CN107324391A - A kind of individual layer hydration tungstic trioxide nano-slice and preparation method thereof - Google Patents
A kind of individual layer hydration tungstic trioxide nano-slice and preparation method thereof Download PDFInfo
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Abstract
Tungstic trioxide nano-slice is hydrated the invention provides a kind of individual layer, provides and is hydrated tungstic trioxide nano-slice thickness and substantially reduces, be individual layer nanometer sheet, and better crystallinity degree, pattern is uniform.Present invention also offers the preparation method that the individual layer is hydrated tungstic trioxide nano-slice, its preparation process is simple and easy to apply, low for equipment requirements, is easy to large-scale production.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of individual layer hydration tungstic trioxide nano-slice and its preparation
Method.
Background technology
Tungstic acid (WO3) it is a kind of n-type wide bandgap semiconductor oxide, the WO of ordered nano-structure3Or hydration WO3Tool
There are the characteristics such as quantum effect specific to nano material, skin effect, have in fields such as gas sensing, photocatalysis, energy storage devices
Wide application prospect.It is well known that the performance of semi-conducting material and application have very big association with its microstructure and pattern, its
In, the two-dimensional nano WO with high specific surface area3Or hydration WO3With unique photoelectric characteristic, more and more closed
Note.
At present, the preparation method of the tungstic acid of two-dimensional nanostructure or hydration tungstic acid is broadly divided into " from bottom to top "
Method (such as high temperature gas phase method, chemical synthesis) and " from top to bottom " method (such as mechanical stripping method, chemical stripping method).Wherein, have not
The tungstic acid or hydration tungstic acid of few two-dimensional nanostructure are made by chemical stripping method, such as Application No.
200710054544.6 Chinese patent application discloses a kind of area for (100~800) nm × (100~800) nm, apparent thickness
Spend the WO for 5~40nm3Nanometer sheet and preparation method thereof；The Chinese patent application of Application No. 2012103776091 is disclosed
One kind prepares WO using thermal oxidation method3The method of nanometer sheet, WO made from the method3The thickness of nanometer sheet is 0.2~2 μm；There is document
(Chem.Mater.2010,22,5660-5666) report a kind of concentrated nitric acid chemical stripping tungsten paper tinsel and prepare WO3The side of nanometer sheet
Method, WO made from this method3Nanometer sheet thickness is only 1.4nm or so；Separately there is document (Sci.Rep.2013,3,1936) to report
A kind of chemical stripping wolframic acid prepares WO3The method of nanometer sheet, WO made from the method3Nanometer sheet thickness is also only 1.4nm or so.
Obtained by prior art is all with certain thickness multilayer WO3Nanometer sheet or hydration WO3Nanometer sheet, however, WO3
Nanometer sheet or hydration WO3Nanometer sheet thickness is smaller, and its pliability is more preferable, specific surface area is bigger, moreover, its band gap is wider, work content
Number is smaller, with more preferable electric conductivity.Therefore, how to reduce its thickness or to obtain individual layer nanometer sheet significant.
The content of the invention
In view of this, the invention provides a kind of individual layer hydration tungstic trioxide nano-slice and preparation method thereof, the present invention is carried
The hydration tungstic trioxide nano-slice of confession is individual layer nanometer sheet, and thickness is substantially reduced.
Tungstic trioxide nano-slice is hydrated the invention provides a kind of individual layer, the length of the nanometer sheet is 0.1~2 μm, wide
Spend for 0.1~2 μm, thickness is 0.5~0.7nm.
It is preferred that, the length-width ratio of the nanometer sheet is (1~20): 1.
It is preferred that, the hydration tungstic trioxide nano-slice is orthorhombic phase.
It is preferred that, the hydration tungstic trioxide nano-slice is two hydration tungstic trioxide nano-slices.
