CN106984334A - 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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- CN106984334A CN106984334A CN201710146654.9A CN201710146654A CN106984334A CN 106984334 A CN106984334 A CN 106984334A CN 201710146654 A CN201710146654 A CN 201710146654A CN 106984334 A CN106984334 A CN 106984334A
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- nanobelt
- titanium sheet
- package assembly
- cobalt
- titanium
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- 239000010936 titanium Substances 0.000 title claims abstract description 161
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 111
- 239000002127 nanobelt Substances 0.000 title claims abstract description 99
- 239000000758 substrate Substances 0.000 title claims abstract description 81
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000010189 synthetic method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 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 17
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 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
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 12
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 11
- 230000036571 hydration Effects 0.000 claims description 11
- 238000006703 hydration reaction Methods 0.000 claims description 11
- 238000005538 encapsulation Methods 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
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 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
- 230000008859 change Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000004073 vulcanization Methods 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
- 238000004458 analytical method Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000010406 interfacial reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 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
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 6
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-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
- 230000008901 benefit Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 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
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 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
- 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
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 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
- 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
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 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
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 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
- 230000001172 regenerating effect Effects 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 238000005406 washing 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 method of cobalt disulfide nanobelt package assembly in titanium sheet substrate, the steps such as the 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, prepare cobalt disulfide nanobelt package assembly in titanium sheet substrate.Compared with prior art, simple and easy to apply, reproducible, obtained cobalt disulfide nanobelt novel in shape of the invention, is evenly distributed on titanium-based basal surface, Stability Analysis of Structures, and with titanium substrate rigid contact, be conducive to electric transmission and interfacial reaction.This product can be widely used in electro-catalysis field directly as two-dimensional electrode material, with excellent electrolysis water H2-producing capacity.
Description
Technical field
The present invention relates to a kind of synthetic method for producing hydrogen catalyst, received more particularly, to cobalt disulfide in a kind of titanium sheet substrate
Synthetic method of the rice with package assembly.
Background technology
Hydrogen energy source is as a kind of emerging regenerative resource, and its development technique is along with the research and development of production hydrogen catalyst material
Continue to develop.Therefore develop with efficient catalytic performance, cost be low, free of contamination production hydrogen electrode material, have become hydrogen energy source
The focus in field.Nano-electrode material has larger specific surface area and surface-active due to it, and hydrogen field exhibition is produced in electro-catalysis
Good electrochemical applications value is revealed.At present, platinum-group noble metals material is known most efficient electro-catalysis production hydrogen material,
But it is due to that its reserves is limited, cost is too high, causes its application to be restricted, therefore develop base metal production hydrogen and urges
Agent, as metal sulfide, metal selenide, metal carbides etc. are cheap, easily made from new material, be just increasingly subject to
The extensive concern of people.
In electrolysis aquatic products hydrogen system, the main function that production hydrogen catalyst is played is the change for reducing free energy in course of reaction
Dynamic amplitude, so that evolving hydrogen reaction can be carried out smoothly descent.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, this structure with biosystem
Liberation of hydrogen catalyst hydrogenase avtive spot it is similar, it is particularly conductive with metalloid therefore with the performance of catalysis production hydrogen
Property cobalt disulfide, show excellent catalytic activity in electrolysis aquatic products hydrogen field.At present, the growth in situ in conductive substrates
Two dimension or three-diemsnional electrode material, the features such as being in close contact due to it without the fixation of adhesive, electrode material and substrate, from
And the advantages such as transmission are more easy to easy to operate, electronics, it is increasingly becoming the study hotspot of production hydrogen electrode material.
The pattern of cobalt disulfide is grown in conductive substrates includes nano wire, nanometer sheet, pyrometric cone etc., but is due to pure phase
The catalysis H2-producing capacity of cobalt disulfide can not have further lifting, therefore most work depend on and cobalt disulfide is doped
Or synthesis bimetallic sulfide composite, cause that the flow for preparing material is cumbersome, controllability is not strong, product heterogeneity.
Based on above mentioned problem, we have developed a kind of synthetic method of the package assembly cobalt disulfide nanobelt using titanium sheet as substrate, production
Product novel in shape, Stability Analysis of Structures, yield is high and is evenly distributed, and easy to operate controllable, H2-producing capacity has a certain degree of lifting,
And better than the catalytic performance for the non-package assembly cobalt disulfide nanobelt being transformed by solution phase precursor, it is expected to extensive use
In fields such as ultracapacitor, lithium ion battery, full electrolysis aquatic products hydrogen production oxygen.
