CN108321388A - The synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate - Google Patents
The synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate Download PDFInfo
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- CN108321388A CN108321388A CN201810026458.2A CN201810026458A CN108321388A CN 108321388 A CN108321388 A CN 108321388A CN 201810026458 A CN201810026458 A CN 201810026458A CN 108321388 A CN108321388 A CN 108321388A
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- titanium sheet
- nickel
- sheet substrate
- ferrous disulfide
- nano
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000010936 titanium Substances 0.000 title claims abstract description 113
- 239000002070 nanowire Substances 0.000 title claims abstract description 92
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 87
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 62
- 239000000758 substrate Substances 0.000 title claims abstract description 61
- 229940095991 ferrous disulfide Drugs 0.000 title claims abstract description 48
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 20
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 claims abstract description 18
- 229910052786 argon Inorganic materials 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 17
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 229910002588 FeOOH Inorganic materials 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 230000036571 hydration Effects 0.000 claims description 7
- 238000006703 hydration reaction Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 229910052960 marcasite Inorganic materials 0.000 description 24
- 229910052683 pyrite Inorganic materials 0.000 description 24
- 239000000463 material Substances 0.000 description 17
- 238000003491 array Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052976 metal sulfide Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002708 enhancing effect 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to the synthetic methods that nickel in titanium sheet substrate adulterates ferrous disulfide nanowire array structure, prepare the mixed aqueous solution containing molysite, nickel salt, sodium sulphate and urea, clean titanium sheet is put into, obtained growth in situ through hydro-thermal reaction adulterates iron oxide hydroxide nano-wire array in the nickel of titanium sheet substrate surface；Presoma is placed in tube furnace and carries out high temperature gas-phase presulfiding using argon gas progress atmosphere protection, has obtained the nickel doping ferrous disulfide nano-wire array for being assembled in titanium sheet substrate.The method of the present invention is easy to operate, reproducible, obtained product structure is stablized, it can uniformly and firmly be distributed in titanium plate surface, it can be applied in electrochemical apparatus directly as two-dimensional electrode material, it is tested simultaneously through electrolysis water, it was found that the doping of nickel significantly improves the electro-catalysis production hydrogen activity and stability of ferrous disulfide, and it is expected to further promote its performance boost in fields such as energy storage, photocatalysis, extends its application range.
Description
Technical field
The present invention relates to a kind of synthetic methods of doping type transient metal sulfide, more particularly, in a kind of titanium sheet substrate
Nickel adulterates the synthetic method of ferrous disulfide nanowire array structure.
Background technology
Now with the development of society, every profession and trade is also continuing to increase the demand of the energy, therefore designs and develop
The high nanometer energy and material of high-performance, low cost, effect then becomes the direction that scientific workers pay close attention to.Especially in electricity
Catalysis and electrochemical energy storage field, the functional limitation sex chromosome mosaicism assistant officer of nano-electrode material are to be solved.Sulphur member in metal sulfide
Element, outermost electron structure are 3S23P4, the empty 3d tracks and 3s, 3p orbital energy level having are close, therefore d tracks are certain
Under the conditions of there are a variety of bonding modes so that the structure of metal sulfide has diversity, shows abundant property, has wide
General application range.Such as cobalt disulfide, ferrous disulfide, curing nickel etc. can be applied to electrolysis aquatic products hydrogen production oxygen, super
Capacitor and field of lithium ion battery.In order to further enhance performance of the metal sulfide in terms of electrochemistry, increasingly multiclass
The material of type is invented, such as multiphase compound material, alloy-type material, doping type material.Wherein, the doping of miscellaneous element is because of tool
There is easy to operate, selective wide, performance boost obviously to become a research hotspot.Such as inside cobalt disulfide nano material into
The doping of row nickel element, or selenium doping is carried out to molybdenum disulfide, so that electro-catalysis H2-producing capacity has been significantly improved.
