CN106477633B - A kind of bimetal-doped group vib metal oxide nano-material and the preparation method and application thereof - Google Patents
A kind of bimetal-doped group vib metal oxide nano-material and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses a kind of bimetal-doped group vib metal oxide nano-material and the preparation method and application thereof.The chemical formula of group vib metal oxide nano-material of the present invention is AxByMO3, wherein M is group vib element, A and B be in the form of metal cation existing for doped chemical, O is oxygen element, and 0≤x≤1,0≤y≤1, A and B are one of not identical and self-existent main group or subgroup element.Metal oxide nano-material is prepared using compound, reducing agent and the substance containing A, B element of the metallic element containing group vib in the present invention under hydrothermal conditions.The bimetal-doped group vib oxide nano particles of preparation have very strong near-infrared screening capacity, can be applied to the fields such as light control materials and device, glass energy-saving.
Description
Technical field
The present invention relates to inorganic oxide material and its preparation fields.More particularly, to a kind of bimetal-doped group vib
Metal oxide nano-material and the preparation method and application thereof.
Background technique
It steps into after 21 century, modern civilization society is faced with lot of challenges.Wherein, it is sustainable to become society for energy crisis
One of biggest obstacle of development.World architecture energy consumption proportion in entire energy consumption is 30%~40%, is entirely being built
In the energy loss built, about 50% consumption is on door and window.According to measuring and calculating, the built building 90% in China is not energy-efficient at present,
And predict the year two thousand twenty China construction area and be up to 70,000,000,000 square metres, it means that building energy consumption will sharply increase.If
Do not take energy conservation measure, it is therefore foreseen that arrive the year two thousand twenty, Chinese architecture energy consumption is up to 1,100,000,000 tons of standard coals, and wherein summer air-conditioning freezes
Peak load will consume 10 the three gorges hydropower plants generated energy at full capacity.So building energy conservation is a great society sustainable development in China
The theme of exhibition, and the exploitation of door glass high transparency heat-barrier material and application are the most important things of current building energy conservation.
The energy of solar radiation is concentrated mainly on wavelength as that can be broadly divided into three areas in the range of 200~2500nm
Domain: ultra-violet (UV) band (200-380nm), it is seen that light area (380-780nm) and infrared region (780-2500nm).Solar energy is in these three areas
The energy of domain distribution is not quite similar, and ultraviolet about 5%, it is seen that light is about 45%, infrared by about 45%.Wherein there was only visible light pair
The visual activity of people has an impact.And it is infrared not only to people's vision without any contribution, but also existed in the form of heat.Therefore,
The energy conservation of door and window obstructs infrared light mainly under the premise of guaranteeing indoor lighting, weakens the heat of indoor and outdoor
Transmitting, to achieve the purpose that reduce indoor heating and the consumed energy that freezes.
The product of some glass heat-proofs currently on the market is mainly metal coating or heat reflection pad pasting, these products every
The function of heat drop temperature is achieved by the energy of reflective portion sunlight.But that there are service lifes is short for it, prepares required
The problems such as process conditions are more complex and equipment is expensive, and marketing difficulty is big.Glass heat-insulating coating, reach same high transparency and
While heat-proof quality, also have production cost low, it is easy to operate, the advantages that high-weatherability.
Group vib metal oxide includes CrO3、MoO3And WO3.The study found that pure group vib oxide to visible light and
Infrared light does not respond significantly, and when the group vib metallic element in this type oxide is in partial reduction state, such object
Confrontation infrared light has absorption, and to visible light transmission still with higher.For example, by WO3In inert atmosphere or vacuum
Under be heated to high temperature and obtain the group vib protoxide (WO with oxygen defect3-x) or WO is added in metallic element3, obtain metal
The tungsten bronze material of element doping, all has infrared absorption.
A kind of preparation method of reduction-state ammonium tungsten bronze nanoparticle is disclosed in Chinese patent application CN103496744B,
Its main contents, which is disclosed, has been prepared reduction-state ammonium tungsten using organic tungsten source and organic higher boiling amine under the conditions of solvent heat
Bronze nanoparticle.
