CN105688943B - A kind of stratiform MoS2‑TiO2The preparation method of nano composite material - Google Patents
A kind of stratiform MoS2‑TiO2The preparation method of nano composite material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 79
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002360 explosive Substances 0.000 claims abstract description 19
- -1 aromatic thioether Chemical class 0.000 claims abstract description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 235000019441 ethanol Nutrition 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 238000007873 sieving Methods 0.000 claims description 20
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical group OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 150000003568 thioethers Chemical class 0.000 claims description 9
- 150000004984 aromatic diamines Chemical class 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 229910052961 molybdenite Inorganic materials 0.000 abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005411 Van der Waals force Methods 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 abstract description 2
- 230000032798 delamination Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002131 composite material Substances 0.000 description 11
- 239000004408 titanium dioxide Substances 0.000 description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000005909 ethyl alcohol group Chemical group 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000008236 heating water Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- 238000005461 lubrication Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/22—Compounds containing sulfur, selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
Abstract
The invention provides a kind of stratiform MoS2‑TiO2The preparation method of nano composite material, molybdenum disulfide powder is added in layering solution and carries out layering reaction, is filtered after the completion of reaction, is dried, obtain being layered molybdenum disulfide powder；Added after butyl titanate, diethanol amine are mixed with absolute ethyl alcohol in distilled water, carry out chelatropic reaction, obtain precursor solution, xerogel is obtained after precursor solution evaporation drying, grinding obtains dry gel powder；Dry gel powder and burster are added into layering molybdenum disulfide powder, carries out explosive reaction, explosive reaction product is taken out after being cooled to room temperature, that is, obtains stratiform MoS2‑TiO2Nano composite material.The present invention utilizes the close sulphur property of aromatic thioether, reduces the interlayer Van der Waals force of molybdenum disulfide material powder, delamination is carried out to it with reference to blast impulse.The present invention is combined by sol-gal process with blast high temperature impact, only completes TiO with a step2Rapid reduction and MoS2Stripping, be successfully prepared stratiform MoS2‑TiO2Nano composite material.
Description
Technical field
The invention belongs to metal molybdenum technical field, is related to molybdenum disulfide composite, and in particular to a kind of stratiform MoS2-
TiO2The preparation method of nano composite material.
Background technology
Class graphene molybdenum disulfide (the Graphene-like MoS being made up of individual layer or few layer molybdenum disulfide2) it is a kind of
New Two Dimensional (2D) lamellar compound with similar graphene-structured and performance, in recent years with its unique physics, chemically
Matter and turn into emerging study hotspot.Class graphene molybdenum disulfide is made up of the single or multiple lift molybdenum disulfide of hexagonal crystal system
Two dimensional crystal material with " sandwich " layer structure, individual layer molybdenum disulfide are made up of three layers of atomic layer, middle one layer
For molybdenum atom layer, upper and lower two layers is sulphur atom layer, and molybdenum atom layer forms class " sandwich " structure folded by two layers of sulphur atom layer,
Molybdenum atom forms two-dimensional atomic crystal with sulphur atom with Covalent bonding together；Multilayer molybdenum disulfide is by some individual layer molybdenum disulfide groups
Into being usually no more than five layers, interlayer has weak Van der Waals force, and interlamellar spacing is about 0.65nm.
As a kind of important two-dimensional layer nano material, individual layer or few layer molybdenum disulfide are with its unique " sandwich folder
The heart " layer structure is widely used in various fields such as lubricant, catalysis, energy stores, composites.Compared to the zero of graphene
Regulatable band gap be present, brighter prospect possessed in field of photoelectric devices in band gap, class graphene molybdenum disulfide；Compare
In the three-dimensional bulk structure of silicon materials, class graphene molybdenum disulfide has the two-dimensional layered structure of nanoscale, can be used to make
Manufacturing semiconductor or the electronic chip that specification is smaller, efficiency is higher, will be obtained extensively in fields such as follow-on nano-electric devices
Using.