Pyrite-type ferrous disulfide in metal sulfide belongs to cubic system, earth's surface rich reserves, of low cost, taboo
Bandwidth is 0.95eV, is a kind of using wide semi-conducting material.The ferrous disulfide of Nano grade can be used as with potentiality
Electrode material be widely used in the fields such as photoelectrocatalysis, electrochemical energy storage.Existing work report at present, in ferrous disulfide material
The middle doping for carrying out cobalt ions, at the same it is compound with carbon nanotube, and electrolysis water H2-producing capacity is relative to pure phase ferrous disulfide and carbon
Nanometer tube composite materials, which have, to be obviously improved.Therefore, heteroatomic to adulterate for ferrous disulfide material carrying in terms of producing hydrogen
Prodigious contribution function has been risen to, while being also expected to promote its performance in terms of energy storage, there is certain research significance.Together
When can be built efficient electrochemical energy devices directly as energy device, have in the nano material of conductive substrates over-assemble
The advantages such as easy to operate, active area is big, charge easily transmission.But the metal sulfide of current doping type is numerous due to preparation method
It is trivial, electric conductivity is not excellent enough, and in acidic electrolysis bath produce stabilized hydrogen it is poor, to make its application receive certain limit
System.Based on above-mentioned problem, we have developed the synthesis of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate
Method, preparation process is simple and easy to operate, and product morphology is uniform, reproducible, and structure is relatively stablized, and the doping of nickel makes material
In 0.5M H2SO4The production hydrogen catalysis activity for being substantially better than pure ferrous disulfide nano-wire array and long-acting steady is shown in electrolyte
It is qualitative, and it is expected to be widely applied to the fields such as energy storage, photocatalysis, full electrolysis water.
Invention content
The purpose of the present invention is exactly the limitation in order to overcome above-mentioned ferrous disulfide material in terms of chemical property, development
The synthetic method of nickel doping ferrous disulfide nanowire array structure in a kind of titanium sheet substrate.
The purpose of the present invention can be achieved through the following technical solutions：
The synthetic method of nickel doping ferrous disulfide nanowire array structure, includes the following steps in titanium sheet substrate：
(1) in titanium sheet substrate growth in situ nickel doping iron oxide hydroxide nano-wire array synthesis：By molysite, nickel salt,
Sodium sulphate and urea, which are dissolved in deionized water, obtains reaction solution, and the clean naked titanium sheet for putting into sonicated mistake is placed on high temperature
Lower reaction, takes out titanium sheet, is rinsed well successively with ethyl alcohol and deionized water after reaction, in 80 DEG C of drying, obtains life in situ
Long nickel doping iron oxide hydroxide nano-wire array (Ni-FeOOH/Ti)；
(2) in titanium sheet substrate nickel doping ferrous disulfide nanowire array structure synthesis：Nickel made from step (1) is taken to adulterate
Iron oxide hydroxide nano-wire array is placed in tube furnace, and weighs the air source port that enough sulphur powders are placed in tube furnace, by tubular type
Stove is rinsed with argon gas repeatedly to empty air, under the argon gas atmosphere protection of certain flow rate, carries out high temperature gas-phase presulfiding,
Reaction unit cooled to room temperature is waited for after reaction, takes out the nickel doping ferrous disulfide nanometer linear array for being assembled in titanium sheet substrate
Row, are cleaned successively with ethyl alcohol and deionized water, in 80 DEG C of drying, that is, nickel doping ferrous disulfide nano-wire array knot are prepared
Structure.
Molysite described in step (1) is Iron(III) chloride hexahydrate, and the nickel salt is six hydration Nickel Chlorides, described
Sodium sulphate is anhydrous sodium sulfate.A concentration of 20~30mM of molysite in reaction solution, a concentration of 0~30mM of nickel salt but be 0,
A concentration of 40~60mM of sodium sulphate, a concentration of 0~50mM of urea but be 0.The temperature of pyroreaction is 110~130 DEG C,
Reaction time is 6~12h.