Chinese patent CN104402065B discloses the preparation method of spherical cobalt disulfide nano-powder, will be analytically pure
CoCl2·6H2O, which is added in deionized water, obtains solution A；Analytically pure thiocarbamide SC (NH are added into solution A2)2, obtain molten
Liquid B；Watery hydrochloric acid is added into solution B or sodium hydroxide solution regulation pH obtains solution C.The solution C of above-mentioned preparation is poured into hydro-thermal
In reactor, reactor is then sealed, reactor is put into warm-pressing double-control microwave oven, selection temperature control mode carries out hydro-thermal
Reaction, is then respectively adopted watery hydrochloric acid, and carbon disulfide, deionized water, absolute ethyl alcohol washing both obtains the spherical CoS of black2Nanometer
Powder.The reaction system of the patent needs to carry out the regulation and calibration of pH value, and needs progress sufficiently clear after product is collected
Wash to remove accessory substance.
The content of the invention
It is controllable it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is easy to operate
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：Cobalt salt and surfactant are weighed, water and N, N- diformazans is dissolved in
The mixed liquor of base formamide (DMF), is added dropwise hydrogenperoxide steam generator, is then transferred to reactor, the clean naked titanium sheet of input, envelope
Dress, is placed under high temperature and reacts, take out titanium sheet, clean and dry with ethanol and deionized water rinsing successively, obtains 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 atmosphere3O4/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 is placed at the inlet end of tube furnace, under argon gas atmosphere protection, high temperature vulcanized reaction is carried out, then dry in the air naturally to
Room temperature, takes out the titanium sheet for being loaded with cobalt disulfide nanobelt, i.e. CoS2/ Ti, is cleaned and dried successively with carbon disulfide and ethanol,
Prepare cobalt disulfide nanobelt package assembly in titanium sheet substrate.
Surfactant described in step (1) is hexadecyltrimethylammonium chloride, and described 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 and DMF described in step (1) is 0.8:1~1.2:1, mixed liquor is with adding
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%.
Controlling reaction temperature is 140~160 DEG C in reactor 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 added in step (3)3O4/ Ti proportionate relationship 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 is 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 is used
Band, novel in shape, crystallinity is high, Stability Analysis of Structures, is in close contact and is evenly distributed with titanium substrate, so as to ensure that the smooth of electronics
Transmission and the sufficiently reaction of production hydrogen, easy to operate, controllability is strong.The hydrogen test of electrolysis aquatic products is carried out to product, and and by solution
The cobalt disulfide nanobelt that presoma conversion is obtained is contrasted, test result indicates that in the curing of titanium substrate over-assemble structure
More preferably, electric conductivity is stronger for cobalt nanobelt H2-producing capacity, therefore the material can be widely applied to electro-catalysis production hydrogen field.
In above-mentioned preparation technology parameter, the material proportional quantity of synthesis presoma cobalt hydroxide, and gas-phase presulfiding reaction
Temperature, time, there is conclusive influence on the pattern of final product, structural stability and performance.Material proportional quantity is to hydrogen-oxygen
Changing the pattern of cobalt nanobelt and the stability of structure has conclusive effect, if proportional quantity exceeds suitable scope, material
A certain degree of change 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
Change the temperature and time of reaction, performance and structural stability to final product cobalt disulfide nanobelt can have an impact, temperature mistake
The low and time is too short, product can be caused to vulcanize insufficient, thing is mutually impure, so that degradation, temperature is too high to cause product knot
Structure bad stability, again such that performance is affected.
The reaction system of the present invention is independent of accurate pH value, and product is uniformly distributed in substrate surface, stabilized structure, only
The titanium sheet for loading product need to be carried out into simple infiltration to clean, and gas phase reaction is simple, and accessory substance is few, success rate
It is high.Simultaneously when carrying out the hydrogen test of electrolysis aquatic products, product of the present invention can carry out production hydrogen directly as working electrode, it is not necessary to carry out
Drop coating, adhesive such as fix at the processing, with the advantage such as easy to operate, active area is big.And material closely connects with conductive substrates
Touch, help lend some impetus to electric charge transfer, reaction barrier is reduced, so as to contribute to the lifting of the electrocatalysis characteristic of material.