Although platelike molybdenumdisulfide has good greasy property and photoelectric properties, it has in all many performances
Treat further to be lifted, molybdenum disulfide is used in combination with other organic or inorganic particulates, be lifting using their cooperative effect
One of method of molybdenum disulfide performance.Titanium dioxide has excellent photocatalysis performance, is one of conventional photochemical catalyst, this
Outside, titanium dioxide also has certain greasy property.Research shows that titanium dioxide exists with molybdenum disulfide cooperates with lubrication with cooperateing with
Catalytic action, it is the lubrication for improving molybdenum disulfide and titanium dioxide by chemical method synthesis of carbon/molybdenum disulfide-titanium dioxide compound
With one of the effective way of catalytic performance (Tribology Letters, 2011,43:77-87).
Chinese invention patent CN201410369695 discloses a kind of molybdenum disulfide-titanium dioxide compound and its preparation side
Method, exist using titanium dioxide with molybdenum disulfide and cooperate with lubrication to be acted on concerted catalysis, pass through chemical method synthesis of carbon/molybdenum disulfide-two
Titanium oxide compound is one of effective way for the lubrication and catalytic performance for improving molybdenum disulfide and titanium dioxide；Chinese invention is special
Sharp ZL201010524516.8 adds a certain amount of titanium dioxide when molybdate and thioacetamide react under strongly acidic conditions
Titanium, titanium dioxide surface is activated using the strong acid of reaction system, the titanium dioxide surface of activation, which can provide, is more available for presoma
The core of precipitation, so as to which forerunner's physical efficiency is deposited in the surface of titanium dioxide fine particles in a short period of time, form spherical structure
Molybdenum disulfide-titanium dioxide compound；And if with vulcanized sodium substitution thioacetamide above, react generation is then sheet
Structure molybdenum disulfide-titanium dioxide compound (Journal of Materials Science, 2010,45:2640-
2648)。
Although MoS has been made using chemical synthesis in mean disclosed above2-TiO2Nano composite material, but it prepares stream
Journey is complicated, and energy consumption is big, is not suitable for industrialized production, and for using raw material as graininess MoS2Laminar composite is prepared not have
There is proposition effective workaround, and for the MoS of rich in mineral resources2Material, it is rationalized, higher value application is mesh
The trend of preceding development.Therefore, explore one kind and use particle MoS2Stratiform MoS is prepared for raw material2-TiO2The letter of nano composite material
Easy method is very necessary.
The content of the invention
Based on problems of the prior art, the present invention proposes a kind of stratiform MoS2-TiO2The system of nano composite material
Preparation Method, obtain with nanoscale, the stratiform MoS of superior performance2-TiO2Nano composite material, solves existing MoS2-
TiO2Composite preparation flow is complicated, and energy consumption is big, is not suitable for industrialized production, and cause photocatalysis and lubricity for graininess
The poor technical problem of energy.
It should be noted that the stratiform MoS in the application2-Fe3O4MoS in nano composite material2It is individual layer or few layer
MoS2Nano material, described few layer refer to 2 layers to 5 layers.
In order to solve the above-mentioned technical problem, the application, which adopts the following technical scheme that, is achieved：
A kind of stratiform MoS2-TiO2The preparation method of nano composite material, this method comprise the following steps：
Step 1, molybdenum disulfide powder is added in layering solution and carries out layering reaction, is filtered after the completion of reaction, is dried,
Obtain being layered molybdenum disulfide powder；
Step 2, add in distilled water, chelate instead after butyl titanate, diethanol amine are mixed with absolute ethyl alcohol
Should, precursor solution is obtained, xerogel is obtained after precursor solution evaporation drying, grinding obtains dry gel powder；
Step 3, dry gel powder and burster are added into layering molybdenum disulfide powder, explosive reaction is carried out, is cooled to
Explosive reaction product is taken out after room temperature, that is, obtains stratiform MoS2-TiO2Nano composite material.
The present invention also has following distinguishing feature：
Described layering solution is the ethanol solution of aromatic thioether；Described burster is picric acid.
