CN105126874A - Tungsten disulfide/titanium dioxide composite and preparation method thereof - Google Patents
Tungsten disulfide/titanium dioxide composite and preparation method thereof Download PDFInfo
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- CN105126874A CN105126874A CN201510416849.1A CN201510416849A CN105126874A CN 105126874 A CN105126874 A CN 105126874A CN 201510416849 A CN201510416849 A CN 201510416849A CN 105126874 A CN105126874 A CN 105126874A
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Abstract
A tungsten disulfide/titanium dioxide composite and a preparation method thereof. The invention relates to the technical field of lubricants and photo-catalysts. The tungsten disulfide/attapulgite composite is in a laminar structure formed from tungsten disulfide and titanium dioxide in a manner of mutual uniform dispersion, wherein the titanium dioxide is in an anatase crystal form and the tungsten disulfide is in a hexagonal 2H crystal form. The tungsten disulfide particle is in a lamella structure, wherein the titanium dioxide, which is in the form of a cluster, is deposited on the surface of the tungsten disulfide particle. The surface of the titanium dioxide is activated through a strong acidic solution, and meanwhile, tungstate is reacted with acid to generate tungstic acid precipitate (tungsten oxide hydrate), which is reacted with the activated titanium dioxide surface, to form uniformly-mixed tungsten acid/titanium dioxide composite. The composite is then mixed with elementary sulfur to carry out heating sulfurization to convert the tungsten oxide into tungsten disulfide. Finally, the mixture is heated and roasted to remove sulfur and finally is cooled to prepare the composite. The method is simple in process, is quick in reaction, is easy-to-control in reaction conditions, is low in production cost and is suitable for large-scale production.
Description
Technical field
The present invention relates to lubricant and photocatalyst technology field, specifically relate 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; Nearest research shows that titanium dioxide also has certain greasy property, can be used as lubricating additive.Titanium dioxide and other inorganic additive such as its catalysis and greasy property after molybdenum bisuphide compound also can promote further, therefore be one of the important channel of its catalysis of lifting and greasy property (TribologyLetters by the compound of chemical method synthesis of titanium dioxide, 2011,43:77-87; JournalofMaterialsScience, 2010,45:2640-2648).
Tungsten disulfide is similar to molybdenum bisuphide performance, has both had excellent greasy property, also has excellent catalytic performance, always the concern of extremely people.Although tungsten disulfide excellent performance, its performance still needs further lifting in many situations, and forming compound with other inorganic matter is one of method promoting its performance.
Tungsten disulfide/titanium dioxide compound has organically combined the advantage of tungsten disulfide and titanium dioxide two kinds of components, there is collaborative lubrication and concerted catalysis function, thus develop tungsten disulfide/titanium dioxide compound and be with a wide range of applications between two kinds of components.By chemical synthesis, utilize strong acid to activate titanium dioxide surface, sulfide hydrolysis produces H
2s carrys out molybdenum sulfide hydrochlorate, can obtain molybdenum bisuphide/titanium dioxide compound (Chinese patent 201010524516.8) finally by after calcining desulfurization.But be difficult to prepare tungsten disulfide/titanium dioxide compound by said method, mainly because tungstates easily generates the oxide (Chinese patent 201210078592.X) of wolframic acid or tungsten in acid condition.
Summary of the invention
In order to overcome the above-mentioned defect existed in prior art, an object of the present invention is the tungsten disulfide/titanium dioxide compound providing a kind of superior performance, for realizing this object, present invention employs following technical scheme:
A kind of tungsten disulfide/titanium dioxide compound, mutually be uniformly dispersed by tungsten disulfide and titanium dioxide and form layer structure, in compound, titanium dioxide, tungsten disulfide exist with anatase crystal, six side 2H crystal formations respectively, tungsten disulfide particulate is lamellar, and the cluster body piled up at tungsten disulfide microparticle surfaces is titanium dioxide.