The sulphur powder being added in step (2) and the proportionate relationship of nickel doping iron oxide hydroxide nano-wire array be 1~2g/1~
2cm2.The reaction temperature of high temperature gas-phase presulfiding is 350~450 DEG C, and the reaction time is 1~3h.Argon gas flow velocity is 25sccm.
The nickel doping ferrous disulfide nano-wire array being prepared uniformly firmly is distributed in titanium plate surface, and nano wire is put down
Equal length is 200~250nm, and average diameter is 30~50nm.
In above-mentioned preparation technology parameter, the material proportional quantity and gas-phase presulfiding of presoma Ni-FeOOH nano wires are synthesized
The temperature of reaction, time have decisive impact the pattern of final product, structural stability and Product size.Raw material is matched
Proportion has conclusive effect to the patterns of Ni-FeOOH nano wires and the structural stability for being assembled in titanium sheet substrate, if
Proportional quantity exceeds suitable range, and a degree of variation can occur for the pattern of material, steady in the structure of growth in situ in substrate
It is qualitative also can phase strain differential；The temperature and time of gas-phase presulfiding reaction, to final product Ni-FeS2The performance and structure of nano wire
Stability can have an impact, and temperature is too low and the time is too short, product vulcanization can be caused insufficient, object is mutually impure, to make its performance
It may be deteriorated, temperature is excessively high can be so that product structure bad stability, it is equally possible to can 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 to simple infiltration cleaning, and gas phase reaction is simple, by-product is few, success rate
It is high.Material direct-assembling is in titanium sheet substrate surface simultaneously, can be directly as when carrying out lithium battery encapsulation and electro-catalysis is tested
Working electrode uses, and without a series of cumbersome electrode preparation flows such as the auxiliary of bonding agent and spice, films, avoids and leads
Electrical reduction has the advantages such as easy to operate, active area is big.
Compared with prior art, nickel adulterates ferrous disulfide nanometer linear array in the titanium sheet substrate for the method synthesis that the present invention uses
Row, pattern is uniform, is uniformly dispersed, can it is fine and close, be firmly distributed in titanium sheet substrate surface, and reproducible, synthesis side
Method is simple and easy to do.The doping of nickel is expected to further be promoted ferrous disulfide nano-wire array in electro-catalysis production hydrogen, lithium ion battery side
The performance in face, has a good application prospect.
Description of the drawings
A in Fig. 1, b are respectively the FeOOH nano-wire arrays and Ni- of growth in situ in the titanium sheet substrate of the preparation of embodiment 1,2
The electron scanning micrograph of FeOOH nano-wire arrays；
A in Fig. 2, b are respectively the FeS of titanium sheet substrate over-assemble prepared by embodiment 3,42Nano-wire array and Ni-FeS2
The electron scanning micrograph of nano-wire array；
Fig. 3 is the Ni-FeS of titanium sheet substrate over-assemble prepared by embodiment 42The X ray diffracting spectrum of nano-wire array；
Fig. 4 is the FeS for the titanium sheet substrate over-assemble that embodiment 6 obtains2And Ni-FeS2Nano-wire array and naked titanium sheet three
The linear volt-ampere of person produces hydrogen curve；
Fig. 5 is the Ni-FeS for the titanium sheet substrate over-assemble that embodiment 6 obtains2Nano-wire array (Fig. 5 a) and FeS2Nano wire
The production hydrogen cyclical stability test chart of array (Fig. 5 b)；
Fig. 6 is the FeS for the titanium sheet substrate over-assemble that embodiment 6 obtains2And Ni-FeS2The electrochemical impedance of nano-wire array
Spectrogram.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
The synthesis of the FeOOH nano-wire arrays of growth in situ in titanium sheet substrate
Iron(III) chloride hexahydrate and sodium sulphate are dissolved in deionized water and obtain reaction solution, molysite is dense in reaction solution
Degree is 25mM, a concentration of 50mM of sodium sulphate, and is transferred in reaction kettle, and the clean of sonicated mistake is put into reaction system
Naked titanium sheet encapsulates kettle, is placed at 120 DEG C and reacts 12 hours.Titanium sheet is taken out after reaction, uses ethyl alcohol and deionized water successively
It rinses well, in 80 DEG C of drying, obtains the FeOOH nano-wire arrays of growth in situ.Shown in obtained sample such as Fig. 1 (a), sweep
It retouches Electronic Speculum and shows that FeOOH is nanowire array structure of the homoepitaxial in titanium sheet substrate, the diameter range of single nano-wire is about
For 50~80nm.