United States Patent (USP) U.S.20110248225, which is disclosed, has K based on preparation under the conditions of plasma torchxCsyWO3(x+y
≤ 1,2≤z≤3) Potassium cesium tungsten bronze method.
However, in disclosed document and patent few codope group vib metal oxide materials report, it is most of to make
Standby is traditional single doping group vib metal oxide materials, due to single doping group vib metal oxide materials free electron
Limited amount causes it poor for the absorbability of infrared light especially near infrared light.In the codope of a small number of open reports
It is usually the form for thering is nonmetalloid to carry out alternative dopings to oxygen element, but this kind of doping way in group vib metal oxide
Distortion effect easily is generated to the microstructure of product especially lattice, to form electronics capture or scattering center, and then is reduced
Free electronic concentration increases its effective mass, this is unfavorable for the raising of infrared property for obscuring.Other codope group vib gold
Belong to oxide and although take the preparation methods such as bimetal-doped, but using plasma, complex process is not suitable for extensive raw
It produces.
Accordingly, it is desirable to provide a kind of prepare easy and low-cost bimetal-doped group vib metal oxide nano material
Material and preparation method thereof.
Summary of the invention
The first purpose of this invention is to provide a kind of bimetal-doped group vib metal oxide nano-material.
Second object of the present invention is to provide a kind of preparation of bimetal-doped group vib metal oxide nano-material
Method.
Third object of the present invention is to provide a kind of answering for bimetal-doped group vib metal oxide nano-material
With.
Freely electricity in a kind of group vib metal oxide materials of bimetal element doping of the invention rich in higher concentration
Son and there is very strong near-infrared screening effect in entire near infrared region, while the material preparation process is simple, it is low in cost,
The fields such as light control materials and device, glass energy-saving have broad application prospects.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of bimetal-doped group vib metal oxide nano-material, the bimetal-doped group vib metal oxide
Chemical formula is AxByMO3, wherein M is group vib element, A and B be in the form of metal cation existing for doped chemical, O is oxygen member
Element, 0≤x≤1,0≤y≤1, A and B are one of not identical and self-existent main group or subgroup element.A and B can be equal
It can also be subgroup element or A main group B subgroup, A subgroup B main group, four kinds of modes for major element.
Preferably, the valence state of the group vib element is+6, or the combination of one or both of+6 valences and+5 ,+4 valences.
The valence state of group vib element contains+6 valence states certainly, because part group vib element is to be restored to+5 and/or+4 valences from+6 valences, no
Group vib element that may be all is reduced.
Preferably, the major element be lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca),
Germanium (Ge), tin (Sn), aluminium (Al), gallium (Ga) and indium (In)；The subgroup element is silver (Ag), golden (Au), titanium (Ti) and zirconium
(Zr)。
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of bimetal-doped group vib metal oxide nano-material as described above, including walk as follows
It is rapid:
1) compound of the element containing group vib is dissolved in the water, obtains the chemical combination that concentration is 0.1mmol/L-0.5mol/L
Object aqueous solution；
2) substance of the substance containing metal element A and the B containing metallic element is added into the compound water solution in step 1)
And reducing agent, it is uniformly mixed, hydro-thermal reaction 1-72 hours under the conditions of 150-300 DEG C；It is described to contain metal element A and contain metal
The molar ratio of the compound of the total amount and element containing group vib of two kinds of substances of element B is 0.1-1:1；The reducing agent with contain group vib
The molar ratio of the compound of element is 0.5-20:1.
3) sediment after reaction in step 2) is obtained to bimetal-doped group vib gold after centrifugation, washing and drying
Belong to oxide-based nanomaterial.