The invention provides the preparation method that the individual layer described in a kind of above-mentioned technical proposal is hydrated tungstic trioxide nano-slice, bag
Include following steps：
A) yellow wolframic acid is mixed with up-stripping agent, it is ultrasonically treated, obtain the first tungstate-base nonwoven fabric from filaments；
The up-stripping agent is selected from the organic polar solvent of carbon chain lengths≤4；
B) the first tungstate-base nonwoven fabric from filaments is mixed with main remover, heating response, obtain the second tungstate-base nonwoven fabric from filaments；
The main remover is selected from the organic amine that carbon chain lengths are 10~18；
C) the second tungstate-base nonwoven fabric from filaments is mixed with nitric acid liquid, filtered, obtain individual layer hydration tungstic trioxide nano-slice.
It is preferred that, in the step a), up-stripping agent is selected from methanol, ethanol, ether, butyraldehyde, formic acid, butyric acid and acetone
In one or more.
It is preferred that, in the step a), the mol ratio of the yellow wolframic acid and up-stripping agent is 1: (5~30).
It is preferred that, in the step b), main remover in ten amine, lauryl amine, tetradecy lamine, cetylamine and oleyl amine one
Plant or several.
It is preferred that, the mol ratio of the yellow wolframic acid and main remover is 1: (10~75).
It is preferred that, in the step b), the temperature of the heating response is 120~220 DEG C；
After the heating response, in addition to precipitating reagent will be added into gained reaction solution and be precipitated, filtered, and obtain the
Two tungstate-base nonwoven fabric from filaments；
In the step c), the mass ratio of the second tungstate-base nonwoven fabric from filaments and nitric acid liquid is 1: (25~75)；
The concentration of the nitric acid liquid is 2~8mol/L.
Tungstic trioxide nano-slice is hydrated the invention provides a kind of individual layer, hydration tungstic trioxide nano-slice thickness is provided big
Big reduction, is individual layer nanometer sheet, and better crystallinity degree, and pattern is uniform.Tungsten trioxide nano is hydrated present invention also offers the individual layer
The preparation method of piece, its preparation process is simple and easy to apply, low for equipment requirements, is easy to large-scale production.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the X-ray diffractogram of the products therefrom of embodiment 1；
Fig. 2 is the transmission electron microscope of the products therefrom of embodiment 1；Wherein, Fig. 2 a and Fig. 2 b are the transmission electron microscope under different multiples
Figure；
Fig. 3 characterizes analysis diagram for the atomic force microscopy of the products therefrom of embodiment 1；Wherein, Fig. 3 a characterize for atomic force microscopy
Figure, Fig. 3 b are the pattern analysis diagram at difference in Fig. 3 a；
Fig. 4 is the uv-visible absorption spectroscopy figure of the products therefrom of embodiment 1；
Fig. 5 is the Raman spectrogram of the products therefrom of embodiment 1.
Embodiment
Tungstic trioxide nano-slice is hydrated the invention provides a kind of individual layer, the length of the nanometer sheet is 0.1~2 μm, wide
Spend for 0.1~2 μm, thickness is 0.5~0.7nm.
In the present invention, the length-width ratio of the nanometer sheet is preferably (1~20): 1.
In the present invention, the hydration tungstic trioxide nano-slice is preferably orthorhombic phase.
In the present invention, the hydration tungstic trioxide nano-slice is preferably two hydration tungstic trioxide nano-slices.In some implementations
In example, the hydration tungstic trioxide nano-slice apparent colour is in yellow, and the corresponding X-ray diffraction standard card of its crystal formation is
JCPDS#18-1420。
Present invention also offers the preparation method that above-mentioned individual layer is hydrated tungstic trioxide nano-slice, comprise the following steps：
A) yellow wolframic acid is mixed with up-stripping agent, it is ultrasonically treated, obtain the first tungstate-base nonwoven fabric from filaments；
The up-stripping agent is selected from the organic polar solvent of carbon chain lengths≤4；
B) the first tungstate-base nonwoven fabric from filaments is mixed with main remover, heating response, obtain the second tungstate-base nonwoven fabric from filaments；
The main remover is selected from the organic amine that carbon chain lengths are 10~18；
C) the second tungstate-base nonwoven fabric from filaments is mixed with nitric acid liquid, filtered, obtain individual layer hydration tungstic trioxide nano-slice.
