CN107804872B - A kind of rutile phase hypovanadic oxide and preparation method thereof of porous laminated structure - Google Patents
A kind of rutile phase hypovanadic oxide and preparation method thereof of porous laminated structure Download PDFInfo
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- CN107804872B CN107804872B CN201610810435.1A CN201610810435A CN107804872B CN 107804872 B CN107804872 B CN 107804872B CN 201610810435 A CN201610810435 A CN 201610810435A CN 107804872 B CN107804872 B CN 107804872B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000001413 cellular Effects 0.000 claims abstract description 11
- 238000010276 construction Methods 0.000 claims abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000009825 accumulation Methods 0.000 claims abstract description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 35
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 27
- 229910000906 Bronze Inorganic materials 0.000 claims description 16
- VWBLQUSTSLXQON-UHFFFAOYSA-O [NH4+].[V+5] Chemical compound [NH4+].[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-O 0.000 claims description 16
- 239000010974 bronze Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical compound [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 235000019253 formic acid Nutrition 0.000 claims description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000011858 nanopowder Substances 0.000 abstract description 8
- 239000000843 powder Substances 0.000 description 33
- 239000011521 glass Substances 0.000 description 13
- 238000010586 diagram Methods 0.000 description 12
- 230000003287 optical Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing Effects 0.000 description 4
- 239000011449 brick Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011031 large scale production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 229910052904 quartz Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910001456 vanadium ion Inorganic materials 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000004301 light adaptation Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a kind of rutile phase hypovanadic oxides and preparation method thereof of porous laminated structure, the rutile phase hypovanadic oxide of the porous laminated structure is that the cellular construction of single layered porous or the multilayered structure as made of the cellular construction accumulation of the single layered porous, the cellular construction of the single layered porous are interconnected to form the stratiform two-dimensional structure with hole by particulate oxidation vanadium.The rutile phase hypovanadic oxide of porous laminated structure prepared by the present invention be nanometer emptying aperture is combined to inside nano-powder so that the rutile phase hypovanadic oxide material of porous laminated structure guarantee material the sun be adjustable efficiency it is constant while improve visible light transmittance.
Description
Technical field
The present invention relates to a kind of rutile phase hypovanadic oxides, and in particular to a kind of Rutile Type dioxy of porous laminated structure
Change vanadium and preparation method thereof, belongs to Material Field.
Background technique
Due to the sustainable growth of world energy consumption, make people to the utilization of novel renewable energy and the development of new technology
Produce urgent demand.The discharge of carbon dioxide and other polluted gas not only causes pollution to environment, to the body of people
Body health also results in influence.Therefore, it to the demand of the energy and using one of the factor for improving people's living standard is become, saves
Energy emission reduction has become the current top priority in various countries.It is estimated that having 1/3 in social total energy consumption, the above are building energy consumptions, therefore
Promoting building energy conservation is one of energy-saving and emission-reduction, the emphasis for realizing sustainable development.Since significant portion is used for sky in building energy consumption
It adjusts, more than half in air conditioner energy source is lost by window and extraneous heat exchange, therefore the intelligent power saving for passing through development of new
Window can be effectively reduced energy consumption, reduce the discharge of greenhouse gases, be finally reached energy-saving and environment-friendly purpose.
Currently, the energy-saving glass of market sale or energy saving pad pasting (abbreviation Energy Saving Windows) belong to low-launch-rate (Low~E)
Scope, its main feature is that visible light transmittance with higher and lower far infrared transmissivity (winter is heat-insulated), can realize every
While heat heat preservation, high blocking (being suitable for hot area) is carried out to the infrared part in sunlight or high transmission (is suitable for trembling with fear
Cryogenic region).But its price is higher and cannot carry out real-time monitoring to sunlight with the variation of ambient temperature, and it is " passive to belong to
Response " type, it is difficult to adapt to the most of climatic environments cold in winter and hot in summer in China.Other " active response " type energy-saving glass, such as
Electrochomeric glass, gas-discoloration glass, its structure is complicated, involves great expense, and is difficult to popularize in a short time.In contrast, it utilizes
The thermochromism energy-saving glass of huge optical change development caused by vanadium dioxide phase transformation, due to the temperature change that can accord with one's environment
It realizes the automatic adjustment of photo-thermal transflector, is not necessarily to any artificial energy source, it is considered to be one of energy-saving glass material of most low-carbon environment-friendly.