Brief description of the drawings
Fig. 1 be embodiment 1-4 prepare different the hydro-thermal reaction times (1,5,10,20h) Co (OH) in corresponding titanium substrate3
The electron scanning micrograph of nanobelt；
Fig. 2 is the CoS in titanium substrate over-assemble structure prepared by embodiment 52The SEM 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
Collection of illustrative plates；
Fig. 4 is solution Co (OH) prepared by embodiment 63The non-package assembly CoS that nanobelt and conversion are obtained2Nanobelt
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.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.Following examples will be helpful to this area
Technical staff further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the general of this area
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
The hydration cobaltous dichlorides of 0.0065g six and 0.0125g hexadecyltrimethylammonium chlorides (CTAC) are weighed, 5mL is dissolved in
The mixed liquor of water and 5mL DMFs (DMF), is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reactor, the treated clean naked titanium sheet of input, encapsulation is placed at 150 DEG C and reacted 1 hour, takes out titanium sheet, successively with ethanol and
Deionized water rinsing is clean, in 60 DEG C of drying, obtains the Co (OH) of self assembly type3Nanobelt.Resulting sample such as Fig. 1 (a)
Shown, when ESEM is shown in the reaction time for 1h, titanium-based basal surface is dendrimer materials, does not grow up to nanobelt pattern also,
Illustrate Co (OH)3Really in titanium substrate surface in situ nucleation and start growth in situ.
Embodiment 2
Co (OH) in titanium sheet substrate3The synthesis of nanobelt
The hydration cobaltous dichlorides of 0.0065g six and 0.0125g hexadecyltrimethylammonium chlorides (CTAC) are weighed, 5mL is dissolved in
The mixed liquor of water and 5mL DMFs (DMF), is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reactor, the treated clean naked titanium sheet of input, encapsulation is placed at 150 DEG C and reacted 5 hours, takes out titanium sheet, successively with ethanol and
Deionized water rinsing is clean, in 60 DEG C of drying, obtains the Co (OH) of self assembly type3Nanobelt.Resulting sample such as Fig. 1 (b)
Shown, when ESEM is shown in the reaction time for 5h, titanium-based basal surface has occurred in that length is about 3 microns, and width is about 1
The Co (OH) of micron3Nanobelt, illustrates Co (OH)3The pattern of small nanotube band has been grown into via 1h dendroid.
Embodiment 3
Co (OH) in titanium sheet substrate3The synthesis of nanobelt
The hydration cobaltous dichlorides of 0.0065g six and 0.0125g hexadecyltrimethylammonium chlorides (CTAC) are weighed, 5mL is dissolved in
The mixed liquor of water and 5mL DMFs (DMF), is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reactor, the treated clean naked titanium sheet of input, encapsulation is placed at 150 DEG C and reacted 10 hours, takes out titanium sheet, ethanol is used successively
It is clean with deionized water rinsing, in 60 DEG C of drying, obtain the Co (OH) of self assembly type3Nanobelt.Resulting sample such as Fig. 1
(c) shown in, when ESEM is shown in the reaction time for 10h, Co (OH)3Nanobelt has been evenly distributed on titanium-based basal surface,
Stability Analysis of Structures, and substrate is overgrowed with, size has further increase compared with 5h again.
Embodiment 4
Co (OH) in titanium sheet substrate3The synthesis of nanobelt
The hydration cobaltous dichlorides of 0.0065g six and 0.0125g hexadecyltrimethylammonium chlorides (CTAC) are weighed, 5mL is dissolved in
The mixed liquor of water and 5mL DMFs (DMF), is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reactor, the treated clean naked titanium sheet of input, encapsulation is placed at 150 DEG C and reacted 20 hours, takes out titanium sheet, ethanol is used successively
It is clean with deionized water rinsing, in 60 DEG C of drying, obtain the Co (OH) of self assembly type3Nanobelt.Resulting sample such as Fig. 1
(d) shown in, when ESEM is shown in the reaction time for 20h, Co (OH)3What the size and degree of distribution and 10h of nanobelt were obtained
Sample is quite similar, illustrates that nanobelt is fully self-assembled to substrate surface.