Described aromatic thioether is polyphenylene sulfide or aromatic diamine monomer thioether, the ethanol solution of aromatic thioether
Mass concentration is 10%~60%.
In step 1, the detailed process of described layering reaction is：Molybdenum disulfide powder is ground to the sieving of 200 mesh, will
Molybdenum disulfide powder is added in the ethanol solution of aromatic thioether, is heated to 30~70 DEG C and is stirred 5~12h, filters, drying,
Obtain being layered molybdenum disulfide powder.
In step 1, the mass ratio of described molybdenum disulfide powder and aromatic thioether is 1:(10~40).
In step 2, the detailed process of chelatropic reaction is：Add after butyl titanate, diethanol amine are mixed with absolute ethyl alcohol
Enter in distilled water, precursor solution is obtained after 3~10h of stirring chelating at 45~80 DEG C, by precursor solution 100~130
Xerogel is obtained at DEG C after 6~15h of evaporation drying, and is ground to 200 mesh and sieves to obtain dry gel powder.
In step 2, described described butyl titanate, diethanol amine, the mass volume ratio of absolute ethyl alcohol and distilled water
For 1g:(10~20) ml:(15~30) ml:(5~20) ml.
In step 3, the detailed process of described explosive reaction is：Will layering molybdenum disulfide powder, dry gel powder and hardship
It is sour well mixed, it is fitted into autoclave, autoclave is vacuumized and is passed through argon gas, is heated to 350~600 DEG C of hairs
Raw blast, explosive reaction thing is taken out after cooling to room temperature with the furnace, that is, obtains stratiform MoS2-TiO2Nano composite material.
In step 3, described layering molybdenum disulfide powder, dry gel powder and the mass ratio of picric acid mixing are 1:
(0.5~5):(0.5~3).
Compared with prior art, beneficial has the technical effect that the present invention：
(I) present invention utilizes the close sulphur property of aromatic thioether, reduces the interlayer Van der Waals force of molybdenum disulfide material powder,
Delamination is carried out to it with reference to blast impulse.
(II) present invention is combined by sol-gel process with blast high temperature impact, only completes TiO with a step2It is fast
Speed reduction and MoS2Stripping, be successfully prepared stratiform MoS2-TiO2Nano composite material.
(II) product prepared by the present invention is platelike molybdenumdisulfide and TiO with high carrier mobility2Nano particle
Compound nano material, and TiO2Nano particle is uniformly attached on individual layer molybdenum disulfide lamella, improves its catalysis and lubrication
Performance, greatly expand the application of molybdenum disulfide.
(IV) present invention prepares stratiform MoS2-TiO2Nano composite material, it is simple to operate, it is not necessary to complicated and cumbersome system
Standby device, preparation efficiency is high, and yield is big, is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the stratiform MoS in embodiment 12-TiO2The Raman collection of illustrative plates of nano composite material.
Fig. 2 is the stratiform MoS in embodiment 12-TiO2The TEM figures of nano composite material.
Fig. 3 is the MoS in comparative example 12-TiO2The Raman collection of illustrative plates of composite.
Fig. 4 is the MoS in comparative example 12-TiO2The TEM figures of composite.
The particular content of the present invention is described in more detail below in conjunction with drawings and examples.
Embodiment
Above-mentioned technical proposal is deferred to, specific embodiment of the invention given below is, it is necessary to which explanation is the present invention not office
It is limited to specific examples below, all equivalents done on the basis of technical scheme each fall within the protection model of the present invention
Enclose.The present invention is described in further details with reference to embodiment.
Embodiment 1：
The present embodiment provides a kind of stratiform MoS2-TiO2The preparation method of nano composite material, this method specifically include following
Step：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 10%, contain
In the ethanol solution of 100g polyphenylene sulfides, heating water bath is to 30 DEG C and stirs 12h, filters and dries filter cake, is ground to 200 mesh
Sieving, obtain 3.1g layering molybdenum disulfide powders.