According to the present invention, yellow wolframic acid is mixed with up-stripping agent first, ultrasonically treated, obtain the first tungstate-base stratiform
Thing.
In the present invention, the source of the yellow wolframic acid is not particularly limited, and is general commercially available product, and its molecular formula is
WO3·H2O.In the present invention, the up-stripping agent is the organic polar solvent of carbon chain lengths≤4；Carbon chain lengths are long, it is difficult to
Intercalation is peeled off to form layer structure；In certain embodiments, specially methanol, ethanol, ether, butyraldehyde, formic acid, butyric acid and acetone
In one or more.In the present invention, yellow wolframic acid and the mol ratio of up-stripping agent are preferably 1: (5~30).Yellow wolframic acid with it is auxiliary
Help remover mix and carry out it is ultrasonically treated, the present invention in, the ultrasonically treated power is preferably 90~110W, in some realities
Apply in example is 100W.In the present invention, the ultrasonically treated time is preferably 5~60min.It is described it is ultrasonically treated after, obtain
First tungstate-base nonwoven fabric from filaments.
According to the present invention, after the first tungstate-base nonwoven fabric from filaments is obtained, by the first tungstate-base nonwoven fabric from filaments and main remover
Mixing, heating response, obtain the second tungstate-base nonwoven fabric from filaments.
In the present invention, the main remover is selected from the organic amine that carbon chain lengths are 10~18；Carbon chain lengths are long or too short,
It is difficult to obtain individual layer hydration tungstic trioxide nano-slice；In certain embodiments, specially ten amine, lauryl amine, tetradecy lamine, 16
One or more in amine and oleyl amine.In the present invention, when the first tungstate-base nonwoven fabric from filaments is mixed with main remover, the mol ratio of the two
Preferably 1: (10~75).After mixing, carrying out in heating response, the present invention, the temperature of the heating response is preferably 120~
220℃；The time of the heating response is preferably 5~24h, is reacted using solvent-thermal method, forms the second tungstate-base stratiform
Thing.
In the present invention, after the heating response, preferably also include the addition precipitating reagent into gained reaction solution and precipitated,
Filtering, obtains the second tungstate-base nonwoven fabric from filaments.In the present invention, the species of the precipitating reagent is not particularly limited, and can fully be dissolved
One or more in the main remover, preferably methanol, ethanol, ether, butyraldehyde, formic acid, butyric acid and acetone；It is more excellent
Elect acetone as.The consumption of the precipitating reagent is not particularly limited, and reactant can be precipitated by introducing enough precipitating reagents.
After the precipitation, filtered, obtain the second tungstate-base nonwoven fabric from filaments.
According to the present invention, after the second tungstate-base nonwoven fabric from filaments is obtained, the second tungstate-base nonwoven fabric from filaments is mixed with nitric acid liquid, mistake
Filter, obtains individual layer hydration tungstic trioxide nano-slice.
In the present invention, the concentration of the nitric acid liquid is preferably 2~8mol/L；The second tungstate-base nonwoven fabric from filaments and nitric acid liquid
Mass ratio be preferably 1: (25~75).After salpeter solution is mixed with the second tungstate-base nonwoven fabric from filaments, by the second tungstate-base nonwoven fabric from filaments
In main remover and up-stripping agent oxidation removal, obtain mixed liquor；Filtered afterwards, by the sediment mistake in mixed liquor
Filter out and；In the present invention, after the filtering, preferably also it is dried, after the drying, obtains individual layer hydration tungstic acid
Nanometer sheet.The feature of gained individual layer hydration tungstic trioxide nano-slice is consistent with above-mentioned technical proposal, will not be repeated here.
