dissolved in 5mL
The mixed liquor of water and 5mL n,N-Dimethylformamide (DMF) is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reaction kettle puts into processed clean naked titanium sheet, and encapsulation is placed at 150 DEG C and react 1 hour, takes out titanium sheet, successively with ethyl alcohol with
Deionized water is rinsed well, is dried in 60 DEG C, is obtained the Co (OH) of self assembly type3Nanobelt.Obtained sample such as Fig. 1 (a)
It is shown, scanning electron microscope be shown in the reaction time be 1h when, titanium-based bottom surface be dendrimer materials, do not grow up to nanobelt pattern also,
Illustrate Co (OH)3Be really nucleated in titanium substrate surface in situ and start growth in situ.
Embodiment 2
Co (OH) in titanium sheet substrate3The synthesis of nanobelt
It weighs 0.0065g six and is hydrated cobaltous dichloride and 0.0125g hexadecyltrimethylammonium chloride (CTAC), be dissolved in 5mL
The mixed liquor of water and 5mL n,N-Dimethylformamide (DMF) is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reaction kettle puts into processed clean naked titanium sheet, and encapsulation is placed at 150 DEG C and react 5 hours, takes out titanium sheet, successively with ethyl alcohol with
Deionized water is rinsed well, is dried in 60 DEG C, is obtained the Co (OH) of self assembly type3Nanobelt.Obtained sample such as Fig. 1 (b)
It is shown, scanning electron microscope be shown in the reaction time be 5h when, it is about 3 microns that titanium-based bottom surface, which has had already appeared length, and width is about 1
The Co (OH) of micron3Nanobelt illustrates Co (OH)3The pattern of small nanotube band has been grown into via the dendroid of 1h.
Embodiment 3
Co (OH) in titanium sheet substrate3The synthesis of nanobelt
It weighs 0.0065g six and is hydrated cobaltous dichloride and 0.0125g hexadecyltrimethylammonium chloride (CTAC), be dissolved in 5mL
The mixed liquor of water and 5mL n,N-Dimethylformamide (DMF) is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reaction kettle, puts into processed clean naked titanium sheet, and encapsulation is placed at 150 DEG C and reacts 10 hours, takes out titanium sheet, successively use ethyl alcohol
It is rinsed well with deionized water, is dried in 60 DEG C, obtain the Co (OH) of self assembly type3Nanobelt.Obtained sample such as Fig. 1
(c) shown in, scanning electron microscope be shown in the reaction time be 10h when, Co (OH)3Nanobelt has been evenly distributed on titanium-based bottom surface,
Stable structure, and substrate is overgrowed with, size has further increase compared with 5h again.
Embodiment 4
Co (OH) in titanium sheet substrate3The synthesis of nanobelt
It weighs 0.0065g six and is hydrated cobaltous dichloride and 0.0125g hexadecyltrimethylammonium chloride (CTAC), be dissolved in 5mL
The mixed liquor of water and 5mL n,N-Dimethylformamide (DMF) is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reaction kettle, puts into processed clean naked titanium sheet, and encapsulation is placed at 150 DEG C and reacts 20 hours, takes out titanium sheet, successively use ethyl alcohol
It is rinsed well with deionized water, is dried in 60 DEG C, obtain the Co (OH) of self assembly type3Nanobelt.Obtained sample such as Fig. 1
(d) shown in, scanning electron microscope be shown in the reaction time be 20h when, Co (OH)3What the size and degree of distribution and 10h of nanobelt obtained
Sample is quite similar, illustrates that nanobelt is sufficiently self-assembled to substrate surface.