Step 2,5g butyl titanates, 50ml diethanol amine is taken to add 25ml distilled water after being mixed with 75ml absolute ethyl alcohols
In, precursor solution is obtained after stirring chelating 3h at 45 DEG C, dry coagulate is obtained after precursor solution is dried into 6h at 100 DEG C
Glue, and be ground to 200 mesh and sieve to obtain dry gel powder.
Step 3, it is equal by mixing with 1.6g dry gel powders, 1.6g picric acid that gained 3.1g is layered molybdenum disulfide powder
In even loading autoclave, vacuumize and be passed through argon gas, reactor is heated into 500 DEG C explodes, and cools to room with the furnace
Explosive reaction thing is taken out after temperature to be rinsed repeatedly with deionized water, and stratiform MoS is obtained after filtration drying2The nano combined materials of-TiO2
Material.
Stratiform MoS prepared by the present embodiment2-TiO2Nano composite material Raman collection of illustrative plates is as shown in figure 1, high-resolution
TEM figures are as shown in Figure 2.
E in Raman collection of illustrative plates in Fig. 12g 1With Ag 1Value is respectively 384.06 and 406.91, displacement difference 22.85, belongs to few layer
Structure MoS2, show MoS in sample prepared by the present embodiment2For stratified material.
Fig. 2 middle high-resolution TEM figures are shown as TiO2Nano particle adheres to MoS2Laminar nano chip architecture surface.
Comprehensive accompanying drawing can show that the sample prepared by the present embodiment is stratiform MoS2-TiO2Nano composite material.
Embodiment 2：
The present embodiment provides a kind of stratiform MoS2-TiO2The preparation method of nano composite material, this method specifically include following
Step：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 20%, contain
In the ethanol solution of 200g polyphenylene sulfides, heating water bath is to 50 DEG C and stirs 5h, filters and dries filter cake, is ground to 200 mesh
Sieving, obtain 3.4g layering molybdenum disulfide powders；
Step 2,5g butyl titanates, 75ml diethanol amine is taken to add 50ml distilled water after being mixed with 100ml absolute ethyl alcohols
In, precursor solution is obtained after stirring chelating 4h at 50 DEG C, dry coagulate is obtained after precursor solution is dried into 7h at 105 DEG C
Glue, and be ground to 200 mesh and sieve to obtain dry gel powder.
Step 3, it is equal by mixing with 3.4g dry gel powders, 3.4g picric acid that gained 3.4g is layered molybdenum disulfide powder
In even loading autoclave, vacuumize and be passed through argon gas, reactor is heated into 480 DEG C explodes, and cools to room with the furnace
Explosive reaction thing is taken out after temperature, is rinsed repeatedly with deionized water, stratiform MoS is obtained after filtration drying2-TiO2Nano combined material
Material.
The present embodiment products therefrom stratiform MoS2-TiO2The character of nano composite material is substantially the same manner as Example 1.
Embodiment 3：
The present embodiment provides a kind of stratiform MoS2-TiO2The preparation method of nano composite material, this method specifically include following
Step：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 30%, contain
In the ethanol solution of 300g polyphenylene sulfides, heating water bath is to 40 DEG C and stirs 8h, filters and dries filter cake, is ground to 200 mesh
Sieving, obtain 2.8g layering molybdenum disulfide powders；
Step 2,5g butyl titanates, 100ml diethanol amine is taken to add 75ml distillations after being mixed with 125ml absolute ethyl alcohols
In water, precursor solution is obtained after stirring chelating 5h at 60 DEG C, dry coagulate is obtained after precursor solution is dried into 9h at 110 DEG C
Glue, and be ground to 200 mesh and sieve to obtain dry gel powder.
Step 3, it is equal by mixing with 4.5g dry gel powders, 5.6g picric acid that gained 2.8g is layered molybdenum disulfide powder
In even loading autoclave, vacuumize and be passed through argon gas, reactor is heated into 450 DEG C explodes, and cools to room with the furnace
Explosive reaction thing is taken out after temperature to be rinsed repeatedly with deionized water, and stratiform MoS is obtained after filtration drying2-TiO2Nano combined material
Material.
