CN107337233A - A kind of method of one step vulcanization method synthesis of titanium dioxide and titanium disulfide composite - Google Patents
A kind of method of one step vulcanization method synthesis of titanium dioxide and titanium disulfide composite Download PDFInfo
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- CN107337233A CN107337233A CN201710414025.XA CN201710414025A CN107337233A CN 107337233 A CN107337233 A CN 107337233A CN 201710414025 A CN201710414025 A CN 201710414025A CN 107337233 A CN107337233 A CN 107337233A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 21
- 238000004073 vulcanization Methods 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910003092 TiS2 Inorganic materials 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 238000012856 packing Methods 0.000 claims abstract description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000008240 homogeneous mixture Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 30
- 238000013019 agitation Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
-
- B01J35/39—
-
- B01J35/40—
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/007—Titanium sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
Abstract
The invention discloses a kind of method of step vulcanization method synthesis of titanium dioxide and titanium disulfide composite, butyl titanate is added dropwise in ethanol solution and forms mixed solution A, ethanol is added in deionized water and forms mixed solution B；Mixed solution A is added dropwise in mixed solution B, ultrasonic echography is then carried out and obtains clear solution C, the pH value for adjusting solution C obtains solution D for 6；Solution D is added in the liner of polytetrafluoroethylene (PTFE), and control packing ratio to be reacted；After the completion of question response, scrubbed, dry and grinding obtains TiO2Presoma；By TiO2Presoma and thioacetamide are put into porcelain boat and cover lid；Entirety is put into low temperature tube furnace and is sintered reaction, and taking-up sample is ground into powder sample when temperature drops to room temperature, that is, obtains TiO2/TiS2Composite.The inventive method is simple, the cycle is short, and the material lumpy sizes being prepared reach tens to hundreds of nanometers, and material purity is high, crystallinity is strong, pattern is uniform.
Description
Technical field
The present invention relates to field of composite material preparation, and in particular to an a kind of step vulcanization method synthesis of titanium dioxide and curing
The method of titanium composite material.
Background technology
TiO2A kind of wider semi-conducting material of energy gap, because its have excellent chemical resistance, heat resistance,
Weatherability and high stability, particularly TiO2The advantages that good photocatalytic of nano material, property are stable, cheap,
It is set to be widely used in the field such as photocatalysis, photocatalytic water and opto-electronic conversion, sensor.TiO2Material generally has three kinds of crystalline substances
Type：Brockite, anatase and rutile-type, different crystal formations have different chemism and purposes.With nano material
Continue to develop, the advantages that size is smaller, and specific surface area is bigger becomes more and more important.At present, TiO2The preparation method of material and
Resulting microscopic appearance is more and more, and preparation method has：Hydro-thermal method, sol-gal process, anodizing, template auxiliary law
Deng, and resulting pattern has：Particle, sheet, nanotube, nano wire and other zero dimensions, one-dimensional, two and three dimensions pattern
Deng.And hydro-thermal method prepares TiO2Material has the advantages of many compared to other methods, such as：Raw material is readily available, is simple to operate,
Reaction condition is also more gentle.The composition that can effectively avoid having in system under conditions of closed volatilizees, meanwhile, carrying out instead
Be advantageous to nucleus generation and the growth of crystal during answering, obtain complete crystal morphology.Chi can above all be obtained
The less sample of very little uniform particle agglomeration.Therefore more TiO2Material be all be prepared by hydro-thermal method it is a variety of
Pattern.
TiS2Belong to IVB:The binary compound of VI races, it is typical hexagonal phase crystallographic system octahedral structure (cell parameter：).And there is layer structure, each layer of layer structure includes the interlayer of sulphur-titanium-sulphur, layer
Between be to be connected by weak Van der Waals force, and by Covalent bonding together, while suitable interlamellar spacing between layers be present.TiS2
This excellent layer structure and cheap resource so that it is not only applied in fields such as photocatalysis, semi-conducting materials, is gone back extensive
The positive and negative electrode material as lithium battery used.At present, researchers prepare chi by a variety of experimental methods
Very little or different structure TiS2, main structure has TiS2Hexagon sheet, petal-shaped, nanotube-shaped or zero dimension, a peacekeeping
Two-dimensional nanostructure, while researcher is also synthesizing the TiS of different structure by different processes2, people are usual
According to the different by TiS of structure2Materials application is particularly most widely used in field of batteries in different fields.And most
A kind of potential sulfide battery material.