Preparing thermochromism intelligent glass, there are two types of modes, i.e., prepare vanadium dioxide plated film glass using extensive magnetron sputtering
The physics preparation method of glass and vanadium dioxide nano powder is prepared with chemical means in advance using nanotechnology, then by nano-powder
The chemical preparation mode of pad pasting energy-saving glass is prepared by modes such as chemicalpistons.Compared with former mode, Hou Zheyou
Simple in equipment, generality is strong, cheap, is easy to the remarkable advantage of large area production and wide application, it is easier to be market
Receive.But since vanadium oxygen system classes of compounds is various, only vanadium dioxide group achievement has a variety of isomerism crystal knots
Structure, how extensive titania phase hypovanadic oxide powder is always challenge to research and production.Titania phase at present
Hypovanadic oxide powder is broadly divided into two methods: one is direct synthesis techniques.Such as patent (Chinese invention patent publication number
CN102120615A) and document (Solar Energy Materials&Solar Cells 95 (2011) 3520) utilizes hydro-thermal
Method is in 260 DEG C or more processing, 24 hours one-step synthesis rutile phase hypovanadic oxide powders.Patent (Chinese invention patent publication number
CN104724757A) pass through solvent thermal reaction one-step synthesis rutile phase hypovanadic oxide powder at a lower temperature.Another kind is
Vanadium dioxide presoma is first synthesized, then passes through the means titania phase hypovanadic oxide powders such as heat treatment or hydro-thermal again.Such as
Patent (Chinese invention patent publication number CN101863511A) obtains B phase VO first with hydro-thermal method2Powder, then by above-mentioned powder
It is encapsulated in closed container resistant to high temperature, anneals within the scope of 350~1200 DEG C, acquire rutile phase hypovanadic oxide powder
Body.As patent (Chinese invention patent publication number CN102120614) is obtained using alkaline reagent processing tetravalent vanadium ion aqueous solution
Suspension presoma, is then transferred to hydrothermal reaction kettle for suspension, and required titanium dioxide can be made through hydro-thermal reaction, dry separation
Vanadium powder body.As document (Materials Research Bulletin 40 (2005) 315) synthesizes (NH first with hydro-thermal method4)0.5V2O5Nano wire, then above-mentioned powder is encapsulated in quartz ampoule, it anneals two hours at 570 DEG C, obtains VO2Nano wire, and
Its electrology characteristic is characterized, and does not apply and is preparing energy-saving coatings, the related neck of energy saving pad pasting or energy-saving glass etc.
Domain.
The final application of nano-powder be it is compound with filmogen, be prepared into intelligent power saving coating, pass through different film forming
Means are prepared into intelligent power saving film.Measure vanadium dioxide energy conservation film properties refer mainly to indicate solar energy regulation rate and visible light is saturating
Cross rate.And solar energy regulation rate is improved by improving vanadium dioxide solid content, it can seriously reduce the visible light transmittance of film.
Solution at present, scheme is first is that reduce the size of nano-powder, and scheme is second is that introduce nanometer emptying aperture.For scheme two,
There are some patents and document to make report, it, will such as document (ACS Appl.Mater.Interfaces 2011,3,135-138)
The precursor liquid of organic film former and tetravalent vanadium ion is compound to be prepared into vanadium dioxide coating liquid, is obtained after film forming by high-temperature process
Vanadium dioxide energy-saving film forms a large amount of emptying aperture, it will be apparent that improve film due to the presence of organic matter after high-temperature process
Visible light transmittance, but this method cannot be mass produced, and need high-temperature process, application range is single；Such as document
(Materials Letters 110 (2013) 241-244), the precursor B phase hypovanadic oxide first synthesized coat dioxy on surface
SiClx is obtained there are laminar VO2 (M)@SiO2 nano-powder of nanometer emptying aperture by heat treatment, is successfully drawn nanometer emptying aperture
Enter into nano-powder, but this nanometer emptying aperture is dispersed between stratum nucleare and shell, needs to coat processing, cumbersome,
Condition is harsh.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of rutile phase hypovanadic oxide of porous laminated structure and
Preparation method.
On the one hand, the present invention provides a kind of rutile phase hypovanadic oxide of porous laminated structure, the porous laminated knots
Made of the rutile phase hypovanadic oxide of structure is the cellular construction of single layered porous or is accumulated as the cellular construction of the single layered porous
The cellular construction of multilayered structure, the single layered porous is interconnected to form the stratiform two dimension knot with hole by particulate oxidation vanadium
Structure.