The present embodiment products therefrom stratiform MoS2-TiO2The character of nano composite material is substantially the same manner as Example 1.
Embodiment 4：
The present embodiment provides a kind of stratiform MoS2-TiO2The preparation method of nano composite material, this method specifically include following
Step：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 40%, contain
In the ethanol solution of 400g aromatic diamine monomer thioethers, heating water bath is to 35 DEG C and stirs 10h, filters and dries filter cake,
The sieving of 200 mesh is ground to, obtains 3.2g layering molybdenum disulfide powders.
Step 2,5g butyl titanates, 50ml diethanol amine is taken to add 100ml distillations after being mixed with 150ml absolute ethyl alcohols
In water, precursor solution is obtained after stirring chelating 6h at 65 DEG C, is done after precursor solution is dried into 11h at 115 DEG C
Gel, and be ground to 200 mesh and sieve to obtain dry gel powder.
Step 3, it is equal by mixing with 6.4g dry gel powders, 1.6g picric acid that gained 3.2g is layered molybdenum disulfide powder
In even loading autoclave, vacuumize and be passed through argon gas, reactor is heated into 550 DEG C explodes, and cools to room with the furnace
Explosive reaction thing is taken out after temperature to be rinsed repeatedly with deionized water, ultrasonic disperse 6h, stratiform MoS is obtained after filtration drying2-TiO2
Nano composite material.
The present embodiment products therefrom stratiform MoS2-TiO2The character of nano composite material is substantially the same manner as Example 1.
Embodiment 5：
The present embodiment provides a kind of stratiform MoS2-TiO2The preparation method of nano composite material, this method specifically include following
Step：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 60%, contain
In the ethanol solution of 300g aromatic diamine monomer thioethers, heating water bath is to 30 DEG C and stirs 12h, filters and dries filter cake,
The sieving of 200 mesh is ground to, obtains 2.6g layering molybdenum disulfide powders.
Step 2,5g butyl titanates, 50ml diethanol amine is taken to add 75ml distilled water after being mixed with 100ml absolute ethyl alcohols
In, precursor solution is obtained after stirring chelating 8h at 70 DEG C, dry coagulate is obtained after precursor solution is dried into 13h at 120 DEG C
Glue, and be ground to 200 mesh and sieve to obtain dry gel powder.
Step 3, gained 2.6g is layered molybdenum disulfide powder and 10g TiO2Nanometer powder, 2.6g picric acid are by mixing
Uniformly it is fitted into autoclave, vacuumizes and be passed through argon gas, reactor is heated into 510 DEG C explodes, and cools to the furnace
Explosive reaction thing is taken out after room temperature to be rinsed repeatedly with deionized water, and stratiform MoS is obtained after filtration drying2-TiO2Nano combined material
Material.
The present embodiment products therefrom stratiform MoS2-TiO2The character of nano composite material is substantially the same manner as Example 1.
Embodiment 6：
The present embodiment provides a kind of stratiform MoS2-TiO2The preparation method of nano composite material, this method specifically include following
Step：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 50%, contain
In the ethanol solution of 200g aromatic diamine monomer thioethers, heating water bath is to 45 DEG C and stirs 8h, filters and dries filter cake,
The sieving of 200 mesh is ground to, obtains 3.3g layering molybdenum disulfide powders.
Step 2,5g butyl titanates, 100ml diethanol amine is taken to add 50ml distilled water after being mixed with 75ml absolute ethyl alcohols
In, precursor solution is obtained after stirring chelating 10h at 80 DEG C, dry coagulate is obtained after precursor solution is dried into 15h at 110 DEG C
Glue, and be ground to 200 mesh and sieve to obtain dry gel powder.
Step 3, gained 3.3g is layered molybdenum disulfide powder and 16.5g TiO2Nanometer powder, 5.4g picric acid are by mixed
Conjunction is uniformly fitted into autoclave, vacuumizes and is passed through argon gas, reactor is heated into 500 DEG C explodes, furnace cooling
Explosive reaction thing is taken out after to room temperature to be rinsed repeatedly with deionized water, and stratiform MoS is obtained after filtration drying2-TiO2It is nano combined
Material.