Embodiment 2
The synthesis of the Ni-FeOOH nano-wire arrays of growth in situ in titanium sheet substrate
Iron(III) chloride hexahydrate, six hydration Nickel Chlorides, sodium sulphate and urea are dissolved in deionized water and obtain reacting molten
Liquid, a concentration of 25mM, a concentration of 25mM of nickel salt, a concentration of 50mM of sodium sulphate of molysite, the concentration of urea in reaction solution
It for 50mM, and is transferred in reaction kettle, the clean naked titanium sheet of sonicated mistake is put into reaction system, encapsulate kettle, be placed in
It is reacted 12 hours at 120 DEG C.Titanium sheet is taken out after reaction, is rinsed well successively with ethyl alcohol and deionized water, is dried in 80 DEG C,
Obtain the Ni-FeOOH nano-wire arrays of growth in situ.Shown in obtained sample such as Fig. 1 (b), scanning electron microscope shows Ni-
FeOOH homoepitaxials are nanowire array structure in titanium sheet substrate, the diameter range of single nano-wire is about 40~
60nm。
Embodiment 3
FeS in titanium sheet substrate2The synthesis of nanowire array structure
Iron(III) chloride hexahydrate and sodium sulphate are dissolved in deionized water and obtain reaction solution, molysite is dense in reaction solution
Degree is 25mM, a concentration of 50mM of sodium sulphate, and is transferred in reaction kettle, and the clean of sonicated mistake is put into reaction system
Naked titanium sheet encapsulates kettle, is placed at 120 DEG C and reacts 12 hours.Titanium sheet is taken out after reaction, uses ethyl alcohol and deionized water successively
It rinses well, in 80 DEG C of drying, obtains the FeOOH nano-wire arrays of growth in situ.Then FeOOH/Ti obtained is cut into
2cm2, it is placed in tube furnace, and weigh the air source port that 2g sulphur powders are placed in tube furnace, tube furnace is rinsed repeatedly with argon gas
To empty air, under the argon gas atmosphere protection of 25sccm flow velocitys, 450 DEG C of vulcanization 3h wait for that reaction unit naturally cools to room
Temperature is taken out the nickel doping ferrous disulfide nano-wire array for being assembled in titanium sheet substrate, is cleaned successively with ethyl alcohol and deionized water, in 80
DEG C drying, preserve.Shown in obtained sample such as Fig. 2 (a), scanning electron microscope shows FeS2It is homoepitaxial in titanium sheet substrate
The diameter range of nanowire array structure, single nano-wire is about 40~70nm.