The invention provides the preparation method that a kind of individual layer is hydrated tungstic trioxide nano-slice, by yellow wolframic acid and specific auxiliary
Remover is mixed, and up-stripping agent functions simultaneously as solvent and remover, is mixed again with specific main remover afterwards, makes master
Stripping is easier to insert and struts yellow wolframic acid layer structure, under the successively cooperation of specific release effect, realizes individual layer hydration
The preparation of tungstic trioxide nano-slice.The preparation method that the present invention is provided not only successfully prepares individual layer hydration tungstic trioxide nano-slice,
And its preparation process is simple and easy to apply, cost is low, is convenient for large-scale production.
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
The preparation of 1.1 samples
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 0.5mL methanol (12mmol) and under 100W after ultrasonically treated 5min,
Add 10mL tetradecy lamines (38mmol), the solvent thermal reaction 24h at 120 DEG C, backward gained mixed liquor in add enough acetone,
Formed and precipitate and filter；Gained white precipitate is mixed with 50mL concentration for 4mol/L nitric acid liquid, mistake after magnetic agitation 36h
Filter, the yellow mercury oxide that will filter out is dried, and obtains the hydration tungstic trioxide nano-slice of individual layer two.
The sign of 1.2 samples
(1) X-ray diffraction test is carried out to products therefrom, as a result as shown in Figure 1；The powder x-ray diffraction of products therefrom
Collection of illustrative plates correspondence standard card JCPDS#18-1420, it is the water tungstic acid of orthorhombic phase two, (010) high preferred orientation with height,
Crystallinity is high.
(2) transmissioning electric mirror test is carried out to products therefrom, as a result (wherein, Fig. 2 a and Fig. 2 b are different multiples as shown in Figure 2
Under transmission electron microscope picture)；As can be seen that products therefrom is high, the transparent single sheet structure of crystallinity, its area is (0.1~2)
μ m (0.1~2) μm, length-width ratio is (1~20): 1.
(3) atomic force microscopy characterization test is carried out to products therefrom, as a result (wherein, Fig. 3 a are aobvious for atomic force as shown in Figure 3
Micro- phenogram, Fig. 3 b are the pattern analysis diagram at difference in Fig. 3 a)；As can be seen that the thickness of nanometer sheet is 0.5~0.7nm,
Average thickness isThat is 0.6nm.(data are by standard by the theoretical interplanar distance d=0.695nm of (010) crystal face of 2 θ=12.7 °
Card JCPDS#18-1420 can be obtained), and the thickness of present invention gained hydration tungstic trioxide nano-slice is even slightly less than theoretical value,
Further prove that it is hydrated tungstic trioxide nano-slice for individual layer.
(4) uv-visible absorption spectra test and Raman spectrum is carried out to products therefrom to test, as a result respectively such as Fig. 4 and
(Fig. 4 is the uv-visible absorption spectroscopy figure that individual layer is hydrated tungstic trioxide nano-slice shown in Fig. 5；Fig. 5 is that individual layer is hydrated three oxygen
Change the Raman spectrogram of tungsten nanometer sheet)；As seen from Figure 4, products therefrom can absorb below 520nm visible ray.Can by Fig. 5
To find out, 275cm-1And 315cm-1The peak at place belongs to O-W-O flexural vibrations, 720cm-1And 810cm-1The peak at place belongs to O-W-O and stretched
Contracting vibration；Different from traditional WO3Nano material, individual layer produced by the present invention be hydrated tungstic trioxide nano-slice at 950 for no reason key-
W=O, illustrates that the W in gained individual layer hydration tungstic trioxide nano-slice of the invention is connected with O with singly-bound.