Composition, pattern, size due to material etc. can affect to the various performances of sample.Two dimension, three-dimensional
And multidimensional or porous structure and morphology are advantageous to the lifting of performance.And particle is smaller, specific surface area is bigger, then the property of material
Can be also better.
At present, nanometer TiS2The preparation method of material mainly has solid reaction process [M.J.McKelvy.W.S.Glaunsing
er.Synthesis and characterization of nearly stoichiometric titanium disulfide
[J].Journal of Solid State Chemistry.1987,66:181-188], liquid phase method [Yuping Liu,
Hongtao Wang,Liang Cheng,Na Han,etc.TiS2nanoplates:A high-rate and stable
electrode material for sodium ion batteries[J].Nano Energy.2016,20:168–175]、
Gas phase synthesis method [Alexander Margolin, Ronit Popovitz-Biro, etc.Inorganic fullerene-
like nanoparticles of TiS2[J].Chemical Physics Letters.2005,411(1–3,5):162–
166], sol-gal process [Alexandru L.Let, David E.Mainwaring, etc.Thio sol-gel synthesis
of titanium disulfide thin films and powders using titanium alkoxide
precursors[J].Journal of Non-Crystalline Solids.2008,354(15-16):1801–1807.]、
Gas-phase transport method [Jun Chen, Suo-Long Li, Zhan-Liang Tao, etc.Titanium Disulfide
Nanotubes as Hydrogen-Storage Materials[J].J.AM.CHEM.SOC.2003,125:5284-
5285.].Wherein solid reaction process has the advantages that not need solvent, equipment simple and easy control of reaction conditions, but due to anti-
It should be carried out in solid phase, generally reaction is not thorough, and yield is relatively low, and the cycle of sulphur powder and titanium valve reaction is oversize.Liquid phase method is usually used in
Obtain highly crystalline TiS2Nanometer sheet and petal-like structures, but the nanometer sheet yield very little that this method obtains, and controllability is non-
It is often poor, it may be only available for the scientific research on basis.The too difficult control of the condition of reaction, operability are not very strong.And collosol and gel
Method is reacted using Titanium alkoxides and hydrogen sulfide gas, and hydrogen sulfide gas has toxicity, and the flow velocity of course of reaction is not easy
Control, easily causes danger.Vapor phase method is synthesized using hydrogen sulfide gas as raw material, and hydrogen sulfide gas has poison
Property, and the flow velocity of course of reaction is difficult to control, yield is relatively low.Gas-phase transport method is carried out using materials such as iodine as agent delivery
Reaction.The difficult control of the course of reaction, higher is required to experiment condition, the product of gained is impure, and yield is also than relatively low.
The content of the invention
It is an object of the invention to provide the side of a kind of step vulcanization method synthesis of titanium dioxide and titanium disulfide composite
Method, the defects of to overcome above-mentioned prior art to exist, the inventive method is simple, the cycle is short, the material lumpy sizes being prepared
Reach tens to hundreds of nanometers, and material purity is high, crystallinity is strong, pattern is uniform, can apply photocatalysis, photocatalytic water or
The fields such as battery.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of method of step vulcanization method synthesis of titanium dioxide and titanium disulfide composite, comprises the following steps：
1) butyl titanate is added dropwise in ethanol solution under stirring, homogeneous mixture solotion A is formed, wherein often
2~6ml butyl titanates are added in 8~10ml ethanol；Ethanol is added in the presence of stirring again in deionized water and formed
Even mixed solution B, wherein adding 1~3ml ethanol in per 40ml deionized waters；
2) mixed solution A is added dropwise in mixed solution B in the presence of stirring, then carries out ultrasonic echography and obtain
To clear solution C, the pH value for adjusting solution C obtains solution D for 6；
3) solution D is added in the liner of polytetrafluoroethylene (PTFE), and controls packing ratio to be reacted；
4) after the completion of question response, distinguish centrifuge washing through deionized water and ethanol, be then dried in vacuo and grind to obtain
TiO2Presoma；
5) according to elemental mole ratios nTi:nS=(0.3~2.7)：(5.2~23.6) weigh TiO2Presoma and thioacetyl
Amine, by TiO2Presoma is put into small porcelain boat, and thioacetamide is put into big porcelain boat, and small porcelain boat then is put into big porcelain boat middle cover
Good lid obtains porcelain boat combination；
6) porcelain boat combination is put into low temperature tube furnace, after the air in pipe is excluded totally, then will be pumped into pipe true
Altitude；
7) reaction and then by low temperature tube furnace is sintered, after question response stops, argon gas is passed through and is protected, treat temperature
Low temperature tube furnace, which is opened, when dropping to room temperature takes out porcelain boat combination；
8) sample in porcelain boat combination is poured into mortar the sample that is ground into powder, that is, obtains TiO2/TiS2Composite wood
Material.
