CN105126874B - A kind of tungsten disulfide/titanium dioxide compound and preparation method thereof - Google Patents
A kind of tungsten disulfide/titanium dioxide compound and preparation method thereof Download PDFInfo
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- CN105126874B CN105126874B CN201510416849.1A CN201510416849A CN105126874B CN 105126874 B CN105126874 B CN 105126874B CN 201510416849 A CN201510416849 A CN 201510416849A CN 105126874 B CN105126874 B CN 105126874B
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Abstract
A kind of tungsten disulfide/titanium dioxide compound and preparation method thereof, is related to lubricant and photocatalyst technology field.Tungsten disulfide/titanium dioxide compound is mutually uniformly dispersed by tungsten disulfide and titanium dioxide and forms layer structure, titanium dioxide, tungsten disulfide exist with anatase crystal, six side 2H crystal formations respectively in compound, tungsten disulfide particulate is in lamellar, is titanium dioxide in the cluster body of tungsten disulfide microparticle surfaces accumulation.Titanium dioxide surface is activated using strongly acidic solution, tungstates reacts with acid simultaneously, wolframic acid (aqua oxidation tungsten) precipitation and the titanium dioxide surface of activation of generation act on, form well mixed wolframic acid/titanium dioxide compound, the compound and elemental sulfur are mixed and heated into vulcanization again makes tungsten oxide be changed into tungsten disulfide, then calcining desulfurization is reheated, finally cooling obtains.Preparation technology is simple, and rapid reaction, reaction condition is easily controllable, and production cost is low, is adapted to batch production.
Description
Technical field
The present invention relates to lubricant and photocatalyst technology field, and it is multiple to be specifically related to a kind of tungsten disulfide/titanium dioxide
Compound and preparation method thereof.
Background technology
Titanium dioxide is one of the most frequently used photochemical catalyst, and it has irreplaceable advantage in photocatalysis field；Recently
Research shows that titanium dioxide also has certain greasy property, may be used as lubricating additive.Titanium dioxide inorganic adds with other
Its catalysis can also be lifted further with greasy property after adding agent such as molybdenum disulfide compound, therefore pass through chemical method synthesis of titanium dioxide
Compound be lifted one of its catalysis and important channel of greasy property (Tribology Letters, 2011,43：77-87；
Journal of Materials Science, 2010,45：2640-2648).
Tungsten disulfide is similar to molybdenum disulfide performance, both with excellent greasy property, also with excellent catalytic performance,
Always by the concern of people.Although tungsten disulfide excellent performance, its performance stills need further to be lifted in many situations,
It is one of the method that lifts its performance with other inorganic matters composition compound.
Tungsten disulfide/titanium dioxide compound has organically combined the advantages of tungsten disulfide and two kinds of components of titanium dioxide, and two
Exist between kind component and cooperate with lubrication and concerted catalysis function, thus exploitation tungsten disulfide/titanium dioxide compound has widely
Application prospect.By chemical synthesis, titanium dioxide surface is activated using strong acid, sulfide hydrolysis produces H2S carrys out molybdenum sulfide
Salt, finally by calcining desulfurization after can obtain molybdenum disulfide/titanium dioxide compound (Chinese patent 201010524516.8).But
It by the above method is difficult to prepare tungsten disulfide/titanium dioxide compound to be, is primarily due to tungstates in acid condition
The easily oxide (Chinese patent 201210078592.X) of generation wolframic acid or tungsten.
The content of the invention
In order to overcome drawbacks described above present in prior art, an object of the present invention is to provide a kind of superior performance
Tungsten disulfide/titanium dioxide compound, to realize the purpose, present invention employs following technical scheme：
A kind of tungsten disulfide/titanium dioxide compound, is mutually uniformly dispersed by tungsten disulfide and titanium dioxide and forms stratiform
Structure, titanium dioxide, tungsten disulfide exist with anatase crystal, six side 2H crystal formations respectively in compound, and tungsten disulfide particulate is in
Lamellar, it is titanium dioxide in the cluster body of tungsten disulfide microparticle surfaces accumulation.
Another object of the present invention is to provide a kind of preparation method of tungsten disulfide/titanium dioxide compound, to realize
The purpose, present invention employs following technical scheme：
A kind of preparation method of tungsten disulfide/titanium dioxide compound, titanium dioxide surface is activated using strongly acidic solution,
Tungstates reacts with acid simultaneously, and wolframic acid (aqua oxidation tungsten) precipitation and the titanium dioxide surface of activation of generation act on, shape
Into well mixed wolframic acid/titanium dioxide compound, then the compound and elemental sulfur are mixed and heated into vulcanization turns tungsten oxide
It is changed into tungsten disulfide, then reheats calcining desulfurization, finally cooling obtains tungsten disulfide/titanium dioxide compound.