Embodiment 2
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 6mL ether (58mmol) and under 100W after ultrasonically treated 60min,
Add the amine of 20mL ten (100mmol), the solvent thermal reaction 12h at 140 DEG C, backward gained mixed liquor in add enough acetone,
Formed and precipitate and filter；Gained white precipitate is mixed with 75mL concentration for 2mol/L nitric acid liquid, mistake after magnetic agitation 72h
Filter, the yellow mercury oxide that will filter out is dried, and obtains the hydration tungstic trioxide nano-slice of individual layer two.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, the X-ray of products therefrom
Diffracting spectrum correspondence standard card JCPDS#18-1420, it is the hydration tungstic trioxide nano-slice of individual layer two of orthorhombic phase, its area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, the thickness of nanometer sheet is 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 3
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 3mL butyraldehyde (33mmol) and under 100W after ultrasonically treated 45min,
Add 45mL cetylamines (150mmol), the solvent thermal reaction 5h at 220 DEG C, backward gained mixed liquor in add enough acetone,
Formed and precipitate and filter；Gained white precipitate is mixed with 75mL concentration for 8mol/L nitric acid liquid, mistake after magnetic agitation 24h
Filter, the yellow mercury oxide that will filter out is dried, and obtains the hydration tungstic trioxide nano-slice of individual layer two.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, the X-ray of products therefrom
Diffracting spectrum correspondence standard card JCPDS#18-1420, it is the hydration tungstic trioxide nano-slice of individual layer two of orthorhombic phase, its area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, the thickness of nanometer sheet is 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 4
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 2mL formic acid (53mmol) and under 100W after ultrasonically treated 30min,
Add 30mL oleyl amines (93mmol), the solvent thermal reaction 10h at 160 DEG C, backward gained mixed liquor in add enough acetone, shape
Into precipitating and filter；Gained white precipitate is mixed with 50mL concentration for 5mol/L nitric acid liquid, filtered after magnetic agitation 36h,
The yellow mercury oxide that will filter out is dried, and obtains the hydration tungstic trioxide nano-slice of individual layer two.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, the X-ray of products therefrom
Diffracting spectrum correspondence standard card JCPDS#18-1420, it is the hydration tungstic trioxide nano-slice of individual layer two of orthorhombic phase, its area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, the thickness of nanometer sheet is 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 5
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 5mL butyric acid (54mmol) and under 100W after ultrasonically treated 45min,
Add 25mL lauryl amines (108mmol), the solvent thermal reaction 8h at 180 DEG C, backward gained mixed liquor in add enough acetone,
Formed and precipitate and filter；Gained white precipitate is mixed with 30mL concentration for 6mol/L nitric acid liquid, mistake after magnetic agitation 48h
Filter, the yellow mercury oxide that will filter out is dried, and obtains the hydration tungstic trioxide nano-slice of individual layer two.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, the X-ray of products therefrom
Diffracting spectrum correspondence standard card JCPDS#18-1420, it is the hydration tungstic trioxide nano-slice of individual layer two of orthorhombic phase, its area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, the thickness of nanometer sheet is 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 6
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 4mL acetone (54mmol) and under 100W after ultrasonically treated 60min,
Add 40mL oleyl amines (124mmol), the solvent thermal reaction 6h at 140 DEG C, backward gained mixed liquor in add enough acetone, shape
Into precipitating and filter；Gained white precipitate is mixed with 75mL concentration for 3mol/L nitric acid liquid, filtered after magnetic agitation 48h,
The yellow mercury oxide that will filter out is dried, and obtains the hydration tungstic trioxide nano-slice of individual layer two.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, the X-ray of products therefrom
Diffracting spectrum correspondence standard card JCPDS#18-1420, it is the hydration tungstic trioxide nano-slice of individual layer two of orthorhombic phase, its area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, the thickness of nanometer sheet is 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 7