The rutile phase hypovanadic oxide of porous laminated structure prepared by the present invention is that nanometer emptying aperture is combined to nano-powder
Inside, so that the rutile phase hypovanadic oxide material of porous laminated structure is adjustable constant same of efficiency in the sun for guaranteeing material
Shi Tigao visible light transmittance.
Preferably, the particle size of the particulate oxidation vanadium in the rutile phase hypovanadic oxide of the porous laminated structure is
100nm~2 μm, preferably 100nm~1 μm, pore-size are 20nm~150nm, preferably 20nm~80nm, porosity ranges 1%
~20%, preferably 10%~20%.
Preferably, stratiform thickness >=200nm, preferably 200nm of the rutile phase hypovanadic oxide of the porous laminated structure
~2 μm, longest is on one side and the ratio of stratiform thickness is (1~100): 1, preferably (10~60): 1.
On the other hand, the present invention also provides a kind of preparation method of the rutile phase hypovanadic oxide of porous laminated structure,
Include:
The ammonium vanadium bronze phase (NH of layer structure4)0.6V2O5The preparation of vanadium dioxide presoma；
By the ammonium vanadium bronze phase (NH of layered structure4)0.6V2O5Vanadium dioxide presoma is in vacuum 400~900
It is heat-treated 5~120 minutes at DEG C, obtains the rutile phase hypovanadic oxide of porous laminated structure.
Preferably, utilizing the ammonium vanadium bronze phase (NH of hydro-thermal method synthesis layer structure4)0.6V2O5Vanadium dioxide presoma.
Also, preferably, hydro-thermal reaction 6~100 hours, obtain at 220~300 DEG C using ammonium metavanadate and formic acid as raw material
To the ammonium vanadium bronze phase (NH of layered structure4)0.6V2O5Vanadium dioxide presoma, wherein the ammonium metavanadate and formic acid rub
You are than being 3.3:1~1:2.6.
The rutile phase hypovanadic oxide powder of the resulting porous laminated structure of the present invention can be used for energy-saving coatings, energy saving pad pasting
Or the related fieldss such as energy-saving glass.Present invention process is simple, at low cost, reproducible, high income, and reaction process safety is not required to
Protection of reducing atmosphere is wanted, large-scale production, the hypovanadic oxide powder good dispersion obtained, stability height are suitble to.
Detailed description of the invention
Fig. 1 is the XRD diagram of vanadium dioxide presoma prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of vanadium dioxide presoma prepared by embodiment 1；
Fig. 3 is the XRD diagram of the rutile phase hypovanadic oxide of porous laminated structure prepared by embodiment 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of the rutile phase hypovanadic oxide of porous laminated structure prepared by embodiment 1；
Fig. 5 is film obtained by the rutile phase hypovanadic oxide powder of porous laminated structure prepared by embodiment 1 25
DEG C and 90 DEG C at a temperature of optical transmittance curve；
Fig. 6 is the XRD diagram of vanadium dioxide presoma prepared by embodiment 2；
Fig. 7 is the scanning electron microscope (SEM) photograph of vanadium dioxide presoma prepared by embodiment 2；
Fig. 8 is the XRD diagram of the rutile phase hypovanadic oxide of porous laminated structure prepared by embodiment 2；
Fig. 9 is the scanning electron microscope (SEM) photograph of the rutile phase hypovanadic oxide of porous laminated structure prepared by embodiment 2；
Figure 10 is film obtained by the rutile phase hypovanadic oxide powder for the porous laminated structure for implementing 2 preparations at 25 DEG C
With the optical transmittance curve at a temperature of 90 DEG C；
Figure 11 is the XRD diagram of vanadium dioxide presoma prepared by embodiment 3；
Figure 12 is the scanning electron microscope (SEM) photograph of vanadium dioxide presoma prepared by embodiment 3；
Figure 13 is the XRD diagram of the rutile phase hypovanadic oxide of the porous laminated structure of embodiment preparation；
Figure 14 is the scanning electron microscope (SEM) photograph of the rutile phase hypovanadic oxide of porous laminated structure prepared by embodiment 3；
Figure 15 is film obtained by the rutile phase hypovanadic oxide powder of porous laminated structure prepared by embodiment 3 25
DEG C and 90 DEG C at a temperature of optical transmittance curve.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention is by by ammonium vanadium bronze phase (NH4)0.6V2O5The heat treatment of one step of vanadium dioxide presoma, obtains having porous
The rutile phase hypovanadic oxide powder of layer structure, sandwich are the cellular construction of single layered porous or the list of single layered porous
Multilayered structure made of meta structure accumulation.