Further, the ultrasonic time is 0.5~2h in step 2).
Further, using 0.1mol/L HCl solution regulation pH in step 2).
Further, packing ratio is controlled 40%~60% in step 3).
Further, at 160 DEG C~200 DEG C, the reaction time is controlled in 12h~20h for reaction temperature control in step 3).
Further, centrifuge washing is distinguished 3~6 times using deionized water and ethanol in step 4).
Further, vacuum drying temperature is 80 DEG C in step 4), and the time is 6~10h.
Further, the temperature of sintering reaction is 500 DEG C~900 DEG C in step 7), and the time is 1~4h.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention is that have by a step vulcanization method synthesis of titanium dioxide and titanium disulfide composite, prepared material
Preparation method simply and cycle short advantage, in addition, material lumpy sizes reach tens to hundreds of nanometers, and material purity height,
Crystallinity is strong, pattern is uniform, can apply in fields such as photocatalysis, photocatalytic water or batteries.
Compare from preparation method, low temperature tube furnace, which carries out vulcanization, has simple technique, short preparation period and reaction condition
The characteristic being easily controlled, the process of reaction and pattern size, the composition of thing phase can be controlled using different temperature, suitable
At a temperature of can obtain different thing phase compositions and special structure and morphology.The different electrochemistry to battery of thing phase and appearance structure
Performance has large effect, in addition, low temperature tubular type stove has, reaction rate is very fast, reaction fully thoroughly, grain growth it is controllable and
The advantages such as even size distribution, the reaction that it avoids conventional method are difficult to and difficult control, high energy consumption, low yield and technique
The shortcomings of complicated.
The inventive method H mainly as caused by decomposing thioacetamide (TAA)2S gases and homemade TiO2Material is carried out
Reaction.Influence of the control of temperature to its product is very big, is reacted in relatively low temperature, then what is prepared is pure phase
TiO2Material, and reacted to obtain the titanium sulfide material of other dephasigns at a higher temperature, because during the course of the reaction,
Temperature is relatively low, H caused by thioacetamide (TAA) decomposition2S gases have little time and TiO2Reaction just as in pipe concentration difference and to
The both ends diffusion of pipe, causes unreacted sulphur source to be all deposited on the both ends of pipe.TiO simultaneously2In oxygen atom can not be former by sulphur
Son is replaced and obtains TiS2Material.If raise temperature, H2S gases can be produced and expanded rapidly, H in pipe2The concentration of S gases
It is very big, TiO under higher temperature2In oxygen atom can by sulphur atom replace and obtain TiS2Material even other non-stoichiometry
The titanium sulfide material of ratio, therefore the temperature of rational control vulcanization is extremely important.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention 2 the titanium dioxide and the titanium disulfide composite that are prepared by a step vulcanization method
XRD；
Fig. 2 is that the embodiment of the present invention 2 passes through a step vulcanization method synthesis of titanium dioxide and the SEM of titanium disulfide composite
Figure.