Embodiment 5
The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate
The hydration cobaltous dichlorides of 0.0065g six and 0.0125g hexadecyltrimethylammonium chlorides (CTAC) are weighed, 5mL is dissolved in
Water and 5mLN, the mixed liquor of dinethylformamide (DMF) are added dropwise 2mL hydrogen peroxide (30%) solution, are transferred to 50mL anti-
Answer kettle, the treated clean naked titanium sheet of input, encapsulation is placed at 150 DEG C and reacted 20 hours, takes out titanium sheet, successively with ethanol and
Deionized water rinsing is clean, in 60 DEG C of drying, obtains the Co (OH) of self assembly type3Nanobelt.Then by Co (OH)3/ Ti is placed in pipe
In formula stove, tube furnace does not encapsulate two ends, it is passed through 300 DEG C in atmosphere, 2h high annealing occurs hot dehydration and decomposes anti-
Should, obtain the Co of self assembly type3O4Nanobelt.By obtained Co3O4/ Ti is placed in tube furnace, is put at the inlet end of tube furnace
2g sulphur powders are put, in flow velocity under 25sccm argon gas atmosphere protection, 400 DEG C vulcanize 6 hours, and question response device dries in the air to room naturally
Temperature, takes out the titanium sheet for being loaded with cobalt disulfide nanobelt, i.e. CoS2/ Ti, is cleaned successively with carbon disulfide and ethanol, in 60 DEG C of bakings
It is dry.Resulting sample is long as shown in Fig. 2 Fig. 2 (a), the ESEM of (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 up of little crystal grain, be polycrystalline structure, and with compared with
Good crystallinity.Fig. 3 (a), (b) show have the CoS of package assembly2The XRD of the nanobelt and CoS of pure phase2Correspondence, and drawing completely
Graceful further testimonial material is pure phase CoS2。
Embodiment 6
The synthesis of the cobalt disulfide nanobelt of non-package assembly without substrate
The hydration cobaltous dichlorides of 0.0065g six and 0.0125g hexadecyltrimethylammonium chlorides (CTAC) are weighed, 5mL is dissolved in
The mixed liquor of water and 5mL DMFs (DMF), is added dropwise 2mL hydrogen peroxide (30%) solution, is transferred to 50mL
Reactor, encapsulation is placed at 150 DEG C and reacted 20 hours, collects solution product, is washed successively with ethanol and deionized water centrifugation
Wash, rotating speed is 5000r/min, in 60 DEG C of drying, obtain the Co (OH) of non-self assembly type3Shown in nanobelt, such as 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 two ends, makes it in sky
By 300 DEG C of 2h high annealing in gas, occur hot dehydration decomposition reaction, obtain the Co of non-self assembly type3O4Nanobelt.Will system
The Co of the non-self assembly type obtained3O4Nanobelt is placed in tube furnace, and 2g sulphur powders are placed at the inlet end of tube furnace, are in flow velocity
Under 25sccm argon gas atmosphere protection, 400 DEG C vulcanize 6 hours, and question response device dries in the air to room temperature naturally, take out product, i.e., it is non-from
Packaging CoS2Nanobelt, is cleaned successively with carbon disulfide and ethanol, in 60 DEG C of drying.The CoS of gained2As shown in Fig. 4 (b), still
It is so nanobelt pattern, with the CoS in substrate over-assemble2It is identical.
Embodiment 7
In titanium sheet substrate over-assemble cobalt disulfide nanobelt and non-assembling cobalt disulfide nanobelt electrolysis aquatic products hydrogen
Experiment.
Laboratory apparatus：CHI660E electrochemical workstations
Three-electrode system：Reference electrode (saturated calomel electrode), to electrode (coated graphite rod electrrode), working electrode (assembling tie
Structure CoS2/ Ti, non-package assembly CoS2(aq.)-Ti, naked titanium sheet)
Produce hydrogen electrolyte：Prepare 0.5M H2SO4Solution, 1M KOH solutions, and tested with acidometer and record two kinds of electrolysis
The pH value of liquid.
Produce hydrogen method of testing：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 solutions), it is 2mV/s to sweep speed；Electrochemical impedance：Amplitude 5mV, frequency range 0.01Hz~105Hz。
The structure 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
Connect as working electrode, be connected by platinum plate electrode folder with electrochemical workstation；
(2) non-package assembly cobalt disulfide nanobelt (non-package assembly CoS2(aq.)-Ti)：
Quantitative cobalt disulfide nanobelt powder is weighed, is scattered in ethanol and water mixed liquid that (ethanol and water volume ratio are 1:
1), oscillator vibration 30min, drop coating is in clean naked titanium sheet, it is ensured that material load amount is 0.7mg/cm2, then drip successively
Plus the Nafion ethanol dilution of 2.5 microlitre 0.05% (mass fraction) three times, pass through platinum plate electrode folder and electrochemistry after drying
Work station is connected；
(3) naked titanium sheet, platinum filament are used to contrast as working electrode, and cling with insulating tape many of naked titanium sheet and platinum filament
Remaining part position, to ensure the production hydrogen area of electrode as fixed value.