The present embodiment products therefrom stratiform MoS2-TiO2The character of nano composite material is substantially the same manner as Example 1.
Comparative example 1：
This comparative example provides a kind of MoS2-TiO2The preparation method of composite, this method specifically include following steps：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 5%, contain
In the ethanol solution of 50g aromatic diamine monomer thioethers, heating water bath is to 25 DEG C and stirs 5 h, filters and dries filter cake, grinds
The sieving of 200 mesh is milled to, obtains 3.2g layering molybdenum disulfide powders.
Step 2,5g butyl titanates, 20ml diethanol amine is taken to add 20ml distilled water after being mixed with 50ml absolute ethyl alcohols
In, precursor solution is obtained after stirring chelating 2h at 40 DEG C, xerogel is obtained after precursor solution is dried into 8h at 90 DEG C,
And it is ground to 200 mesh and sieves to obtain dry gel powder.
Step 3, gained 3.2g is layered molybdenum disulfide powder and presses and is well mixed with 0.5g dry gel powders, 1g picric acid
It is fitted into autoclave, vacuumizes and be passed through argon gas, reactor is heated into 600 DEG C explodes, and cools to room temperature with the furnace
Explosive reaction thing is taken out afterwards to be rinsed repeatedly with deionized water, and MoS is obtained after filtration drying2-TiO2Compound.
To MoS made from this comparative example2-TiO2Compound carries out Raman spectrum analyses and tem analysis.
Raman spectrum are as shown in figure 3, its E2g 1With Ag 1Value is respectively 381.65 and 406.91, displacement difference 25.26, is belonged to
Block structure MoS2。
TEM image is as shown in figure 4, illustrate this product MoS2Block is accumulated, and sandwich construction is presented, and in MoS2Surface or week
Enclose and do not find obvious TiO2Particle, it is not belonging to individual layer or few layer MoS2Nano composite material.
Comparative example 2：
This comparative example provides a kind of MoS2-TiO2The preparation method of composite, this method specifically include following steps：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 70%, contain
In the ethanol solution of 500g aromatic diamine monomer thioethers, heating water bath is to 60 DEG C and stirs 4h, filters and dries filter cake, grinds
The sieving of 200 mesh is milled to, obtains 3g layering molybdenum disulfide powders.
Step 2,5g butyl titanates, 50ml diethanol amine is taken to add 100ml distilled water after being mixed with 20ml absolute ethyl alcohols
In, precursor solution is obtained after stirring chelating 3h at 90 DEG C, dry coagulate is obtained after precursor solution is dried into 5h at 100 DEG C
Glue, and be ground to 200 mesh and sieve to obtain dry gel powder.
Step 3, gained 3g is layered molybdenum disulfide powder and 18g TiO2Nanometer powder, 0.5g picric acid are equal by mixing
In even loading autoclave, vacuumize and be passed through argon gas, reactor is heated into 650 DEG C explodes, and cools to room with the furnace
Explosive reaction thing is taken out after temperature to be rinsed repeatedly with deionized water, and MoS is obtained after filtration drying2-TiO2Compound.
MoS made from this comparative example2-TiO2Composite block as comparative example 1 is accumulated, and TiO2Particle appears in
MoS2Block surface and surrounding, it is not belonging to individual layer or few layer molybdenum disulfide nano-composite material.
Comparative example 3：
This comparative example provides a kind of MoS2-TiO2The preparation method of composite, this method specifically include following steps：
Step 1, take 10g molybdenum disulfide powders to be ground to the sieving of 200 mesh, be added into mass concentration and be 8%, contain
In the ethanol solution of 60g aromatic diamine monomer thioethers, heating water bath is to 25 DEG C and stirs 5 h, filters and dries filter cake, grinds
The sieving of 200 mesh is milled to, obtains 3.5g layering molybdenum disulfide powders.