Embodiment 4
Ni-FeS in titanium sheet substrate2The synthesis of nanowire array structure
Iron(III) chloride hexahydrate, six hydration Nickel Chlorides, sodium sulphate and urea are dissolved in deionized water and obtain reacting molten
Liquid, a concentration of 25mM, a concentration of 25mM of nickel salt, a concentration of 50mM of sodium sulphate of molysite, the concentration of urea in reaction solution
It for 50mM, and is transferred in reaction kettle, the clean naked titanium sheet of sonicated mistake is put into reaction system, encapsulate kettle, be placed in
It is reacted 12 hours at 120 DEG C.Titanium sheet is taken out after reaction, is rinsed well successively with ethyl alcohol and deionized water, is dried in 80 DEG C,
Obtain the Ni-FeOOH nano-wire arrays of growth in situ.Then Ni-FeOOH/Ti obtained is cut into 2cm2, it is placed in tube furnace
In, and the air source port that 2g sulphur powders are placed in tube furnace is weighed, tube furnace is rinsed with argon gas repeatedly to empty air,
Under the argon gas atmosphere protection of 25sccm flow velocitys, 450 DEG C of vulcanization 3h wait for that reaction unit cooled to room temperature, taking-up are assembled in titanium
The nickel of piece substrate adulterates ferrous disulfide nano-wire array, is cleaned successively with ethyl alcohol and deionized water, in 80 DEG C of drying, preserves.Institute
Shown in obtained sample such as Fig. 2 (b), scanning electron microscope shows Ni-FeS2For nano-wire array of the homoepitaxial in titanium sheet substrate
The average length of structure, nano wire is 250nm, average diameter 50nm.
Embodiment 5
Ni-FeS in titanium sheet substrate2The synthesis of nanowire array structure
Iron(III) chloride hexahydrate, six hydration Nickel Chlorides, sodium sulphate and urea are dissolved in deionized water and obtain reacting molten
Liquid, a concentration of 25mM, a concentration of 25mM of nickel salt, a concentration of 50mM of sodium sulphate of molysite, the concentration of urea in reaction solution
It for 50mM, and is transferred in reaction kettle, the clean naked titanium sheet of sonicated mistake is put into reaction system, encapsulate kettle, be placed in
It is reacted 6 hours at 110 DEG C.Titanium sheet is taken out after reaction, is rinsed well successively with ethyl alcohol and deionized water, is dried in 80 DEG C,
Obtain the Ni-FeOOH nano-wire arrays of growth in situ.Then Ni-FeOOH/Ti obtained is cut into 1cm2, it is placed in tube furnace
In, and the air source port that 1g sulphur powders are placed in tube furnace is weighed, tube furnace is rinsed with argon gas repeatedly to empty air,
Under the argon gas atmosphere protection of 25sccm flow velocitys, 350 DEG C of vulcanization 1h wait for that reaction unit cooled to room temperature, taking-up are assembled in titanium
The nickel of piece substrate adulterates ferrous disulfide nano-wire array, is cleaned successively with ethyl alcohol and deionized water, in 80 DEG C of drying, preserves.It receives
The average length of rice noodles is 200nm, average diameter 30nm.
Embodiment 6
The electrolysis aquatic products hydrogen experiment of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate.
Laboratory apparatus：CHI 660E electrochemical workstations.
Three-electrode system：Saturated calomel electrode (reference electrode), coated graphite rod electrrode (to electrode), Ni-FeS2/ Ti (work
Electrode), FeS2/ Ti (working electrode), naked titanium sheet (working electrode).
Produce hydrogen electrolyte：Prepare 0.5M H2SO4Solution is used in combination acidometer to test its pH value.
Produce hydrogen test method：Linear voltammetry, cyclic voltammetry, Electrode with Electrochemical Impedance Spectroscopy.
The structure of working electrode：
(1) nickel doping ferrous disulfide nano-wire array (Ni-FeS2Nano-wire array)：
With the titanium sheet substrate of the supported catalyst material of the certain area of scissors clip, and wipe the material of long position off,
By titanium sheet substrate directly as working electrode, is pressed from both sides by platinum plate electrode and be connected with electrochemical workstation；
(2) ferrous disulfide nano-wire array (Ni-FeS2Nano-wire array)：
With the titanium sheet substrate of the supported catalyst material of the certain area of scissors clip, and wipe the material of long position off,
By titanium sheet substrate directly as working electrode, is pressed from both sides by platinum plate electrode and be connected with electrochemical workstation；
(3) working electrode is compared：
Using the naked titanium sheet of certain area as working electrode for comparing, insulating tape is used in combination to cling the excess portion of naked titanium sheet
Position, to ensure the production hydrogen area of electrode as fixed value.