Specifically, the preparation method of tungsten disulfide/titanium dioxide compound, step are as follows：
1., by following proportioning prepare raw material
The mass ratio of tungstates and titanium dioxide is 1: 0.01~100；
The mass ratio of tungstates and elemental sulfur is 1: 0.2~20；
The mass ratio of tungstates and water is 1: 10~10000；
2., tungstates and titanium dioxide be placed in water, 0~100 DEG C is heated to, with salt acid for adjusting pH value to being less than or wait
In 1, wolframic acid/titanium dioxide compound is obtained by coprecipitation reaction, mixed after filtering, wash and drying with enough elemental sulfurs
Close, be then placed in N2 or rare gas protective atmosphere and heat vulcanization, then heating and calcining desulfurization, by responseless elemental sulfur
Evaporative removal, most obtain tungsten disulfide/titanium dioxide compound through cooling afterwards.
As the further improvement of the preparation method of tungsten disulfide/titanium dioxide compound of the present invention, the tungstates
For at least one of sodium tungstate, ammonium tungstate and potassium tungstate.Heat curing temperature be 250~445 DEG C, heating cure time be 5~
200 minutes.It is 446~1000 DEG C to calcine desulfurization temperature, and calcining desulfurization time is 5~200 minutes.
The preparation method of tungsten disulfide/titanium dioxide compound, is reacted as follows：
Step 1 (surface active, precipitation reaction)：
(surface active)
WO4 2-+2H++TiO2→H2WO4(WO3·H2O)/TiO2↓
Step 2 (heats, with N in protective atmosphere2Exemplified by, 250-445 DEG C)：
(heating evaporation removes responseless sulphur to step 3 in protective atmosphere, with N2Exemplified by, 446-1000 DEG C)；
Compared with prior art, beneficial effects of the present invention are shown：
1), tungsten disulfide/titanium dioxide compound is mutually uniformly dispersed by tungsten disulfide and titanium dioxide and forms stratiform knot
Structure, titanium dioxide, tungsten disulfide exist with anatase crystal, six side 2H crystal formations respectively in compound, and tungsten disulfide particulate is in layer
Sheet, it is titanium dioxide in the cluster body of the surface sediment of tungsten disulfide particulate.Tungsten disulfide/the titanium dioxide compound is profit
With the collaboration lubrication and synergic catalytic effect of tungsten disulfide and titanium dioxide, can give full play to the greasy properties of two kinds of components with
Catalytic performance, and then it is had in known or tera incognita and more broadly apply.
2), preparation method of the invention avoids directly synthesis tungsten sulfide/titanium dioxide compound presoma, then by adding
Thermally desulfurizing obtains required compound, but first synthesizes wolframic acid/titanium dioxide compound presoma, then passes through high temperature sulphur
Change, it is final to obtain the tungsten disulfide/titanium dioxide compound that applications well prospect with catalytic field in lubrication be present.
3), the preparation method of tungsten disulfide/titanium dioxide compound can either reduce synthesis cost, shorten generated time,
The dispersiveness between tungsten disulfide and titanium dioxide component can also be improved, with further improve the greasy property of the compound with
Catalytic performance.Preparation technology is simple, and rapid reaction, reaction condition is easily controllable, and production cost is low, is adapted to batch production.
Brief description of the drawings
Fig. 1 is the powder x-ray diffraction of the tungsten disulfide/titanium dioxide compound synthesized by method provided by the invention
Collection of illustrative plates.
According to numbering be 841398 and 894921 PDF cards, all main diffraction peaks can index tungsten disulfide or
Titanium dioxide, show successfully to synthesize tungsten disulfide/titanium dioxide compound.It is related to titanium dioxide in compound to spread out
It is consistent with the diffraction data of No. 894921 contained anatase titanium dioxides of PDF cards to penetrate peak, shows titanium dioxide with anatase
Type is present in compound；Tungsten disulfide is then consistent with six side's 2H type tungsten disulfides that No. 841398 PDF cards are contained, shows two sulphur
It is typical 2H layer structures to change tungsten.
Fig. 2 is the scanning electron microscopy of the tungsten disulfide/titanium dioxide compound synthesized by method provided by the invention
Mirror photo, Fig. 3 are Fig. 2 high magnification photos.