Step 2,5g butyl titanates, 100ml diethanol amine is taken to add 150ml distillations after being mixed with 10ml absolute ethyl alcohols
In water, precursor solution is obtained after stirring chelating 4h at 85 DEG C, dry coagulate is obtained after precursor solution is dried into 4h at 110 DEG C
Glue, and be ground to 200 mesh and sieve to obtain dry gel powder.
Step 3, it is equal by mixing with 1.5g dry gel powders, 1.5g picric acid that gained 3.5g is layered molybdenum disulfide powder
In even loading autoclave, vacuumize and be passed through argon gas, reactor is heated into 620 DEG C explodes, and cools to room with the furnace
Explosive reaction thing is taken out after temperature, obtains MoS2-TiO2Compound.
MoS made from this comparative example2-TiO2Composite block as comparative example 1 is accumulated, and TiO2Particle appears in
MoS2Block surface and surrounding, it is not belonging to individual layer or few layer molybdenum disulfide nano-composite material.
Claims (4)
- A kind of 1. stratiform MoS2-TiO2The preparation method of nano composite material, it is characterised in that：This method comprises the following steps：Step 1, molybdenum disulfide powder is added in layering solution and carries out layering reaction, is filtered after the completion of reaction, dries, obtains It is layered molybdenum disulfide powder；Described layering solution is the ethanol solution of aromatic thioether；Described aromatic thioether is polyphenylene sulfide or aromatic diamine monomer thioether, the quality of the ethanol solution of aromatic thioether Concentration is 10%~60%；The detailed process of described layering reaction is：Molybdenum disulfide powder is ground to the sieving of 200 mesh, by molybdenum disulfide powder plus In the ethanol solution for entering aromatic thioether, it is heated to 30~70 DEG C and stirs 5~12h, filter, drying, obtain being layered curing Molybdenum powder；Step 2, added after butyl titanate, diethanol amine are mixed with absolute ethyl alcohol in distilled water, carry out chelatropic reaction, obtain To precursor solution, xerogel is obtained after precursor solution evaporation drying, grinding obtains dry gel powder；The detailed process of described chelatropic reaction is：Distillation is added after butyl titanate, diethanol amine are mixed with absolute ethyl alcohol In water, precursor solution is obtained after 3~10h of stirring chelating at 45~80 DEG C, precursor solution is steamed at 100~130 DEG C Xerogel is obtained after dry dry 6~15h, and is ground to 200 mesh and sieves to obtain dry gel powder；Step 3, dry gel powder and burster are added into layering molybdenum disulfide powder, explosive reaction is carried out, is cooled to room temperature Explosive reaction product is taken out afterwards, that is, obtains stratiform MoS2-TiO2Nano composite material；Described burster is picric acid；The detailed process of described explosive reaction is：Layering molybdenum disulfide powder, dry gel powder and picric acid are well mixed, It is fitted into autoclave, autoclave is vacuumized and is passed through argon gas, is heated to 350~600 DEG C and explodes, it is cold with stove But to taking-up explosive reaction thing after room temperature, that is, stratiform MoS is obtained2-TiO2Nano composite material.
- 2. preparation method as claimed in claim 1, it is characterised in that：In step 1, described molybdenum disulfide powder and fragrance The mass ratio of race's thioether is 1:(10~40).
- 3. preparation method as claimed in claim 1, it is characterised in that：In step 2, described butyl titanate, diethanol The mass volume ratio of amine, absolute ethyl alcohol and distilled water is 1g:(10~20) ml:(15~30) ml:(5~20) ml.
- 4. preparation method as claimed in claim 1, it is characterised in that：In step 3, described layering molybdenum disulfide powder, do Gel powder and the mass ratio of picric acid mixing are 1:(0.5~5):(0.5~3).
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| KR20190026751A (en) * | 2016-07-13 | 2019-03-13 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | Method for preparing molybdenum disulfide nanoparticles supported on titania phase |
| CN107803209A (en) * | 2017-10-20 | 2018-03-16 | 上海应用技术大学 | A kind of preparation method of individual layer molybdenum disulfide and nano titania hetero-junctions |
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