In the present invention, the cellular construction of the single layered porous is that stratiform two dimension knot is interconnected to form by particulate oxidation vanadium
Structure, and there are a large amount of holes in structure.Particulate oxidation vanadium obtains particle size 100nm~2 μm, and pore-size 20nm~
150nm, porosity ranges 1%~20%.
In the present invention, stratiform thickness >=200nm of the rutile phase hypovanadic oxide of the porous laminated structure, preferably
200nm~2 μm.Longest is on one side and the ratio of stratiform thickness can be (1~100): 1, preferably (10~60): 1.
Illustrate to following exemplary that the present invention provides the preparation method of the rutile phase hypovanadic oxide of porous laminated structure.
Synthesize the ammonium vanadium bronze phase (NH of layer structure4)0.6V2O5Vanadium dioxide presoma.Specifically, hydro-thermal is first passed through
Reaction is contained (NH4)0.6V2O5The mixed solution (alternatively referred to as hydro-thermal reaction solution) of powder, then by gained hydro-thermal reaction solution
The ammonium vanadium bronze phase (NH obtained after being filtered (filtering) drying4)0.6V2O5Powder (ammonium vanadium bronze phase (NH4)0.6V2O5Vanadium dioxide
Presoma).
As an example, using ammonium metavanadate and formic acid as raw material, the hydro-thermal reaction 6-100h at 220-300 DEG C.Inclined vanadium
The molar ratio of sour ammonium and formic acid is 3.3:1-1:2.6.
To ammonium vanadium bronze phase (NH4)0.6V2O5Vanadium dioxide presoma is heat-treated, and the golden red of porous laminated structure is obtained
Stone phase hypovanadic oxide.Heat treatment is to carry out under vacuum.Heat treatment temperature can be 400-900 DEG C.Heat treatment time can be 5-120
Minute.
The hypovanadic oxide powder good dispersion that the present invention is obtained, stability are high；Preparation method is also easy, at low cost, repeats
Property good, high income, be suitble to large-scale production.Powder prepared by the present invention can be widely used for the energy-saving coatings of building and automobile,
The related fieldss such as energy saving pad pasting and energy-saving glass.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
Step A) 1.733g ammonium metavanadate and 0.205g formic acid are weighed, it is stirred 10 minutes in 40mL deionized water.It is transferred to
In 100mL water heating kettle, is reacted 6 hours under the conditions of 300 DEG C, after cold filtration clean dry, obtain vanadium dioxide presoma；
Step B) appropriate above-mentioned vanadium dioxide presoma is weighed, it is warming up to 400 DEG C under vacuum conditions, keeps the temperature 120 minutes,
The rutile phase hypovanadic oxide powder of porous laminated structure is obtained after cooling；
Using XRD, vanadium dioxide presoma, the step B of SEM and spectrophotometer to step A)) porous laminated structure
The performance of rutile phase hypovanadic oxide powder characterized.
Fig. 1 is obtained the XRD diagram of vanadium dioxide presoma by step A), and display presoma is rendered as (NH4)0.6V2O5Single crystalline substance
Phase.
Fig. 2 is obtained the scanning electron microscope (SEM) photograph of vanadium dioxide presoma by step A), shows to be in square brick layer structure, and length-width ratio≤
2, thickness >=200nm, longest is on one side and the ratio of stratiform thickness is (1~100): 1.
Fig. 3 is obtained the XRD diagram of the rutile phase hypovanadic oxide of porous laminated structure by step B), shows ammonium vanadium bronze
(NH4)0.6V2O5Vanadium dioxide presoma is all converted to rutile phase hypovanadic oxide powder.
Fig. 4 is obtained the scanning electron microscope (SEM) photograph of the rutile phase hypovanadic oxide of porous laminated structure, size and Re Chu by step B)
Variation less, still keeps the layer structure of presoma, thickness >=200nm, length-width ratio≤2, longest one side and stratiform before managing
The ratio of thickness is (1~100): 1.Simultaneously because heat treatment has NH3Generation, make it have porosity.Vanadium oxide particle size
100nm~2 μm, pore-size 20nm~150nm, porosity ranges 1%~20%.
Fig. 5 is film obtained by the rutile phase hypovanadic oxide powder of porous laminated structure at a temperature of 25 DEG C and 90 DEG C
Optical transmittance curve.The rutile phase hypovanadic oxide of synthesized porous laminated structure has thermal discoloration as seen from the figure
Energy.