Another object of the present invention is to the preparation method that a kind of tungsten disulfide/titanium dioxide compound is provided, for realizing this object, present invention employs following technical scheme:
A kind of preparation method of tungsten disulfide/titanium dioxide compound, strongly acidic solution is utilized to activate titanium dioxide surface, tungstates and acid simultaneously reacts, wolframic acid (aqua oxidation tungsten) precipitation generated and the titanium dioxide surface effect activated, form the wolframic acid/titanium dioxide compound mixed, this compound being mixed also baking with elemental sulfur makes tungsten oxide change tungsten disulfide into again, then heating and calcining desulfurization again, and finally cooling obtains tungsten disulfide/titanium dioxide compound.
Concrete, the preparation method of tungsten disulfide/titanium dioxide compound, step is as follows:
1., raw material is prepared by following proportioning
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 are 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 coprecipitation reaction; filtration, washing mix with enough elemental sulfurs with after drying, then put into N2 or rare gas protective atmosphere baking, then heating and calcining desulfurization; by responseless elemental sulfur evaporative removal, obtain tungsten disulfide/titanium dioxide compound finally by cooling.
As the further improvement of the preparation method of tungsten disulfide/titanium dioxide compound of the present invention, described tungstates is at least one in sodium tungstate, ammonium tungstate and potassium tungstate.Baking temperature is 250 ~ 445 DEG C, and the baking time is 5 ~ 200 minutes.Calcining desulfurization temperature is 446 ~ 1000 DEG C, and calcining desulfurization time is 5 ~ 200 minutes.
The preparation method of tungsten disulfide/titanium dioxide compound, reacts according to following process:
Step one (surface active, precipitation reaction):
(surface active)
WO
4 2-+2H
++TiO
2→H
2WO
4(WO
3·H
2O)/TiO
2↓
Step 2 (heats in protective atmosphere, with N
2for example, 250-445 DEG C):
(in protective atmosphere, heating evaporation removes responseless sulphur to step 3, with N
2for example, 446-1000 DEG C);
Compared with prior art, beneficial effect of the present invention shows:
1), tungsten disulfide/titanium dioxide compound is mutually uniformly dispersed by tungsten disulfide and titanium dioxide and forms layer structure, in compound, titanium dioxide, tungsten disulfide exist with anatase crystal, six side 2H crystal formations respectively, tungsten disulfide particulate is lamellar, is titanium dioxide at the cluster body of the surface sediment of tungsten disulfide particulate.This tungsten disulfide/titanium dioxide compound is the collaborative lubrication and the synergic catalytic effect that utilize tungsten disulfide and titanium dioxide, can give full play to greasy property and the catalytic performance of two kinds of components, and then makes it have in known or tera incognita to apply more widely.
2), preparation method of the present invention avoids and directly synthesizes tungsten sulfide/titanium dioxide compound presoma, again by adding the compound required for thermally desulfurizing acquisition, but first synthesize wolframic acid/titanium dioxide compound presoma, again by high temperature vulcanized, final acquisition is lubricating the tungsten disulfide/titanium dioxide compound that there is applications well prospect with catalytic field.
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, to improve greasy property and the catalytic performance of this compound further.Preparation technology is simple, and fast, reaction condition is easy to control, and production cost is low, is applicable to batch production in reaction.
Accompanying drawing explanation
Fig. 1 is the x-ray diffractogram of powder spectrum of the tungsten disulfide/titanium dioxide compound synthesized by method provided by the invention.
According to the PDF card being numbered 841398 and 894921, all main diffraction peak all can index tungsten disulfide or titanium dioxide, show successfully to synthesize tungsten disulfide/titanium dioxide compound.The diffraction data of diffraction maximum relevant to titanium dioxide in compound and No. 894921 contained anatase titanium dioxides of PDF card is consistent, shows that titanium dioxide is present in compound with Detitanium-ore-type; Then contained with No. 841398 PDF cards six side 2H type tungsten disulfides of tungsten disulfide are consistent, show that tungsten disulfide is typical 2H layer structure.