Experimental procedure：
(1) appropriate 0.5M H are taken2SO4Solution leads to nitrogen about 20min, then builds three electrode assemblies in electrolytic cell, point
Ni-FeS is not tested2/Ti、FeS2The linear volt-ampere curve (sweeping fast 2mV/s) of/Ti, naked titanium sheet；
(2) appropriate 0.5M H are taken2SO4Solution leads to nitrogen about 20min, then builds three electrode assemblies in electrolytic cell, point
Ni-FeS is not tested2/Ti、FeS2The volt-ampere curve linear for the first time (sweeping fast 2mV/s) of/Ti, and through 2000 Rapid Circulation volt-ampere
Linear volt-ampere curve (sweeping fast 2mV/s) after (sweeping fast 100mV/s)；
(3) appropriate 0.5M H are taken2SO4Solution leads to nitrogen about 20min, then builds three electrode assemblies in electrolytic cell, point
Ni-FeS is not tested2/Ti、FeS2The electrochemical impedance spectrogram of/Ti, test voltage be -440mV, frequency range be 0.1Hz~
105Hz, voltage amplitude 5mV.
Every time before test, electrolyte, which is intended to logical nitrogen 20min, makes saturation, removes the extra oxygen of dissolving.Linear volt-ampere
Curve is through manual ohm compensation deals.It is reversible hydrogen electrode that potential, which is tested, by following formula correction：E (RHE)=E (SCE)+
0.242+0.059pH。
Interpretation of result：
(1) Fig. 4 is the Ni-FeS obtained after tested2/Ti、FeS2/ Ti and and naked titanium sheet linear volt-ampere curve, by contrast
It can find, the Ni-FeS adulterated through nickel2/ Ti is shown better than pure phase FeS2The production hydrogen activity of/Ti has lower production
Higher current density under Hydrogen over potential and identical voltage；
(2) Fig. 5 is Ni-FeS2/Ti、FeS2The cyclical stability of both/Ti, Fig. 5 a show Ni-FeS2/ Ti is passing through
Still have after 2000 Rapid Circulation tests and compare higher repeatability with production hydrogen line volt-ampere curve for the first time, shows preferably
Catalytic stability, and Fig. 5 b then show FeS2/ Ti has poor catalytic stability, the production hydrogen after 2000 cycles bent
Line relative to hydrogen curve is produced and active apparent decaying for the first time, and production Hydrogen over potential is significantly raised, therefore Fig. 5 can be shown that the doping of nickel not
It only helps to promote FeS2Production hydrogen catalysis activity, reduce production Hydrogen over potential, while being obviously improved its and producing hydrogen catalysis stability.
(3) Fig. 6 is Ni-FeS2/Ti、FeS2The electrochemical impedance spectrogram of both/Ti, it can be found that under identical voltage,
Ni-FeS2/ Ti has more good electric conductivity.
The result of above-mentioned performance test further proves that the doping of nickel has been obviously improved the production hydrogen catalysis of ferrous disulfide material
Performance includes optimization, the increase of electric conductivity and the enhancing of catalytic stability of production hydrogen activity.