Embodiment 2
Step A) 1.733g ammonium metavanadate and 1.77g formic acid are weighed, it is stirred 10 minutes in 40mL deionized water.It is transferred to
In 100mL water heating kettle, is reacted 100 hours under the conditions of 220 DEG C, after cold filtration clean dry, obtain vanadium dioxide forerunner
Body；
Step B) appropriate above-mentioned vanadium dioxide presoma is weighed, it is warming up to 900 DEG C under vacuum conditions, keeps the temperature 5 minutes, it is cold
But the rutile phase hypovanadic oxide powder of porous laminated structure is obtained afterwards；
Using XRD, vanadium dioxide presoma, the step B of SEM and spectrophotometer to step A)) porous laminated structure
The performance of rutile phase hypovanadic oxide powder characterized.
Fig. 6 is obtained the XRD diagram of vanadium dioxide presoma by step A), and display presoma is rendered as (NH4)0.6V2O5Single crystalline substance
Phase.
Fig. 7 is obtained the scanning electron microscope (SEM) photograph of vanadium dioxide presoma by step A), shows to be in square brick layer structure, and length-width ratio≤
2, thickness >=200nm, longest is on one side and the ratio of stratiform thickness is (2~80): 1.
Fig. 8 is obtained the XRD diagram of the rutile phase hypovanadic oxide of porous laminated structure by step B), shows ammonium vanadium bronze
(NH4)0.6V2O5Vanadium dioxide presoma is all converted to rutile phase hypovanadic oxide powder.
Fig. 9 is obtained the scanning electron microscope (SEM) photograph of the rutile phase hypovanadic oxide of porous laminated structure, size and Re Chu by step B)
Variation less, still keeps the layer structure of presoma, thickness >=200nm, length-width ratio≤2, longest one side and stratiform before managing
The ratio of thickness is (2~80): 1.Simultaneously because heat treatment has NH3Generation, make it have porosity.Vanadium oxide particle size
100nm~2 μm, pore-size 20nm~150nm, porosity ranges 1%~20%.
Figure 10 is film obtained by the rutile phase hypovanadic oxide powder of porous laminated structure at a temperature of 25 DEG C and 90 DEG C
Optical transmittance curve.The rutile phase hypovanadic oxide of synthesized porous laminated structure has thermal discoloration as seen from the figure
Energy.The rutile phase hypovanadic oxide powder of structure.
Embodiment 3
Step A) 1.733g ammonium metavanadate and 1.0g formic acid are weighed, it is stirred 10 minutes in 40mL deionized water.It is transferred to
In 100mL water heating kettle, is reacted 50 hours under the conditions of 270 DEG C, after cold filtration clean dry, obtain vanadium dioxide forerunner
Body；
Step B) appropriate above-mentioned vanadium dioxide presoma is weighed, it is warming up to 750 DEG C under vacuum conditions, keeps the temperature 60 minutes,
The rutile phase hypovanadic oxide powder of porous laminated structure is obtained after cooling；
Using XRD, vanadium dioxide presoma, the step B of SEM and spectrophotometer to step A)) porous laminated structure
The performance of rutile phase hypovanadic oxide powder characterized.
Figure 11 is obtained the XRD diagram of vanadium dioxide presoma by step A), and display presoma is rendered as (NH4)0.6V2O5It is single
Crystal phase.
Figure 12 is obtained the scanning electron microscope (SEM) photograph of vanadium dioxide presoma by step A), and display is in square brick layer structure, length-width ratio
≤ 2, thickness >=200nm, longest is on one side and the ratio of stratiform thickness is (1~100): 1.
Figure 13 is obtained the XRD diagram of the rutile phase hypovanadic oxide of porous laminated structure by step B), shows ammonium vanadium bronze
(NH4)0.6V2O5Vanadium dioxide presoma is all converted to rutile phase hypovanadic oxide powder.
Figure 14 is obtained the scanning electron microscope (SEM) photograph of the rutile phase hypovanadic oxide of porous laminated structure, size and Re Chu by step B)
Variation less, still keeps the layer structure of presoma, thickness >=200nm, length-width ratio≤2, longest one side and stratiform before managing
The ratio of thickness is (1~100): 1.Simultaneously because heat treatment has NH3Generation, make it have porosity.Vanadium oxide particle size
100nm~2 μm, pore-size 20nm~150nm, porosity ranges 1%~20%.