Embodiment
Embodiments of the present invention are described in further detail below：
A kind of method of step vulcanization method synthesis of titanium dioxide and titanium disulfide composite, comprises the following steps：
1) butyl titanate is added dropwise in ethanol solution under magnetic agitation effect, forms homogeneous mixture solotion A, its
In 2~6ml butyl titanates are added in every 8~10ml ethanol；Ethanol is added to deionized water in the presence of magnetic agitation again
Middle formation homogeneous mixture solotion B, wherein adding 1~3ml ethanol in per 40ml deionized waters；
2) mixed solution A is added dropwise in mixed solution B in the presence of magnetic agitation, then carries out ultrasonic wave and surpass
0.5~2h of sound obtains clear solution C, uses the pH value of 0.1mol/L HCl solution regulation solution C to obtain solution D for 6；
3) solution D is added in the liner of polytetrafluoroethylene (PTFE), 40%~60%, reaction temperature control exists for packing ratio control
160 DEG C~200 DEG C, the reaction time is controlled in 12h~20h；
4) after the completion of question response, centrifuge washing is distinguished 3~6 times through deionized water and ethanol, then vacuum is done at 80 DEG C
Dry 6~10h and grind obtain TiO2Presoma；
5) according to elemental mole ratios nTi:nS=(0.3~2.7)：(5.2~23.6) weigh TiO2Presoma and thioacetyl
Amine, by TiO2Presoma is put into small porcelain boat, and thioacetamide is put into big porcelain boat, and small porcelain boat then is put into big porcelain boat middle cover
Good lid obtains porcelain boat combination；
6) porcelain boat combination is put into low temperature tube furnace, after the air in pipe is excluded totally, then will be pumped into pipe true
Altitude；
7) carry out reacting after 1~4h of heating at a temperature of 500 DEG C~900 DEG C stopping immediately, be passed through argon gas and protected, treated
Temperature opens low temperature tube furnace when dropping to room temperature and takes out porcelain boat combination；
8) sample in porcelain boat combination is poured into mortar the sample that is ground into powder, that is, obtains TiO2/TiS2Composite wood
Material.
So far, also without occurring by this kind of method preparing titanium dioxide and titanium disulfide composite, because secondly
Titanium oxide has the advantages that excellent chemically and physically characteristic and cheap, while the field in terms of photocatalysis and battery
Also it is relatively broad, but its performance given play to is also very limited, and titanium disulfide is a kind of material of layer structure, and have
Very narrow energy gap, its superior layer structure can not only be used as catalysis material, be also used as battery material and obtain
Using, but complicated preparation technology and performance is difficult to get a promotion and make it that its application is limited, and therefore, passes through step vulcanization
Method prepare titanium dioxide and titanium disulfide composite, not only their application field can be made to be expanded, can be with
Mutually improve the performance between them.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
1) 2ml butyl titanates are weighed to be added dropwise in 8ml ethanol solution under magnetic agitation effect, are formed uniformly mixed
Compound A, then 1ml ethanol is added in 40ml deionized water in the presence of magnetic agitation and forms homogeneous mixture solotion B.
2) mixed solution A is added dropwise in mixed solution B in the presence of stirring, then carries out ultrasonic echography
After 0.5h obtains clear solution C.The HCl regulation pH values that it is possible to additionally incorporate 0.1mol/L obtain solution D for 6.
3) solution D being added in the liner of polytetrafluoroethylene (PTFE), 40%, reaction temperature is controlled at 160 DEG C for packing ratio control,
Reaction time is controlled in 12h.
4) after the completion of question response, centrifuge washing is distinguished 3 times through deionized water and ethanol.Then it is dried in vacuo 6h at 80 DEG C
Afterwards, it is ground to obtain TiO2Presoma.
5) a certain amount of TiO is weighed2Powder, according to elemental mole ratios nTi:nS=0.3:5.2 weigh a certain amount of thio second
Acid amides (TAA), by TiO2Powder is put into small porcelain boat, and thioacetamide is put into big porcelain boat, and small porcelain boat then is put into big porcelain
Lid is covered in boat and obtains A.