Preferably, in step 1), the compound of the element containing group vib is Tungstenic compound or molybdate compound；It is preferred that
Ground, the Tungstenic compound be selected from tungsten hexachloride, tungsten tetrachloride, potassium tungstate, wolframic acid caesium, sodium tungstate, wolframic acid rubidium, ammonium paratungstate,
One of ammonium metatungstate, positive ammonium tungstate, tungsten silicide, tungsten sulfide, chlorine oxygen tungsten and a tungstic acid hydrate are a variety of；Preferably, described
Molybdate compound is selected from metamolybdic acid ammonium, positive ammonium molybdate, ammonium paramolybdate, molybdic acid, molybdenum silicide, molybdenum sulfide, chlorine oxygen molybdenum, alcohol oxygen molybdenum, five
One of molybdenum chloride, molybdenum tetrachloride, molybdenum bromide, molybdenum fluoride, molybdenum carbide, oxidation of coal molybdenum are a variety of.
Preferably, in step 1), it is also necessary to acidic materials be added and adjust the pH to 1-6.5 of solution or alkaline matter tune is added
Save the pH to 7.5-12 of solution；The acidic materials are selected from inorganic acid and/or organic acid；The alkaline matter is selected from inorganic base
And/or organic base.
Preferably, in step 1), the acidic materials are in hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, citric acid and acetic acid
It is one or more；The alkaline matter is selected from sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ethamine, ethanol amine, second
Diamines, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA) and triethanolamine
One of or it is a variety of.
Preferably, in step 2), the substance containing metal element A exists in the form of compound and/or simple substance；It is described
The substance of the B containing metallic element exists in the form of compound and/or simple substance.
Preferably, in step 2), the reducing agent is selected from organic and/or inorganic reducing agent；Preferably, the organic reducing
Agent is selected from oxalic acid, citric acid, methanol, ethyl alcohol, ethylene glycol, 1,2-PD, 1,3-PD, glycerine, ethanol amine, three ethyl alcohol
One of amine, oleyl amine, oleic acid, ethylenediamine, hydrazine hydrate, ammonium oxalate and ammonium hydroxide are a variety of；Preferably, the inorganic reducing agent choosing
From one of sodium borohydride, potassium borohydride, hydrogen sulfide, sodium hypophosphite or a variety of.
To reach above-mentioned third purpose, the present invention is adopted the following technical solutions:
A kind of bimetal-doped group vib metal oxide nano-material as described above answering in near-infrared masking field
With.
In the prior art, in disclosed document and patent few codope group vib metal oxide materials report, greatly
Part preparation is traditional single doping group vib metal oxide materials, since single doping group vib metal oxide materials are free
The limited amount of electronics causes it poor for the absorbability of infrared light especially near infrared light.In a small number of open reports
It is usually the form for thering is nonmetalloid to carry out alternative dopings to oxygen element, but this kind is mixed in codope group vib metal oxide
Miscellaneous mode easily generates distortion effect to the microstructure of product especially lattice, so that electronics capture or scattering center are formed, into
And reduce free electronic concentration or increase its effective mass, this is unfavorable for the raising of infrared property for obscuring.Other codope
Although group vib metal oxide takes the preparation methods such as bimetal-doped, but using plasma, complex process is not suitable for
Large-scale production.Technical solution of the present invention, by hydro-thermal method, a step directly obtains bimetal-doped group vib metal oxide,
It is doped using interstitial site of the various sizes of metal cation to group vib oxide, overcomes traditional tungsten bronze current-carrying
The low disadvantage of sub- concentration.By changing reducing agent and doped raw material, the product of different doped chemicals is obtained.Obtained bimetallic
The group vib metal oxide nanoparticles of doping, crystallinity are high, and particle diameter distribution is narrow, and free electronic concentration is relative to current same
Class product improves a lot, to have very strong screening to entire near infrared region while guaranteeing compared with high visible light transmissivity
Cover effect.