Embodiment 5
The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate
It weighs 0.0065g six and is hydrated cobaltous dichloride and 0.0125g hexadecyltrimethylammonium chloride (CTAC), be dissolved in 5mL
Water and 5mLN, the mixed liquor of dinethylformamide (DMF) are added dropwise 2mL hydrogen peroxide (30%) solution, it is anti-to be transferred to 50mL
Answer kettle, put into processed clean naked titanium sheet, encapsulation is placed at 150 DEG C and react 20 hours, take out titanium sheet, successively with ethyl alcohol with
Deionized water is rinsed well, is dried in 60 DEG C, is obtained the Co (OH) of self assembly type3Nanobelt.Then by Co (OH)3/ Ti is placed in pipe
In formula furnace, tube furnace does not encapsulate both ends, it is made to pass through 300 DEG C in air, and the high annealing of 2h occurs hot dehydration and decomposes instead
It answers, obtains the Co of self assembly type3O4Nanobelt.By Co obtained3O4/ Ti is placed in tube furnace, is put at the inlet end of tube furnace
2g sulphur powder is set, under the argon atmosphere protection that flow velocity is 25sccm, 400 DEG C vulcanize 6 hours, are dried in the air naturally to reaction unit to room
Temperature takes out the titanium sheet that load has cobalt disulfide nanobelt, i.e. CoS2/ Ti is successively cleaned with carbon disulfide and ethyl alcohol, is dried in 60 DEG C
It is dry.Obtained sample is long as shown in Fig. 2, the scanning electron microscope of Fig. 2 (a), (b) show that the width of nanobelt is about 4~5 μm
Degree is about 15~20 μm, CoS2The thickness average value of nanobelt is about~150nm, is illustrated through a series of converted in-situs, nanometer
Band pattern is maintained.Fig. 2 (c), (d) transmission electron microscope show nanobelt be made of little crystal grain, be polycrystalline structure, and have compared with
Good crystallinity.Fig. 3 (a), (b) show the CoS for having package assembly2The XRD of the nanobelt and CoS of pure phase2It is completely corresponding, and draw
Graceful further testimonial material is pure phase CoS2。
Embodiment 6
The synthesis of the cobalt disulfide nanobelt of non-package assembly without substrate
It weighs 0.0065g six and is hydrated cobaltous dichloride and 0.0125g hexadecyltrimethylammonium chloride (CTAC), be dissolved in 5mL
The mixed liquor of water and 5mL n,N-Dimethylformamide (DMF) is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reaction kettle, encapsulation, is placed at 150 DEG C and reacts 20 hours, collect molten liquid product, is successively washed with ethyl alcohol and deionized water centrifugation
It washs, revolving speed 5000r/min, is dried in 60 DEG C, obtain the Co (OH) of non-self assembly type3Nanobelt, as shown in Fig. 4 (a), pattern
With self assembly Co (OH)3It is identical.Then by Co (OH)3Nanobelt is placed in tube furnace, and tube furnace does not encapsulate both ends, makes it in sky
The high annealing for passing through 300 DEG C of 2h in gas, occurs hot dehydration decomposition reaction, obtains the Co of non-self assembly type3O4Nanobelt.It will system
The Co of the non-self assembly type obtained3O4Nanobelt is placed in tube furnace, and 2g sulphur powder is placed at the inlet end of tube furnace, is in flow velocity
Under the argon atmosphere protection of 25sccm, 400 DEG C vulcanize 6 hours, are dried in the air naturally to reaction unit to room temperature, take out product, i.e., it is non-from
Packaging CoS2Nanobelt is successively cleaned with carbon disulfide and ethyl alcohol, is dried in 60 DEG C.Resulting CoS2As shown in Fig. 4 (b), still
It is so nanobelt pattern, with the CoS in substrate over-assemble2It is identical.
Embodiment 7
In the electrolysis aquatic products hydrogen of the cobalt disulfide nanobelt of the cobalt disulfide nanobelt and non-assembling of titanium sheet substrate over-assemble
Experiment.
Laboratory apparatus: CHI660E electrochemical workstation
Three-electrode system: reference electrode (saturated calomel electrode), to electrode (coated graphite rod electrrode), working electrode, (assembling is tied
Structure CoS2/ Ti, non-package assembly CoS2(aq.)-Ti, naked titanium sheet)
It produces hydrogen electrolyte: preparing 0.5M H2SO4Solution, 1M KOH solution, and tested with acidometer and record two kinds of electrolysis
The pH value of liquid.