It can be seen that the tungsten disulfide in compound interconnects with titanium dioxide, is uniformly dispersed by Fig. 2 and Fig. 3, it is multiple
Compound middle level flaky particles are tungsten disulfides, are titanium dioxide in the cluster body of its surface sediment.
Embodiment
Embodiment 1
1 part of sodium tungstate and 0.5 part of titanium dioxide are placed in 133 parts of water, are heated to 80 DEG C, with salt acid for adjusting pH value extremely
0.5, gained strongly acidic solution activates titanium dioxide surface, while tungstates reacts with acid, the wolframic acid of generation precipitation with
The titanium dioxide surface effect of activation, form well mixed wolframic acid/titanium dioxide compound precipitation.Reaction was carried out after terminating
Filter, washing insert N with drying after then wolframic acid/titanium dioxide compound is well mixed with 10 parts of elemental sulfurs2In in 300 DEG C
Lower heating vulcanization 60 minutes, vulcanization are warming up to 600 DEG C and evaporate desulfurization 30 minutes again after terminating, tungsten disulfide/bis- are obtained after cooling
Titanium oxide compound (as shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photos).
Embodiment 2
1 part of ammonium tungstate and 0.5 part of titanium dioxide are placed in 133 parts of water, are heated to 80 DEG C, with salt acid for adjusting pH value extremely
0.5, gained strongly acidic solution activates titanium dioxide surface, while tungstates reacts with acid, the wolframic acid of generation precipitation with
The titanium dioxide surface effect of activation, form well mixed wolframic acid/titanium dioxide compound precipitation.Reaction was carried out after terminating
Filter, washing are inserted in Ar gas in 300 with drying after then wolframic acid/titanium dioxide compound is well mixed with 10 parts of elemental sulfurs
Heating vulcanization 60 minutes at DEG C, vulcanization are warming up to 600 DEG C of evaporation desulfurization 30 minutes again after terminating, obtained after cooling tungsten disulfide/
Titanium dioxide compound (is similar to shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photos).
Embodiment 3
1 part of potassium tungstate and 0.5 part of titanium dioxide are placed in 133 parts of water, are heated to 80 DEG C, with salt acid for adjusting pH value extremely
0.5, gained strongly acidic solution activates titanium dioxide surface, while tungstates reacts with acid, the wolframic acid of generation precipitation with
The titanium dioxide surface effect of activation, form well mixed wolframic acid/titanium dioxide compound precipitation.Reaction was carried out after terminating
Filter, washing insert N with drying after then wolframic acid/titanium dioxide compound is well mixed with 10 parts of elemental sulfurs2In 400 in gas
Heating vulcanization 30 minutes at DEG C, vulcanization are warming up to 450 DEG C of evaporation desulfurization 60 minutes again after terminating, obtained after cooling tungsten disulfide/
Titanium dioxide compound (is similar to shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photos).
Embodiment 4
1 part of sodium tungstate and 10 parts of titanium dioxide are placed in 1000 parts of water, are heated to 40 DEG C, with salt acid for adjusting pH value extremely
0.1, gained strongly acidic solution activates titanium dioxide surface, while tungstates reacts with acid, wolframic acid (the hydration oxygen of generation
Change tungsten) precipitation and the titanium dioxide surface of activation act on, form well mixed wolframic acid/titanium dioxide compound precipitation.Reaction
Filtered, washed with being dried after end, inserted after then wolframic acid/titanium dioxide compound is well mixed with 5 parts of elemental sulfurs
N2Heating vulcanization 180 minutes, vulcanization are warming up to 800 DEG C and evaporate desulfurization 10 minutes again at 280 DEG C after terminating in gas, after cooling
(it is similar to tungsten disulfide/titanium dioxide compound shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photos).
Embodiment 5
1 part of sodium tungstate and 1 part of titanium dioxide are placed in 4000 parts of water, are heated to 90 DEG C, with salt acid for adjusting pH value extremely
0.5, gained strongly acidic solution activates titanium dioxide surface, while tungstates reacts with acid, wolframic acid (the hydration oxygen of generation
Change tungsten) precipitation and the titanium dioxide surface of activation act on, form well mixed wolframic acid/titanium dioxide compound precipitation.Reaction
Filtered, washed with being dried after end, inserted after then wolframic acid/titanium dioxide compound is well mixed with 2 parts of elemental sulfurs
N2Heating vulcanizes 120 minutes at 350 DEG C in gas, and vulcanization is warming up to 450 DEG C and evaporates desulfurization 100 minutes again after terminating, after cooling
Obtain tungsten disulfide/titanium dioxide compound (being similar to shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photos).