6) A is put into low temperature tube furnace, first vacuumized, be re-filled with nitrogen, so in triplicate afterwards by pipe
Air exclude it is clean after, then by the environment that is evacuated in pipe.
7) carry out reacting after heating 4h at a temperature of 500 DEG C stopping immediately, and be passed through argon gas and protected, treat that temperature drops to
Low temperature tube furnace is opened during room temperature and takes out porcelain boat.
8) sample in porcelain boat is poured into mortar and is ground into tiny powdered samples, be i.e. TiO2/TiS2Mixture.
Embodiment 2
1) 4ml butyl titanates are weighed to be added dropwise in 9ml ethanol solution under magnetic agitation effect, are formed uniformly mixed
Compound A, then 2ml ethanol is added in 40ml deionized water in the presence of magnetic agitation and forms homogeneous mixture solotion B.
2) mixed solution A is added dropwise in mixed solution B in the presence of stirring, then carries out ultrasonic echography
After 1.5h obtains clear solution C.The HCl regulation pH values that it is possible to additionally incorporate 0.1mol/L obtain solution D for 6.
3) solution D being added in the liner of polytetrafluoroethylene (PTFE), 50%, reaction temperature is controlled at 180 DEG C for packing ratio control,
Reaction time is controlled in 16h.
4) after the completion of question response, centrifuge washing is distinguished 5 times through deionized water and ethanol.Then it is dried in vacuo 8h at 80 DEG C
Afterwards, it is ground to obtain TiO2Presoma.
5) a certain amount of TiO is weighed2Powder, according to elemental mole ratios nTi:nS=1.0:15.3 weigh it is a certain amount of thio
Acetamide (TAA), by TiO2Powder is put into small porcelain boat, and thioacetamide is put into big porcelain boat, is then put into small porcelain boat greatly
Lid is covered in porcelain boat and obtains A.
6) A is put into low temperature tube furnace, first vacuumized, be re-filled with nitrogen, so in triplicate afterwards by pipe
Air exclude it is clean after, then by the environment that is evacuated in pipe.
7) carry out reacting after heating 2h at a temperature of 700 DEG C stopping immediately, and be passed through argon gas and protected, treat that temperature drops to
Low temperature tube furnace is opened during room temperature and takes out porcelain boat.
8) sample in porcelain boat is poured into mortar and is ground into tiny powdered samples, be i.e. TiO2/TiS2Mixture.
As can be seen from Figure 1 sample prepared by the present embodiment corresponds to standard card PDF 15-0853 (curing respectively
Titanium), PDF 21-1272 (titanium dioxide).It can also be seen that the crystal property of the material is preferable from XRD, thing is mutually also fine；
It is about tens to 200nm or so from the microscopic dimensions for understanding the material in Fig. 2, the thickness of its sheet is about a 50nm left sides
It is right.
Embodiment 3
1) 6ml butyl titanates are weighed to be added dropwise in 10ml ethanol solution under magnetic agitation effect, are formed uniform
Mixture A, then 3ml ethanol is added in 40ml deionized water in the presence of magnetic agitation and forms homogeneous mixture solotion B.
2) mixed solution A is added dropwise in mixed solution B in the presence of stirring, then carries out ultrasonic echography 2h
After obtaining clear solution C.The HCl regulation pH values that it is possible to additionally incorporate 0.1mol/L obtain solution D for 6.
3) solution D being added in the liner of polytetrafluoroethylene (PTFE), 60%, reaction temperature is controlled at 200 DEG C for packing ratio control,
Reaction time is controlled in 20h.
4) after the completion of question response, centrifuge washing is distinguished 6 times through deionized water and ethanol.Then it is dried in vacuo at 80 DEG C
It is ground to obtain TiO after 10h2Presoma.
5) a certain amount of TiO is weighed2Powder, according to elemental mole ratios nTi:nS=2.7:23.6 weigh it is a certain amount of thio
Acetamide (TAA), by TiO2Powder is put into small porcelain boat, and thioacetamide is put into big porcelain boat, is then put into small porcelain boat greatly
Lid is covered in porcelain boat and obtains A.