Beneficial effects of the present invention are as follows:
Under hydrothermal conditions, a step obtains the group vib metal oxide nanoparticles of bimetal-doped.Therefore, of the invention
Major advantage be that preparation step is simple, the microscopic appearance of product is uniform, and crystallinity is high, and particle diameter distribution is narrow, needs not move through ball milling
Process, and the near infrared absorption ability that the group vib metal oxide of bimetal-doped is prepared is strong, it is seen that light transmission rate is high.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the XRD spectrum of lithium potassium tungsten bronze in the embodiment of the present invention 1.
Fig. 2 shows the SEM photographs of lithium potassium tungsten bronze particle in the embodiment of the present invention 1.
Fig. 3 shows the XPS map of lithium potassium tungsten bronze powder in the embodiment of the present invention 2.
Fig. 4 shows the film transmitted spectrum of lithium potassium tungsten bronze in the embodiment of the present invention 2.
Fig. 5 shows the SEM photograph of sodium potassium tungsten bronze particle in the embodiment of the present invention 3.
Fig. 6 shows the SEM photograph of magnesium indium molybdenum bronze particle in the embodiment of the present invention 5.
Fig. 7 shows the TEM photo of lithium caesium tungsten bronze particle in the embodiment of the present invention 7.
Fig. 8 shows the TEM photo of potassium silver tungsten bronze particle in the embodiment of the present invention 9.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
A kind of lithium potassium tungsten bronze Li0.12K0.2WO3Nano particle, preparation method are as follows:
The pH of solution, is adjusted to by the wolframic acid aqueous solutions of potassium 80ml for configuring 0.15mol/L using the hydrochloric acid solution of 3mol/L
2.5.Then 0.0015mol lithium nitrate and 0.002mol potassium nitrate is added, is stirred at room temperature uniformly mixed；It adds
Then 0.15mol glycerine moves to solution in 150ml hydrothermal reaction kettle, react for 24 hours at 160 DEG C in baking oven.Reaction terminates
Product is centrifuged after being cooled to room temperature, then is washed respectively four times with 50ml deionized water and 50ml dehydrated alcohol,
Powder granule is dried in vacuo at 70 DEG C.XRD, SEM test are carried out to obtained lithium potassium tungsten bronze powder granule.If Fig. 1 is this reality
Apply the XRD spectrum of a product.XRD test result shows the appearance position class of NO.79-0769 on its structure and JCPDS standard card
Seemingly, the chemical formula of the product is Li0.12K0.2WO3.Fig. 2 is the SEM photograph of the product.SEM characterization result shows obtained lithium
Potassium tungsten bronze particle is length 20-200nm, and width is the rod-shpaed particle of 5-10nm.
Embodiment 2
A kind of lithium potassium tungsten bronze Li0.29K0.23WO3Nano particle, preparation method are as follows:
The pH of solution, is adjusted to by the wolframic acid aqueous solutions of potassium 80ml for configuring 0.15mol/L using the hydrochloric acid solution of 3mol/L
2.5.Then 0.004mol lithium nitrate and 0.003mol potassium nitrate is added, is stirred at room temperature uniformly mixed；Add 0.15mol
Then glycerine moves to solution in 150ml hydrothermal reaction kettle, react for 24 hours at 160 DEG C in baking oven.Reaction terminates to be cooled to
Product is centrifuged after room temperature, then is washed respectively four times with 50ml deionized water and 50ml dehydrated alcohol, at 70 DEG C
Vacuum drying powder granule.XRD and TEM test result is carried out to powder granule and shows granule crystal structure, pattern, size,
Performance is all similar with the particle that embodiment 1 is prepared.XPS test is carried out, test results are shown in figure 3, the result table
In bright surface element composition, the mixed valence of W presence+6 and+5, wherein W5+Ratio account for the 43% of all W elements.Fig. 4
For the present embodiment product Li0.29K0.23WO3Film transmitted spectrum.Should the result shows that, lithium potassium tungsten bronze near infrared light have very
Strong shielding action, while also can guarantee higher visible light transmittance.