Claims (5)
1. tungsten disulfide/titanium dioxide compound, it is characterised in that：This compound is mutually scattered by tungsten disulfide and titanium dioxide
Layer structure is formed uniformly, titanium dioxide, tungsten disulfide exist with anatase crystal, six side 2H crystal formations respectively in compound, and two
Tungsten sulfide particulate is in lamellar, is titanium dioxide in the cluster body of the surface sediment of tungsten disulfide particulate；
Preparation method is：Titanium dioxide surface is activated using strongly acidic solution, while tungstates reacts with acid, the tungsten of generation
Acid precipitation and the titanium dioxide surface of activation act on, and form well mixed wolframic acid/titanium dioxide compound, then by the compound
Being mixed and heated vulcanization with elemental sulfur makes tungsten oxide be changed into tungsten disulfide, then reheats calcining desulfurization, and finally cooling obtains
Tungsten disulfide/titanium dioxide compound.
A kind of 2. preparation method of tungsten disulfide/titanium dioxide compound, it is characterised in that：Dioxy is activated using strongly acidic solution
Change titanium surface, while tungstates reacts with acid, the wolframic acid precipitation and the titanium dioxide surface of activation of generation act on, and are formed mixed
Uniform wolframic acid/titanium dioxide compound is closed, then the compound is mixed and heated into vulcanization with elemental sulfur is changed into tungsten oxide
Tungsten disulfide, calcining desulfurization is then reheated, finally cooling obtains tungsten disulfide/titanium dioxide compound；Comprise the following steps that：
1., by following proportioning prepare raw material
The mass ratio of tungstates and titanium dioxide is 1: 0.01~100；
The mass ratio of tungstates and elemental sulfur is 1: 0.2~20；
The mass ratio of tungstates and water is 1: 10~10000；
2., tungstates and titanium dioxide be placed in water, be heated to 0~100 DEG C, with salt acid for adjusting pH value to being less than or equal to 1,
Wolframic acid/titanium dioxide compound is obtained by precipitation reaction, mixed after filtering, wash and drying with enough elemental sulfurs, then
It is put into N2Or vulcanization is heated in rare gas protective atmosphere, then heating and calcining desulfurization, the evaporation of responseless elemental sulfur is gone
Remove, most obtain tungsten disulfide/titanium dioxide compound through cooling afterwards.
3. the preparation method of tungsten disulfide/titanium dioxide compound as claimed in claim 2, it is characterised in that：The wolframic acid
Salt is at least one of sodium tungstate, ammonium tungstate and potassium tungstate.
4. the preparation method of tungsten disulfide/titanium dioxide compound as claimed in claim 2, it is characterised in that：Heating vulcanization
Temperature is 250~445 DEG C, and heating cure time is 5~200 minutes.
5. the preparation method of tungsten disulfide/titanium dioxide compound as claimed in claim 2, it is characterised in that：Calcine desulfurization
Temperature is 446~1000 DEG C, and calcining desulfurization time is 5~200 minutes.
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| CN105688940A (en) * | 2016-02-29 | 2016-06-22 | 山东科技大学 | Tungsten sulfide nanosheet/titanium dioxide nanobelt composite and preparation method thereof |
| CN110164695B (en) * | 2019-05-13 | 2021-09-28 | 常州工学院 | Flower-shaped vertical orientation tungsten disulfide modified one-dimensional ordered carbon film coated titanium dioxide nanorod array composite material and preparation method thereof |
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| JP2001070802A (en) * | 1999-09-03 | 2001-03-21 | Toshiba Corp | Photocatalyst film and its production |
| CN101979480A (en) * | 2010-10-27 | 2011-02-23 | 合肥学院 | Molybdenum disulfide nanosphere/titanium dioxide composite material and preparation method thereof |
| CN104759289A (en) * | 2015-03-31 | 2015-07-08 | 华南理工大学 | Preparation method of block WS2 sensitized TiO2 visible light catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001070802A (en) * | 1999-09-03 | 2001-03-21 | Toshiba Corp | Photocatalyst film and its production |
| CN101979480A (en) * | 2010-10-27 | 2011-02-23 | 合肥学院 | Molybdenum disulfide nanosphere/titanium dioxide composite material and preparation method thereof |
| CN104759289A (en) * | 2015-03-31 | 2015-07-08 | 华南理工大学 | Preparation method of block WS2 sensitized TiO2 visible light catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Hydrothermal synthesis, characterization and optical absorption property of nanoscale WS2/TiO2 composites;Shixiu Cao等;《Physica E》;20141226;第68卷;第171-173页 * |
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