Embodiment 7
The synthetic method of nickel doping ferrous disulfide nanowire array structure, includes the following steps in titanium sheet substrate：
(1) in titanium sheet substrate growth in situ nickel doping iron oxide hydroxide nano-wire array synthesis：It is hydrated trichlorine by six
Change iron, six hydration Nickel Chlorides, sodium sulphate and urea to be dissolved in deionized water and obtain reaction solution, molysite is dense in reaction solution
Degree is 30mM, a concentration of 30mM of nickel salt, a concentration of 60mM of sodium sulphate, a concentration of 50mM of urea, and is transferred in reaction kettle,
After putting into the clean naked titanium sheet of sonicated mistake, kettle is encapsulated, 130 DEG C of reaction 6h is placed in, takes out titanium sheet after reaction, successively
It is rinsed well with ethyl alcohol and deionized water, in 80 DEG C of drying, obtains the nickel doping iron oxide hydroxide nano-wire array of growth in situ
(Ni-FeOOH/Ti)；
(2) in titanium sheet substrate nickel doping ferrous disulfide nanowire array structure synthesis：Nickel made from step (1) is taken to adulterate
Iron oxide hydroxide nano-wire array is placed in tube furnace, and weighs the air source port that enough sulphur powders are placed in tube furnace, addition
Sulphur powder and the proportionate relationship of nickel doping iron oxide hydroxide nano-wire array are 2g/1cm2, tube furnace is rushed repeatedly with argon gas
It washes to empty air, under the argon gas atmosphere protection that flow velocity is 25sccm, carries out high temperature gas-phase presulfiding, reaction temperature 450
DEG C, reaction time 1h waits for reaction unit cooled to room temperature after reaction, takes out the nickel doping for being assembled in titanium sheet substrate
Ferrous disulfide nano-wire array is cleaned successively with ethyl alcohol and deionized water, in 80 DEG C of drying, that is, nickel doping curing is prepared
The average length of Fe nanowire array structure, nano wire is 200nm, average diameter 50nm.
Embodiment 8
The synthetic method of nickel doping ferrous disulfide nanowire array structure, includes the following steps in titanium sheet substrate：
(1) in titanium sheet substrate growth in situ nickel doping iron oxide hydroxide nano-wire array synthesis：It is hydrated trichlorine by six
Change iron, six hydration Nickel Chlorides, sodium sulphate and urea to be dissolved in deionized water and obtain reaction solution, molysite is dense in reaction solution
Degree is 20mM, a concentration of 0.1mM of nickel salt, a concentration of 40mM of sodium sulphate, a concentration of 0.1mM of urea, and is transferred to reaction kettle
In, after putting into the clean naked titanium sheet of sonicated mistake, kettle is encapsulated, 110 DEG C of reaction 12h is placed in, takes out titanium sheet after reaction,
It is rinsed well successively with ethyl alcohol and deionized water, in 80 DEG C of drying, obtains the nickel doping iron oxide hydroxide nano wire of growth in situ
Array (Ni-FeOOH/Ti)；
(2) in titanium sheet substrate nickel doping ferrous disulfide nanowire array structure synthesis：Nickel made from step (1) is taken to adulterate
Iron oxide hydroxide nano-wire array is placed in tube furnace, and weighs the air source port that enough sulphur powders are placed in tube furnace, addition
Sulphur powder and the proportionate relationship of nickel doping iron oxide hydroxide nano-wire array are 1g/2cm2, tube furnace is rushed repeatedly with argon gas
It washes to empty air, under the argon gas atmosphere protection that flow velocity is 25sccm, carries out high temperature gas-phase presulfiding, reaction temperature 350
DEG C, reaction time 3h waits for reaction unit cooled to room temperature after reaction, takes out the nickel doping for being assembled in titanium sheet substrate
Ferrous disulfide nano-wire array is cleaned successively with ethyl alcohol and deionized water, in 80 DEG C of drying, that is, nickel doping curing is prepared
The average length of Fe nanowire array structure, nano wire is 250nm, average diameter 30nm.