Experimental procedure：
(1) 15mL0.5M H are taken2SO4Solution is in electrolytic cell, and logical nitrogen about 15min makes electrolyte by nitrogen saturation, installs
Three-electrode system, tests package assembly CoS respectively2/ Ti, non-package assembly CoS2(aq.)-Ti, platinum filament, the linear volt of naked titanium sheet
Pacify curve；
(2) 15mL1M KOH solutions are taken in electrolytic cell, logical nitrogen about 15min makes electrolyte by nitrogen saturation, surveys respectively
Try package assembly CoS2/ Ti, non-package assembly CoS2(aq.)-Ti, platinum filament, the linear volt-ampere curve of naked titanium sheet；
(3) take 15mL 1M KOH solutions in electrolytic cell, logical nitrogen about 15min makes electrolyte by nitrogen saturation, surveys respectively
Try package assembly CoS2/ Ti, non-package assembly CoS2(aq.)-Ti electrochemical impedance；
(4) every time before test, electrolyte, which is intended to logical nitrogen 15min, makes saturation.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.)-Ti H2-producing capacity.Fig. 6 is alkaline electrolysis
In liquid, package assembly CoS2/ Ti, non-package assembly CoS2(aq.)-Ti impedance spectra, it can be found that package assembly CoS2/Ti
With better electric conductivity.The result of performance test is further demonstrated, and assembling effect promotes material and substrate interface
The electric charge transfer at place, and structure of the material of substrate with bigger catalytic active area and stabilization is uniformly distributed in, so that
Improve it and produce 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：It is 0.005 in mass ratio：0.01 weighs six hydration dichlorides
Cobalt and surfactant hexadecyltrimethylammonium chloride, are dissolved in the mixed liquor of water and DMF (DMF), water and
The volume ratio of DMF is 0.8:1, 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, reactor is then transferred to, the clean naked titanium sheet of input, encapsulation is placed in 140
DEG C reaction 10h, takes out titanium sheet, clean and dry with ethanol and deionized water rinsing successively, obtains 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 atmosphere, and reaction temperature is 250 DEG C, and the reaction time is 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 furnace3O4/ Ti proportionate relationship 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, and the reaction time is 6h, the argon gas stream being passed through
Speed is 20sccm, then dries in the air naturally to room temperature, takes out the titanium sheet for being loaded with cobalt disulfide nanobelt, i.e. CoS2/ Ti, uses curing
Carbon and ethanol are cleaned and dried successively, prepare cobalt disulfide nanobelt package assembly in titanium sheet substrate.
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 is 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：It is 0.006 in mass ratio：0.01 weighs six hydration dichlorides
Cobalt and surfactant hexadecyltrimethylammonium chloride, are dissolved in the mixed liquor of water and DMF (DMF), water and
The volume ratio of DMF is 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, reactor is then transferred to, the clean naked titanium sheet of input, encapsulation is placed in 150 DEG C
10h is reacted, titanium sheet is taken out, it is clean and dry with ethanol and deionized water rinsing successively, 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 atmosphere, and reaction temperature is 300 DEG C, and the reaction time is 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 furnace3O4/ Ti proportionate relationship 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, and the reaction time is 3h, the argon gas stream being passed through
Speed is 30sccm, then dries in the air naturally to room temperature, takes out the titanium sheet for being loaded with cobalt disulfide nanobelt, i.e. CoS2/ Ti, uses curing
Carbon and ethanol are cleaned and dried successively, prepare cobalt disulfide nanobelt package assembly in titanium sheet substrate.
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 is 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：It is 0.007 in mass ratio：0.02 weighs six hydration dichlorides
Cobalt and surfactant hexadecyltrimethylammonium chloride, are dissolved in the mixed liquor of water and DMF (DMF), water and
The volume ratio of DMF is 1.2:1, 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, reactor is then transferred to, the clean naked titanium sheet of input, encapsulation is placed in 160
DEG C reaction 20h, takes out titanium sheet, clean and dry with ethanol and deionized water rinsing successively, obtains 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 atmosphere, and reaction temperature is 350 DEG C, and the reaction time is 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 furnace3O4/ Ti proportionate relationship 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, and the reaction time is 2h, the argon gas stream being passed through
Speed is 60sccm, then dries in the air naturally to room temperature, takes out the titanium sheet for being loaded with cobalt disulfide nanobelt, i.e. CoS2/ Ti, uses curing
Carbon and ethanol are cleaned and dried successively, prepare cobalt disulfide nanobelt package assembly in titanium sheet substrate.