Produce hydrogen test method: linear voltammetry, Electrode with Electrochemical Impedance Spectroscopy
Instrument parameter: linear volt-ampere curve: potential range is 0.1v~-0.25V (0.5M H2SO4Solution) and 0.1v~-
0.4V (1M KOH solution), sweeping speed is 2mV/s；Electrochemical impedance: amplitude 5mV, frequency range 0.01Hz~105Hz。
The building of working electrode:
(1) package assembly cobalt disulfide nanobelt (package assembly CoS2/ Ti):
With the substrate with material of the certain area of scissors clip, and wipe the material of long position off, titanium sheet substrate is straight
It connects as working electrode, is pressed from both sides by platinum plate electrode and be connected with electrochemical workstation；
(2) non-package assembly cobalt disulfide nanobelt (non-package assembly CoS2(aq.)-Ti):
Quantitative cobalt disulfide nanobelt powder is weighed, be scattered in ethyl alcohol and water mixed liquid (ethyl alcohol and water volume ratio are 1:
1), oscillator vibrates 30min, and for drop coating in clean naked titanium sheet, guarantee material load amount is 0.7mg/cm2, then successively drip
The Nafion ethyl alcohol dilution for adding 2.5 microlitre 0.05% (mass fraction) three times, passes through platinum plate electrode folder and electrochemistry after drying
Work station is connected；
(3) it is used to compare using naked titanium sheet, platinum filament as working electrode, and clings the more of naked titanium sheet and platinum filament with insulating tape
Remaining part position, to ensure the production hydrogen area of electrode as fixed value.
Experimental procedure:
(1) 15mL0.5M H is taken2SO4For solution in electrolytic cell, logical nitrogen about 15min is saturated electrolyte by nitrogen, installs
Three-electrode system tests package assembly CoS respectively2/ Ti, non-package assembly CoS2(aq.)-Ti, platinum filament, naked titanium sheet linear volt
Pacify curve；
(2) take 15mL1M KOH solution in electrolytic cell, logical nitrogen about 15min is saturated electrolyte by nitrogen, surveys respectively
Try package assembly CoS2/ Ti, non-package assembly CoS2(aq.)-Ti, platinum filament, naked titanium sheet linear volt-ampere curve；
(3) take 15mL 1M KOH solution in electrolytic cell, logical nitrogen about 15min is saturated electrolyte by nitrogen, surveys respectively
Try package assembly CoS2/ Ti, non-package assembly CoS2(aq.) electrochemical impedance of-Ti；
(4) every time before test, electrolyte, which is intended to logical nitrogen 15min, to be made to be saturated.Linearity curve is compensated through manual ohm
Processing.Potential correction is the formula of reversible hydrogen electrode: E (RHE)=E (SCE)+0.242+0.059pH.
Interpretation of result: Fig. 5 (a) and (b) are respectively acidic electrolysis bath (0.5M H2SO4) and alkaline electrolyte (1M KOH)
In, package assembly CoS2/ Ti, non-package assembly CoS2(aq.) the linear volt-ampere curve of-Ti, platinum filament and naked titanium sheet, by contrast may be used
It was found that package assembly CoS2/ Ti is illustrated better than non-package assembly CoS2(aq.) H2-producing capacity of-Ti.Fig. 6 is alkaline electrolysis
In liquid, package assembly CoS2/ Ti, non-package assembly CoS2(aq.) impedance spectra of-Ti, it can be found that package assembly CoS2/Ti
With more good electric conductivity.The result of performance test further demonstrates, and assembling effect promotes material and substrate interface
The electric charge transfer at place, and the material for being uniformly distributed in substrate has bigger catalytic active area and stable structure, thus
It improves it and produces hydrogen catalysis effect.
Embodiment 8
The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate, using following steps:
(1) in titanium substrate cobalt hydroxide nanobelt synthesis: weigh six hydration dichlorides in mass ratio for 0.005:0.01
Cobalt and surfactant hexadecyltrimethylammonium chloride, are dissolved in the mixed liquor of water and n,N-Dimethylformamide (DMF), water and
The volume ratio of n,N-Dimethylformamide is 0.8:1, and the hydrogenperoxide steam generator that mass fraction is 30wt%, mixed liquor is added dropwise
Volume ratio with the hydrogenperoxide steam generator of addition is 4:1, is then transferred to reaction kettle, puts into clean naked titanium sheet, and encapsulation is placed in 140
DEG C reaction 10h, take out titanium sheet, successively rinsed well and dried with ethyl alcohol and deionized water, obtain the Co (OH) of self assembly type3/
Ti；
(2) in titanium substrate cobaltosic oxide nano band preparation: take Co (OH) made from step (1)3/ Ti is placed in tube furnace
In, high annealing, occurs hot dehydration decomposition reaction in air, and reaction temperature is 250 DEG C, and reaction time 5h obtains Co3O4/
Ti；
(3) in titanium substrate cobalt disulfide nanobelt preparation: take Co made from step (2)3O4/ Ti is placed in tube furnace, in
Excessive sulphur powder, the sulphur powder and Co of addition are placed at the inlet end of tube furnace3O4The proportionate relationship of/Ti is 1g/1cm2, in argon gas
Under atmosphere protection, high temperature vulcanized reaction is carried out, high temperature vulcanized reaction temperature is 350 DEG C, reaction time 6h, the argon gas stream being passed through
Speed is 20sccm, is then dried in the air naturally to room temperature, and the titanium sheet that load has cobalt disulfide nanobelt, i.e. CoS are taken out2/ Ti, uses curing
Carbon and ethyl alcohol are successively cleaned and are dried, and cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared.
Cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared, is nano strip of the homoepitaxial in titanium sheet
Cobalt disulfide, the width of nanobelt are about 3~4 μm, and length is about 10~15 μm, and thickness average value is about~130nm.
Embodiment 9
The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate, using following steps:
(1) in titanium substrate cobalt hydroxide nanobelt synthesis: weigh six hydration dichlorides in mass ratio for 0.006:0.01
Cobalt and surfactant hexadecyltrimethylammonium chloride, are dissolved in the mixed liquor of water and n,N-Dimethylformamide (DMF), water and
The volume ratio of n,N-Dimethylformamide be 1:1, be added dropwise mass fraction be 30wt% hydrogenperoxide steam generator, mixed liquor with
The volume ratio of the hydrogenperoxide steam generator of addition is 5:1, is then transferred to reaction kettle, puts into clean naked titanium sheet, and encapsulation is placed in 150 DEG C
10h is reacted, titanium sheet is taken out, is successively rinsed well and dried with ethyl alcohol and deionized water, obtain the Co (OH) of self assembly type3/Ti；
(2) in titanium substrate cobaltosic oxide nano band preparation: take Co (OH) made from step (1)3/ Ti is placed in tube furnace
In, high annealing, occurs hot dehydration decomposition reaction in air, and reaction temperature is 300 DEG C, and reaction time 3h obtains Co3O4/
Ti；
(3) in titanium substrate cobalt disulfide nanobelt preparation: take Co made from step (2)3O4/ Ti is placed in tube furnace, in
Excessive sulphur powder, the sulphur powder and Co of addition are placed at the inlet end of tube furnace3O4The proportionate relationship of/Ti is 1g/2cm2, in argon gas
Under atmosphere protection, high temperature vulcanized reaction is carried out, high temperature vulcanized reaction temperature is 400 DEG C, reaction time 3h, the argon gas stream being passed through
Speed is 30sccm, is then dried in the air naturally to room temperature, and the titanium sheet that load has cobalt disulfide nanobelt, i.e. CoS are taken out2/ Ti, uses curing
Carbon and ethyl alcohol are successively cleaned and are dried, and cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared.
Cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared, is nano strip of the homoepitaxial in titanium sheet
Cobalt disulfide, the width of nanobelt are about 3~4 μm, and length is about 15~20 μm, and thickness average value is about~150nm.
Embodiment 10
The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate, using following steps:
(1) in titanium substrate cobalt hydroxide nanobelt synthesis: weigh six hydration dichlorides in mass ratio for 0.007:0.02
Cobalt and surfactant hexadecyltrimethylammonium chloride, are dissolved in the mixed liquor of water and n,N-Dimethylformamide (DMF), water and
The volume ratio of n,N-Dimethylformamide is 1.2:1, and the hydrogenperoxide steam generator that mass fraction is 30wt%, mixed liquor is added dropwise
Volume ratio with the hydrogenperoxide steam generator of addition is 6:1, is then transferred to reaction kettle, puts into clean naked titanium sheet, and encapsulation is placed in 160
DEG C reaction 20h, take out titanium sheet, successively rinsed well and dried with ethyl alcohol and deionized water, obtain the Co (OH) of self assembly type3/
Ti；
(2) in titanium substrate cobaltosic oxide nano band preparation: take Co (OH) made from step (1)3/ Ti is placed in tube furnace
In, high annealing, occurs hot dehydration decomposition reaction in air, and reaction temperature is 350 DEG C, and reaction time 2h obtains Co3O4/
Ti；
(3) in titanium substrate cobalt disulfide nanobelt preparation: take Co made from step (2)3O4/ Ti is placed in tube furnace, in
Excessive sulphur powder, the sulphur powder and Co of addition are placed at the inlet end of tube furnace3O4The proportionate relationship of/Ti is 2g/3cm2, in argon gas
Under atmosphere protection, high temperature vulcanized reaction is carried out, high temperature vulcanized reaction temperature is 450 DEG C, reaction time 2h, the argon gas stream being passed through
Speed is 60sccm, is then dried in the air naturally to room temperature, and the titanium sheet that load has cobalt disulfide nanobelt, i.e. CoS are taken out2/ Ti, uses curing
Carbon and ethyl alcohol are successively cleaned and are dried, and cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared.
Cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared, is nano strip of the homoepitaxial in titanium sheet
Cobalt disulfide, the width of nanobelt are about 4~5 μm, and length is about 15~20 μm, and thickness average value is about~170nm.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (8)
1. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate, which is characterized in that this method use with
Lower step:
(1) in titanium substrate cobalt hydroxide nanobelt synthesis: weigh cobalt salt and surfactant, be dissolved in water and N, N- dimethyl methyl
The mixed liquor of amide (DMF), is added dropwise hydrogenperoxide steam generator, is then transferred to reaction kettle, puts into clean naked titanium sheet, and encapsulation is set
It is reacted under high temperature, it is 140~160 DEG C that reaction temperature is controlled in reaction kettle, and the reaction time is 1~20h, takes out titanium sheet, successively
It is rinsed well and is dried with ethyl alcohol and deionized water, obtain growth in situ in the Co (OH) of titanium substrate3/Ti；
(2) in titanium substrate cobaltosic oxide nano band preparation: take Co (OH) made from step (1)3/ Ti is placed in tube furnace, In
The annealing of air high temperature, occurs hot dehydration decomposition reaction, obtains Co3O4/Ti；
(3) in titanium substrate cobalt disulfide nanobelt preparation: take Co made from step (2)3O4/ Ti is placed in tube furnace, in tubular type
Excessive sulphur powder is placed at the inlet end of furnace, under argon atmosphere protection, carries out high temperature vulcanized reaction, high temperature vulcanized reaction temperature
It is 350~450 DEG C, the reaction time is 2~6h, and the argon gas flow velocity being passed through is 20~60sccm, then dries in the air to room temperature, takes out naturally
Load has the titanium sheet of cobalt disulfide nanobelt, i.e. CoS2/ Ti is successively infiltrated with carbon disulfide and ethyl alcohol and cleans and dry, prepared
Obtain cobalt disulfide nanobelt package assembly in titanium sheet substrate.
2. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, special
Sign is that surfactant described in step (1) is hexadecyltrimethylammonium chloride, and the cobalt salt is six hydration dichloros
Change cobalt, the cobalt salt of addition and the mass ratio of surfactant are 0.005~0.007:0.01~0.02.
3. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, special
Sign is that the volume ratio of water described in step (1) and n,N-Dimethylformamide is 0.8:1~1.2:1, mixed liquor and addition
Hydrogenperoxide steam generator volume ratio be 4:1~6:1.
4. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, special
Sign is that the mass fraction of hydrogenperoxide steam generator described in step (1) is 30wt%.
5. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, special
Sign is that the temperature of hot dehydration decomposition reaction is 250~350 DEG C in step (2), and the reaction time is 2~5h.
6. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, special
Sign is, the sulphur powder and Co being added in step (3)3O4The proportionate relationship of/Ti is 1~2g/1~3cm2。
7. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, special
Sign is, cobalt disulfide nanobelt package assembly in titanium sheet substrate is prepared, for the nano strip being uniformly assembled in titanium sheet
Cobalt disulfide, the width of nanobelt are 3~5 μm, and length is 10~20 μm, and thickness average value is 130~170nm.
8. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, special
Sign is that cobalt disulfide nanobelt package assembly in titanium sheet substrate, which is prepared, has electrolysis aquatic products hydrogen application.
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