Embodiment 3
A kind of sodium potassium tungsten bronze Na0.2K0.07WO3Nano particle, preparation method are as follows:
The pH of solution, is adjusted to by the wolframic acid sodium water solution 80ml for configuring 0.25mol/L using the hydrochloric acid solution of 3mol/L
7.5.It adds 0.002mol potassium sulfate and 0.0045mol sodium sulphate is stirred at room temperature uniformly mixed, be then added
The reducing agent ethylenediamine of 0.075mol, then moves to solution in 150ml hydrothermal reaction kettle, reacts at 180 DEG C in baking oven
20h.It reacts after being centrifuged, washed to product after terminating to be cooled to room temperature, is dried in vacuo powder granule at 70 DEG C.To powder
Particle carries out SEM test, as a result as shown in figure 5, obtained sodium potassium tungsten bronze particle is length 50-500nm, width 50-
The rod-shpaed particle of 100nm.It is similar with 2 result of embodiment to the shield effectiveness of near infrared light.
Embodiment 4
A kind of sodium potassium tungsten bronze Na0.22K0.1WO3Nano particle, preparation method are as follows:
The pH of solution, is adjusted to by the wolframic acid sodium water solution 80ml for configuring 0.25mol/L using the sulfuric acid solution of 3mol/L
7.5.0.0025mol potassium sulfate and 0.006mol sodium sulphate are added, the reducing agent ethylenediamine of 0.075mol is then added, in room
It is uniformly mixed under temperature；, then solution is moved in 150ml hydrothermal reaction kettle, reacts 20h at 180 DEG C in baking oven.Reaction
End is cooled to after room temperature product is centrifuged, is washed after, be dried in vacuo powder granule at 70 DEG C.Powder granule is carried out
SEM test, granule crystal structure, pattern, size, performance are all similar with the particle that embodiment 3 is prepared.
Embodiment 5
A kind of magnesium indium molybdenum bronze Mg0.15In0.1WO3Nano particle, preparation method are as follows:
The molybdenum pentachloride aqueous solution 100ml of 0.15mol/L is configured, 0.03mol citric acid is then added as reducing agent, then
0.004mol indium nitrate and 0.0025mol magnesium nitrate is added, moves into reaction kettle after stirring.It is reacted at 250 DEG C
36h.After product is centrifuged, is washed after 8 DEG C of vacuum drying, magnesium indium molybdenum bronze powder is obtained.Its SEM characterization result as shown in fig. 6,
Granule crystal structure, pattern, size is all similar with the particle that embodiment 3 is prepared, to the shield effectiveness of near infrared light
It is similar with 3 result of embodiment.
Embodiment 6
A kind of magnesium indium molybdenum bronze Mg0.2In0.18WO3Nano particle, preparation method are as follows:
The molybdenum pentachloride aqueous solution 100ml of 0.15mol/L is configured, 0.0075mol citric acid is then added as reducing agent,
0.005mol indium nitrate and 0.005mol magnesium nitrate are added, moves into reaction kettle after stirring.It is reacted at 250 DEG C
36h.After product is centrifuged, is washed after 80 DEG C of vacuum drying, magnesium indium molybdenum bronze powder is obtained.SEM characterization result shows granulated
Looks be it is rodlike, granular size is similar with the particle that embodiment 3 is prepared, to the shield effectiveness of near infrared light also with embodiment
3 results are similar.
Embodiment 7
A kind of lithium caesium tungsten bronze Li0.2Cs0.08WO3Nano particle, preparation method are as follows:
The tungsten chloride aqueous solution 100ml of 0.05mol/L is configured, 0.03mol oxalic acid is then added as reducing agent, sufficiently stirs
It mixes to after being completely dissolved, then 0.0015mol lithium hydroxide and 0.001mol cesium hydroxide is added thereto.The pale yellow mixture of colours is molten
Liquid is transferred in water heating kettle, reacts 10h at 240 DEG C.After navy blue powder is centrifuged, is washed, it is dried in vacuo at 70 DEG C
Powder granule.Its TEM pattern is as shown in fig. 7, be the lithium caesium tungsten bronze of disk and corynebacterium, average grain diameter 30nm is right
The shield effectiveness of near infrared light is similar with 2 result of embodiment.