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 is about 4~5 μm, and length is about 15~20 μm, and thickness average value is about~170nm.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in 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 the substantive content of the present invention.
Claims (10)
1. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate, it is characterised in that this method use with
Lower step：
(1) in titanium substrate cobalt hydroxide nanobelt synthesis：Cobalt salt and surfactant are weighed, water and N, N- dimethyl methyls is dissolved in
The mixed liquor of acid amides (DMF), is added dropwise hydrogenperoxide steam generator, is then transferred to reactor, and the clean naked titanium sheet of input, encapsulation is put
In being reacted under high temperature, titanium sheet is taken out, it is clean and dry with ethanol and deionized water rinsing successively, growth in situ is obtained in titanium substrate
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,
Air high temperature is annealed, and is occurred hot dehydration decomposition reaction, is obtained 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 stove, under argon gas atmosphere protection, high temperature vulcanized reaction is carried out, then dries in the air naturally to room
Temperature, takes out the titanium sheet for being loaded with cobalt disulfide nanobelt, i.e. CoS2/ Ti, is infiltrated and cleans and dry successively with carbon disulfide and ethanol
It is dry, prepare 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, it is special
Levy and be, the surfactant described in step (1) is hexadecyltrimethylammonium chloride, described 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, it is special
Levy and be, the volume ratio of water and DMF described in step (1) is 0.8:1~1.2:1, mixed liquor is with adding
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, it is special
Levy and be, the mass fraction of the 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, it is special
Levy and be, controlling reaction temperature is 140~160 DEG C in the reactor described in step (1), the reaction time is 1~20h.
6. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, it is special
Levy and be, the temperature of hot dehydration decomposition reaction is 250~350 DEG C in step (2), the reaction time is 2~5h.
7. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, it is special
Levy and be, step (3) high temperature vulcanization reaction temperature is 350~450 DEG C, and the reaction time is 2~6h, and the argon gas flow velocity being passed through is
20~60sccm.
8. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, it is special
Levy and be, the sulphur powder and Co added in step (3)3O4/ Ti proportionate relationship is 1~2g/1~3cm2。
9. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, it is special
Levy and be, prepare cobalt disulfide nanobelt package assembly in titanium sheet substrate, be the uniform nano strip being assembled in titanium sheet
Cobalt disulfide, the width of nanobelt is 3~5 μm, and length is 10~20 μm, and thickness average value is 130~170nm.
10. the synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate according to claim 1, it is special
Levy and be, preparing cobalt disulfide nanobelt package assembly in titanium sheet substrate has electrolysis aquatic products hydrogen application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396330A (en) * | 2018-03-09 | 2018-08-14 | 三峡大学 | A kind of preparation method of molybdenum disulfide nano sheet@cobalt sulfide nanoneedles original position array electrode |
| CN108411322A (en) * | 2018-03-09 | 2018-08-17 | 三峡大学 | A kind of preparation method of the cobalt sulfide with molybdenum disulfide In-situ reaction electrode and its application on water electrolysis hydrogen producing |
| CN114832836A (en) * | 2022-05-16 | 2022-08-02 | 广西民族大学 | Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190334A (en) * | 2010-03-05 | 2011-09-21 | 同济大学 | Method for preparing trihydroxy cobalt hydroxide |
| CN102642874A (en) * | 2012-04-27 | 2012-08-22 | 中南大学 | Ferrous disulfide semiconductor film preparation method |
-
2017
- 2017-03-13 CN CN201710146654.9A patent/CN106984334B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190334A (en) * | 2010-03-05 | 2011-09-21 | 同济大学 | Method for preparing trihydroxy cobalt hydroxide |
| CN102642874A (en) * | 2012-04-27 | 2012-08-22 | 中南大学 | Ferrous disulfide semiconductor film preparation method |
Non-Patent Citations (1)
| Title |
|---|
| CHUAN-PEI LEE，ET AL: ""Beaded stream-like CoSe2 nanoneedle array for efficient hydrogen evolution electrocatalysis"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396330A (en) * | 2018-03-09 | 2018-08-14 | 三峡大学 | A kind of preparation method of molybdenum disulfide nano sheet@cobalt sulfide nanoneedles original position array electrode |
| CN108411322A (en) * | 2018-03-09 | 2018-08-17 | 三峡大学 | A kind of preparation method of the cobalt sulfide with molybdenum disulfide In-situ reaction electrode and its application on water electrolysis hydrogen producing |
| CN114832836A (en) * | 2022-05-16 | 2022-08-02 | 广西民族大学 | Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic |
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