6) A is put into low temperature tube furnace, first vacuumized, be re-filled with nitrogen, so in triplicate afterwards by pipe
Air exclude it is clean after, then by the environment that is evacuated in pipe.
7) carry out reacting after heating 1h at a temperature of 900 DEG C stopping immediately, and be passed through argon gas and protected, treat that temperature drops to
Low temperature tube furnace is opened during room temperature and takes out porcelain boat.
8) sample in porcelain boat is poured into mortar and is ground into tiny powdered samples, be i.e. TiO2/TiS2Mixture.
Claims (8)
1. a kind of method of step vulcanization method synthesis of titanium dioxide and titanium disulfide composite, it is characterised in that including following
Step：
1) butyl titanate is added dropwise in ethanol solution under stirring, forms homogeneous mixture solotion A, wherein every 8~
2~6ml butyl titanates are added in 10ml ethanol；Ethanol is added in the presence of stirring again to be formed in deionized water and uniformly mixed
Solution B is closed, wherein adding 1~3ml ethanol in per 40ml deionized waters；
2) mixed solution A is added dropwise in mixed solution B in the presence of stirring, then carries out ultrasonic echography and obtain
Bright solution C, the pH value for adjusting solution C obtain solution D for 6；
3) solution D is added in the liner of polytetrafluoroethylene (PTFE), and controls packing ratio to be reacted；
4) after the completion of question response, distinguish centrifuge washing through deionized water and ethanol, be then dried in vacuo and grind to obtain TiO2Forerunner
Body；
5) according to elemental mole ratios nTi:nS=(0.3~2.7)：(5.2~23.6) weigh TiO2Presoma and thioacetamide, will
TiO2Presoma is put into small porcelain boat, and thioacetamide is put into big porcelain boat, and then small porcelain boat is put into big porcelain boat and covered
Son obtains porcelain boat combination；
6) porcelain boat combination is put into low temperature tube furnace, by the air in pipe exclude it is clean after, then by the ring that is evacuated in pipe
Border；
7) reaction and then by low temperature tube furnace is sintered, after question response stops, argon gas is passed through and is protected, treat that temperature drops to
Low temperature tube furnace is opened during room temperature and takes out porcelain boat combination；
8) sample in porcelain boat combination is poured into mortar the sample that is ground into powder, that is, obtains TiO2/TiS2Composite.
2. the method for a kind of step vulcanization method synthesis of titanium dioxide according to claim 1 and titanium disulfide composite,
Characterized in that, the ultrasonic time is 0.5~2h in step 2).
3. the method for a kind of step vulcanization method synthesis of titanium dioxide according to claim 1 and titanium disulfide composite,
Characterized in that, using 0.1mol/L HCl solution regulation pH in step 2).
4. the method for a kind of step vulcanization method synthesis of titanium dioxide according to claim 1 and titanium disulfide composite,
Characterized in that, packing ratio control is 40%~60% in step 3).
5. the method for a kind of step vulcanization method synthesis of titanium dioxide according to claim 1 and titanium disulfide composite,
Characterized in that, at 160 DEG C~200 DEG C, the reaction time is controlled in 12h~20h for reaction temperature control in step 3).
6. the method for a kind of step vulcanization method synthesis of titanium dioxide according to claim 1 and titanium disulfide composite,
Characterized in that, centrifuge washing is distinguished 3~6 times using deionized water and ethanol in step 4).
7. the method for a kind of step vulcanization method synthesis of titanium dioxide according to claim 1 and titanium disulfide composite,
Characterized in that, vacuum drying temperature is 80 DEG C in step 4), the time is 6~10h.
8. the method for a kind of step vulcanization method synthesis of titanium dioxide according to claim 1 and titanium disulfide composite,
Characterized in that, the temperature of sintering reaction is 500 DEG C~900 DEG C in step 7), the time is 1~4h.
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| CN112023869A (en) * | 2020-07-31 | 2020-12-04 | 盐城工学院 | Method for preparing mesoporous titanium disulfide adsorbent and application |
| CN113707866A (en) * | 2021-08-30 | 2021-11-26 | 安徽工业大学 | Lifting TiO2Method for storing property of electrode material sodium ion |
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