Embodiment 8
A kind of lithium caesium tungsten bronze Li0.35Cs0.23WO nano particle, preparation method are as follows:
The tungsten chloride aqueous solution 75ml of 0.3mol/L is configured, the 1,2-PD of 0.35mol is then added as reducing agent,
It is stirred well to after being completely dissolved, then 0.02mol lithium hydroxide and 0.005mol cesium hydroxide is added thereto.By pale yellow color contamination
It closes solution to be transferred in water heating kettle, reacts 10h at 240 DEG C.After navy blue powder is centrifuged, is washed, the vacuum at 70 DEG C
Dry powder granule.Characterization result shows granule crystal structure, pattern, size, that performance is all prepared with embodiment 7
Grain is similar.
Embodiment 9
A kind of potassium silver tungsten bronze K0.2Ag0.1WO3Nano particle, preparation method are as follows:
The ammonium metatungstate aqueous solution 100ml for configuring 0.2mol/L, is adjusted to 8 for the pH of solution using the ammonium hydroxide of 2mol/L, so
The potassium nitrate of 0.006mol and the silver nitrate of 0.003mol are added afterwards, is stirred well to after being completely dissolved, then be added thereto
0.2mol ethylene glycol and 0.1mol sodium hypophosphite, solution is transferred in water heating kettle, is reacted for 24 hours at 200 DEG C.By dark blue toner
After body is centrifuged, is washed, the vacuum drying powder granule at 70 DEG C.Its TEM pattern is as shown in figure 8, be sheet and stub
The potassium silver tungsten bronze particle of shape, average grain diameter 50nm.It is similar with 2 result of embodiment to the shield effectiveness of near infrared light.
Embodiment 10
A kind of sodium aluminium molybdenum bronze Na0.13Al0.15WO3Nano particle, preparation method are as follows:
PH value of solution, is adjusted to by the ammonium paramolybdate aqueous solution 100ml for configuring 0.25mol/L using the sodium hydroxide of 2mol/L
9, the pure aluminum and 0.006mol sodium sulphate of 0.005mol is then added, is stirred well to after being completely dissolved, then be added thereto
0.3mol ethyl alcohol, solution is transferred in water heating kettle, reacts 72h at 220 DEG C.After navy blue powder is centrifuged, is washed,
Vacuum drying powder granule at 70 DEG C.Characterization result shows granule crystal structure, pattern, size, and performance is all made with embodiment 9
Standby obtained particle is similar.
Embodiment 11
It is similar to Example 1, the difference is that the potassium tungstate in wolframic acid aqueous solutions of potassium is tuned as tungsten hexachloride, four
Tungsten chloride, wolframic acid caesium, sodium tungstate, wolframic acid rubidium, ammonium paratungstate, ammonium metatungstate, positive ammonium tungstate, tungsten silicide, tungsten sulfide, chlorine oxygen tungsten and
One of one tungstic acid hydrate is a variety of, remaining technological parameter is identical, still is able to prepare lithium potassium tungsten bronze Li0.12K0.2WO3It receives
Rice grain, it is similar with 1 result of embodiment to the screening effect of near infrared light.