Specific embodiments of the present invention are 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 (8)
1. the synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate, which is characterized in that this method includes
Following steps：
(1) in titanium sheet substrate growth in situ nickel doping iron oxide hydroxide nano-wire array synthesis：By molysite, nickel salt, sulfuric acid
Sodium and urea, which are dissolved in deionized water, obtains reaction solution, and the clean naked titanium sheet for putting into sonicated mistake is placed under high temperature instead
It answers, takes out titanium sheet after reaction, rinsed well successively with ethyl alcohol and deionized water, in 80 DEG C of drying, obtain growth in situ
Nickel adulterates iron oxide hydroxide nano-wire array (Ni-FeOOH/Ti)；
(2) in titanium sheet substrate nickel doping ferrous disulfide nanowire array structure synthesis：Nickel made from step (1) is taken to adulterate hydrogen-oxygen
Change oxygen Fe nanowire array to be placed in tube furnace, and weigh the air source port that enough sulphur powders are placed in tube furnace, tube furnace is used
Argon gas is rinsed repeatedly to empty air, under the argon gas atmosphere protection of certain flow rate, carries out high temperature gas-phase presulfiding, reaction
After wait for reaction unit cooled to room temperature, take out the nickel doping ferrous disulfide nano-wire array for being assembled in titanium sheet substrate,
It is cleaned successively with ethyl alcohol and deionized water, in 80 DEG C of drying, that is, nickel doping ferrous disulfide nanowire array structure is prepared.
2. the synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate according to claim 1,
It is characterized in that, the molysite described in step (1) is Iron(III) chloride hexahydrate, and the nickel salt is six hydration Nickel Chlorides, described
Sodium sulphate be anhydrous sodium sulfate.
3. the synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate according to claim 1,
Be characterized in that, a concentration of 20~30mM of molysite in the reaction solution described in step (1), a concentration of 0~30mM of nickel salt but
Be 0, a concentration of 40~60mM of sodium sulphate, a concentration of 0~50mM of urea but be 0.
4. the synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate according to claim 1,
It is characterized in that, the temperature of step (1) high temperature reaction is 110~130 DEG C, and the reaction time is 6~12h.
5. the synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate according to claim 1,
Be characterized in that, the proportionate relationship of the sulphur powder being added in step (2) and nickel doping iron oxide hydroxide nano-wire array be 1~2g/1~
2cm2。
6. the synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate according to claim 1,
It is characterized in that, the reaction temperature of step (2) high temperature gas-phase presulfiding is 350~450 DEG C, and the reaction time is 1~3h.
7. the synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate according to claim 1,
It is characterized in that, argon gas flow velocity is 25sccm in step (2).
8. the synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate according to claim 1,
It is characterized in that, the nickel doping ferrous disulfide nano-wire array being prepared uniformly firmly is distributed in titanium plate surface, nano wire
Average length is 200~250nm, and average diameter is 30~50nm.
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| CN111599980A (en) * | 2020-06-18 | 2020-08-28 | 电子科技大学 | NixFe1-xS2Solid solution cathode material and preparation method thereof |
| CN111710849A (en) * | 2020-07-08 | 2020-09-25 | 广西师范大学 | ZnS/SnS @ NC hollow microsphere anode material for lithium ion/sodium ion battery anode and preparation method thereof |
| CN112820552A (en) * | 2020-12-31 | 2021-05-18 | 延边大学 | Nickel-iron bimetal hydroxide material and preparation method and application thereof |
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| CN102714137A (en) * | 2009-10-16 | 2012-10-03 | 康奈尔大学 | Method and apparatus including nanowire structure |
| CN103872186A (en) * | 2014-03-19 | 2014-06-18 | 浙江大学 | FeS2 thin film and preparation method thereof |
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| CN102714137A (en) * | 2009-10-16 | 2012-10-03 | 康奈尔大学 | Method and apparatus including nanowire structure |
| CN103872186A (en) * | 2014-03-19 | 2014-06-18 | 浙江大学 | FeS2 thin film and preparation method thereof |
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| CN111599980A (en) * | 2020-06-18 | 2020-08-28 | 电子科技大学 | NixFe1-xS2Solid solution cathode material and preparation method thereof |
| CN111710849A (en) * | 2020-07-08 | 2020-09-25 | 广西师范大学 | ZnS/SnS @ NC hollow microsphere anode material for lithium ion/sodium ion battery anode and preparation method thereof |
| CN112820552A (en) * | 2020-12-31 | 2021-05-18 | 延边大学 | Nickel-iron bimetal hydroxide material and preparation method and application thereof |
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