Fig. 2 is the electron scanning micrograph of the tungsten disulfide/titanium dioxide compound synthesized by method provided by the invention, and Fig. 3 is the high magnification photo of Fig. 2.
Can find out that tungsten disulfide in compound and titanium dioxide interconnect, are uniformly dispersed by Fig. 2 and Fig. 3, compound middle level flaky particles is tungsten disulfide, is titanium dioxide at the cluster body of its surface sediment.
Detailed description of the invention
Embodiment 1
1 part of sodium tungstate and 0.5 part of titanium dioxide are placed in 133 parts of water, be heated to 80 DEG C, with salt acid for adjusting pH value to 0.5, gained strongly acidic solution makes titanium dioxide surface activate, tungstates and acid simultaneously reacts, the wolframic acid precipitation generated and the titanium dioxide surface effect of activation, form the wolframic acid/titanium dioxide compound precipitation mixed.Carry out filtering, washing and drying after reaction terminates, after then being mixed with 10 parts of elemental sulfurs by wolframic acid/titanium dioxide compound, insert N
2in at 300 DEG C baking 60 minutes, be warming up to 600 DEG C of evaporation desulfurization 30 minutes after sulfuration terminates again, after cooling, obtain tungsten disulfide/titanium dioxide compound (as shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photo).
Embodiment 2
1 part of ammonium tungstate and 0.5 part of titanium dioxide are placed in 133 parts of water, be heated to 80 DEG C, with salt acid for adjusting pH value to 0.5, gained strongly acidic solution makes titanium dioxide surface activate, tungstates and acid simultaneously reacts, the wolframic acid precipitation generated and the titanium dioxide surface effect of activation, form the wolframic acid/titanium dioxide compound precipitation mixed.Carry out filtering, washing and drying after reaction terminates, then baking is inserted in Ar gas at 300 DEG C after being mixed with 10 parts of elemental sulfurs by wolframic acid/titanium dioxide compound 60 minutes, be warming up to 600 DEG C of evaporation desulfurization 30 minutes after sulfuration terminates again, after cooling, obtain tungsten disulfide/titanium dioxide compound (being similar to shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photo).
Embodiment 3
1 part of potassium tungstate and 0.5 part of titanium dioxide are placed in 133 parts of water, be heated to 80 DEG C, with salt acid for adjusting pH value to 0.5, gained strongly acidic solution makes titanium dioxide surface activate, tungstates and acid simultaneously reacts, the wolframic acid precipitation generated and the titanium dioxide surface effect of activation, form the wolframic acid/titanium dioxide compound precipitation mixed.Carry out filtering, washing and drying after reaction terminates, after then being mixed with 10 parts of elemental sulfurs by wolframic acid/titanium dioxide compound, insert N
2in gas at 400 DEG C baking 30 minutes, be warming up to 450 DEG C of evaporation desulfurization 60 minutes after sulfuration terminates again, after cooling, obtain tungsten disulfide/titanium dioxide compound (being similar to shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photo).
Embodiment 4
1 part of sodium tungstate and 10 parts of titanium dioxide are placed in 1000 parts of water, be heated to 40 DEG C, with salt acid for adjusting pH value to 0.1, gained strongly acidic solution makes titanium dioxide surface activate, tungstates and acid simultaneously reacts, wolframic acid (aqua oxidation tungsten) precipitation generated and the titanium dioxide surface effect of activation, form the wolframic acid/titanium dioxide compound precipitation mixed.Carry out filtering, washing and drying after reaction terminates, after then being mixed with 5 parts of elemental sulfurs by wolframic acid/titanium dioxide compound, insert N
2in gas at 280 DEG C baking 180 minutes, be warming up to 800 DEG C of evaporation desulfurization 10 minutes after sulfuration terminates again, after cooling, obtain tungsten disulfide/titanium dioxide compound (being similar to shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photo).