Figure 15 is film obtained by the rutile phase hypovanadic oxide powder of porous laminated structure at a temperature of 25 DEG C and 90 DEG C
Optical transmittance curve.The rutile phase hypovanadic oxide of synthesized porous laminated structure has thermal discoloration as seen from the figure
Energy.
The foregoing is merely illustrative of the preferred embodiments of the present invention, the substantial technological content model being not intended to limit the invention
It encloses, substantial technological content of the invention is broadly defined in the scope of the claims of application, any technology that other people complete
Entity or method also or a kind of equivalent change, will if identical with defined in the scope of the claims of application
It is considered as being covered by among the scope of the claims.
Claims (4)
1. a kind of rutile phase hypovanadic oxide of porous laminated structure, which is characterized in that the rutile of the porous laminated structure
The cellular construction or the multilayered structure as made of the cellular construction accumulation of the single layered porous that phase hypovanadic oxide is single layered porous, institute
The cellular construction for stating single layered porous is interconnected to form the stratiform two-dimensional structure with hole by particulate oxidation vanadium, described porous
The particle size of particulate oxidation vanadium in the rutile phase hypovanadic oxide of layer structure is 100nm~2 μm, pore-size 20
The nm of nm~150, porosity ranges 1%~20%；
The preparation method of the rutile phase hypovanadic oxide of the porous laminated structure includes:
The ammonium vanadium bronze phase (NH of layer structure4)0.6V2O5The preparation of vanadium dioxide presoma；
By the ammonium vanadium bronze phase (NH of layered structure4)0.6V2O5Vanadium dioxide presoma is in vacuum at 400~900 DEG C
Heat treatment 5~120 minutes, obtains the rutile phase hypovanadic oxide of porous laminated structure.
2. the rutile phase hypovanadic oxide of porous laminated structure according to claim 1, it is characterised in that the porous layer
The stratiform thickness of the rutile phase hypovanadic oxide of shape structure >=200 nm, length-width ratio≤2, longest is on one side and the ratio of stratiform thickness is
(1~100): 1.
3. the rutile phase hypovanadic oxide of porous laminated structure according to claim 1, which is characterized in that utilize hydro-thermal method
Synthesize the ammonium vanadium bronze phase (NH of layer structure4)0.6V2O5Vanadium dioxide presoma.
4. the rutile phase hypovanadic oxide of porous laminated structure according to claim 3, which is characterized in that with ammonium metavanadate
It is raw material with formic acid, hydro-thermal reaction 6~100 hours at 220~300 DEG C obtain the ammonium vanadium bronze phase of layered structure
(NH4)0.6V2O5Vanadium dioxide presoma, wherein the molar ratio of the ammonium metavanadate and formic acid is 3.3:1~1:2.6.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102398919A (en) * | 2010-09-08 | 2012-04-04 | 中国科学院上海硅酸盐研究所 | Preparation method of rutile phase vanadium dioxide |
| CN103531766A (en) * | 2013-10-29 | 2014-01-22 | 福州大学 | Sodium-ion battery positive material ammonium vanadium oxide with graphite-like nitrate structure |
| JP5625172B2 (en) * | 2009-12-28 | 2014-11-19 | 東亞合成株式会社 | Vanadium dioxide fine particles, production method thereof, and thermochromic film |
| CN104402050A (en) * | 2014-10-29 | 2015-03-11 | 中国科学院合肥物质科学研究院 | D-phase vanadium dioxide nano-star powder and preparation method thereof |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5625172B2 (en) * | 2009-12-28 | 2014-11-19 | 東亞合成株式会社 | Vanadium dioxide fine particles, production method thereof, and thermochromic film |
| CN102398919A (en) * | 2010-09-08 | 2012-04-04 | 中国科学院上海硅酸盐研究所 | Preparation method of rutile phase vanadium dioxide |
| CN103531766A (en) * | 2013-10-29 | 2014-01-22 | 福州大学 | Sodium-ion battery positive material ammonium vanadium oxide with graphite-like nitrate structure |
| CN104402050A (en) * | 2014-10-29 | 2015-03-11 | 中国科学院合肥物质科学研究院 | D-phase vanadium dioxide nano-star powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Facile synthesis of graphite nitrate-like ammonium;Hailong Fei等;《Dalton Transactions》;20140903(第43期);第16522–16527页 * |
| Synthesis of novel ammonium vanadium bronze;Yining Ma等;《RSC Advances》;20151019;第2015卷(第5期);第90888-90894页 * |
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