Embodiment 12
It is similar to Example 5, the difference is that the molybdenum pentachloride in molybdenum pentachloride aqueous solution is tuned as metamolybdic acid
Ammonium, positive ammonium molybdate, ammonium paramolybdate, molybdic acid, molybdenum silicide, molybdenum sulfide, chlorine oxygen molybdenum, alcohol oxygen molybdenum, molybdenum tetrachloride, molybdenum bromide, molybdenum fluoride,
One of molybdenum carbide, oxidation of coal molybdenum are a variety of, remaining technological parameter is identical, still are able to prepare magnesium indium molybdenum bronze
Mg0.15In0.1WO3Nano particle, it is similar with 5 result of embodiment to the screening effect of near infrared light.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of bimetal-doped group vib metal oxide nano-material, it is characterised in that: the bimetallic is mixed
The chemical formula of miscellaneous group vib metal oxide is AxByMO3, wherein M is group vib element, and A and B are existed in the form of metal cation
Doped chemical, O is oxygen element, and 0 < x≤1,0 < y≤1, A and B is in not identical and self-existent main group or subgroup element
One kind；
The major element is lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, germanium, tin, aluminium, gallium and indium；The subgroup element is silver, gold, titanium
And zirconium；
The preparation method of the bimetal-doped group vib metal oxide nano-material includes the following steps:
1) compound of the element containing group vib is dissolved in the water, obtains the compound that concentration is 0.1 mmol/L-0.5 mol/L
Aqueous solution；
2) be added in the compound water solution into step 1) the substance containing metal element A and the B containing metallic element substance and
Reducing agent is uniformly mixed, hydro-thermal reaction 1-72 hours under the conditions of 150-300 DEG C；It is described to contain metal element A and contain metallic element
The molar ratio of the compound of the total amount and element containing group vib of two kinds of substances of B is 0.1-1:1；The reducing agent and element containing group vib
Compound molar ratio be 0.5-20:1；
3) sediment after reacting in step 2 is obtained into bimetal-doped group vib metal oxygen after centrifugation, washing and drying
Compound nano material；
Wherein, in step 1), it is also necessary to acidic materials be added and adjust the pH to 1-6.5 of solution or alkaline matter adjusting solution is added
PH to 7.5-12；The acidic materials are selected from inorganic acid and/or organic acid；The alkaline matter is selected from inorganic base and/or has
Machine alkali；
In step 1), the compound of the element containing group vib is Tungstenic compound or molybdate compound.
2. a kind of preparation method of bimetal-doped group vib metal oxide nano-material according to claim 1, special
Sign is: the valence state of group vib element is one of+6 valences and+5 ,+4 valences in the bimetal-doped group vib metal oxide
Or two kinds of combination.
3. the preparation method of bimetal-doped group vib metal oxide nano-material according to claim 1, feature exist
In: the Tungstenic compound is selected from potassium tungstate, wolframic acid caesium, sodium tungstate, wolframic acid rubidium, ammonium paratungstate, ammonium metatungstate and positive ammonium tungstate
One of or it is a variety of.
4. the preparation method of bimetal-doped group vib metal oxide nano-material according to claim 3, feature exist
One of metamolybdic acid ammonium, positive ammonium molybdate and ammonium paramolybdate or a variety of are selected from: the molybdate compound.
5. the preparation method of bimetal-doped group vib metal oxide nano-material according to claim 1, feature exist
In: in step 1), the acidic materials are selected from one of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, citric acid and acetic acid or a variety of；Institute
State alkaline matter be selected from sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ethamine, ethanol amine, ethylenediamine, dimethylamine,
One of trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA) and triethanolamine are more
Kind.
6. the preparation method of bimetal-doped group vib metal oxide nano-material according to claim 1, feature exist
In: in step 2, the substance containing metal element A exists in the form of compound and/or simple substance；The B containing metallic element
Substance exist in the form of compound and/or simple substance.
7. the preparation method of bimetal-doped group vib metal oxide nano-material according to claim 1, feature exist
In: in step 2, the reducing agent is selected from organic and/or inorganic reducing agent.
8. the preparation method of bimetal-doped group vib metal oxide nano-material according to claim 7, feature exist
Oxalic acid, citric acid, methanol, ethyl alcohol, ethylene glycol, 1,2-PD, 1,3-PD, the third three are selected from: the organic reducing agent
One of alcohol, ethanol amine, triethanolamine, oleyl amine, oleic acid, ethylenediamine, hydrazine hydrate and ammonium oxalate are a variety of.
9. the preparation method of bimetal-doped group vib metal oxide nano-material according to claim 7, feature exist
One of sodium borohydride, potassium borohydride, hydrogen sulfide, sodium hypophosphite or a variety of are selected from: the inorganic reducing agent.
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