Embodiment 5
1 part of sodium tungstate and 1 part of titanium dioxide are placed in 4000 parts of water, be heated to 90 DEG C, with salt acid for adjusting pH value to 0.5, gained strongly acidic solution makes titanium dioxide surface activate, tungstates and acid simultaneously reacts, wolframic acid (aqua oxidation tungsten) precipitation generated and the titanium dioxide surface effect of activation, form the wolframic acid/titanium dioxide compound precipitation mixed.Carry out filtering, washing and drying after reaction terminates, after then being mixed with 2 parts of elemental sulfurs by wolframic acid/titanium dioxide compound, insert N
2in gas at 350 DEG C baking 120 minutes, be warming up to 450 DEG C of evaporation desulfurization 100 minutes after sulfuration terminates again, after cooling, obtain tungsten disulfide/titanium dioxide compound (being similar to shown in Fig. 1 collection of illustrative plates and Fig. 2-3 photo).
Claims (6)
1. tungsten disulfide/titanium dioxide compound, it is characterized in that: this compound is mutually uniformly dispersed by tungsten disulfide and titanium dioxide and forms layer structure, in compound, titanium dioxide, tungsten disulfide exist with anatase crystal, six side 2H crystal formations respectively, tungsten disulfide particulate is lamellar, is titanium dioxide at the cluster body of the surface sediment of tungsten disulfide particulate.
2. the preparation method of tungsten disulfide/titanium dioxide compound as claimed in claim 1, it is characterized in that: utilize strongly acidic solution to activate titanium dioxide surface, tungstates and acid simultaneously reacts, wolframic acid (aqua oxidation tungsten) precipitation generated and the titanium dioxide surface effect activated, form the wolframic acid/titanium dioxide compound mixed, this compound being mixed also baking with elemental sulfur makes tungsten oxide change tungsten disulfide into again, then heating and calcining desulfurization again, finally cooling obtains tungsten disulfide/titanium dioxide compound.
3. the preparation method of tungsten disulfide/titanium dioxide compound as claimed in claim 2, is characterized in that: step is as follows:
1., raw material is prepared by following proportioning
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., by tungstates and titanium dioxide being placed in water, being heated to 0 ~ 100 DEG C, with salt acid for adjusting pH value to being less than or equal to 1, obtaining wolframic acid/titanium dioxide compound by coprecipitation reaction, filtration, washing mix with enough elemental sulfurs with after drying, then put into N
2or baking in rare gas protective atmosphere, then heating and calcining desulfurization, by responseless elemental sulfur evaporative removal, obtains tungsten disulfide/titanium dioxide compound finally by cooling.
4. the preparation method of tungsten disulfide/titanium dioxide compound as claimed in claim 2 or claim 3, is characterized in that: described tungstates is at least one in sodium tungstate, ammonium tungstate and potassium tungstate.
5. the preparation method of tungsten disulfide/titanium dioxide compound as claimed in claim 2 or claim 3, it is characterized in that: baking temperature is 250 ~ 445 DEG C, the baking time is 5 ~ 200 minutes.
6. the preparation method of tungsten disulfide/titanium dioxide compound as claimed in claim 2 or claim 3, is characterized in that: calcining desulfurization temperature is 446 ~ 1000 DEG C, and calcining desulfurization time is 5 ~ 200 minutes.
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Cited By (2)
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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 |
| CN110164695A (en) * | 2019-05-13 | 2019-08-23 | 常州工学院 | Flower-shaped upright orientation tungsten disulfide modification one-dimensional ordered carbon films cladding titanium dioxide nano stick array composite material and preparation method |
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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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2015
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Patent Citations (3)
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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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110164695A (en) * | 2019-05-13 | 2019-08-23 | 常州工学院 | Flower-shaped upright orientation tungsten disulfide modification one-dimensional ordered carbon films cladding titanium dioxide nano stick array composite material and preparation method |
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