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 3mL ethanol (53mmol) and under 100W after ultrasonically treated 60min,
Add 25mL oleyl amines (78mmol), the solvent thermal reaction 10h at 150 DEG C, backward gained mixed liquor in add enough acetone, shape
Into precipitating and filter；Gained white precipitate is mixed with 50mL concentration for 4mol/L nitric acid liquid, filtered after magnetic agitation 72h,
The yellow mercury oxide that will filter out is dried, and obtains the hydration tungstic trioxide nano-slice of individual layer two.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, the X-ray of products therefrom
Diffracting spectrum correspondence standard card JCPDS#18-1420, it is the hydration tungstic trioxide nano-slice of individual layer two of orthorhombic phase, its area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, the thickness of nanometer sheet is 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 8
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 2mL methanol (48mmol) and under 100W after ultrasonically treated 60min,
Add 20mL oleyl amines (62mmol), the solvent thermal reaction 10h at 150 DEG C, backward gained mixed liquor in add enough acetone, shape
Into precipitating and filter；Gained white precipitate is mixed with 50mL concentration for 6mol/L nitric acid liquid, filtered after magnetic agitation 72h,
The yellow mercury oxide that will filter out is dried, and obtains the hydration tungstic trioxide nano-slice of individual layer two.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, the X-ray of products therefrom
Diffracting spectrum correspondence standard card JCPDS#18-1420, it is the hydration tungstic trioxide nano-slice of individual layer two of orthorhombic phase, its area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, the thickness of nanometer sheet is 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Comparative example 1
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 3mL octanols (19mmol) and under 100W after ultrasonically treated 5min, plus
Enter 10mL tetradecy lamines (38mmol), the solvent thermal reaction 24h at 120 DEG C, backward gained mixed liquor in add enough acetone, shape
Into precipitating and filter；Gained is precipitated and mixed with 50mL concentration for 4mol/L nitric acid liquid, filters and does after magnetic agitation 36h
It is dry, obtain product.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, products therefrom is still yellow tungsten
Acid.
Comparative example 2
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 0.5mL methanol (12mmol) and under 100W after ultrasonically treated 5min,
Add 15mL hexylamines (114mmol), the solvent thermal reaction 24h at 120 DEG C, backward gained mixed liquor in add enough acetone,
Formed and precipitate and filter；Gained is precipitated and mixed with 50mL concentration for 4mol/L nitric acid liquid, filters and does after magnetic agitation 36h
It is dry, obtain product.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result show, products therefrom is orthorhombic phase
Two hydration tungstic acids, nanometer sheet thickness is 2.8nm.
Comparative example 3
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 0.5mL methanol (12mmol) and under 100W after ultrasonically treated 5min,
Add the double cetylamines (71mmol) of 40mL, the solvent thermal reaction 24h at 120 DEG C, backward gained mixed liquor in add enough third
Ketone, forms and precipitates and filter；Gained is precipitated and mixed with 50mL concentration for 4mol/L nitric acid liquid, is filtered after magnetic agitation 36h
And dry, obtain product.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result show, products therefrom is orthorhombic phase
Two hydration tungstic acids, nanometer sheet thickness is 5.6nm.
Comparative example 4
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 5mL octanols (32mmol) and under 100W after ultrasonically treated 5min, plus
Enter 30mL hexylamines (53mmol), the solvent thermal reaction 24h at 120 DEG C, backward gained mixed liquor in add enough acetone, formed
Precipitate and filter；Gained is precipitated and mixed with 50mL concentration for 4mol/L nitric acid liquid, filters and dries after magnetic agitation 36h,
Obtain product.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, products therefrom is still yellow tungsten
Acid.
Comparative example 5
The yellow wolframic acids (about 2mmol) of 0.5g are mixed with 5mL octanols (32mmol) and under 100W after ultrasonically treated 5min, plus
Enter the double cetylamines (36mmol) of 20mL, the solvent thermal reaction 24h at 120 DEG C, backward gained mixed liquor in add enough acetone,
Formed and precipitate and filter；Gained is precipitated and mixed with 50mL concentration for 4mol/L nitric acid liquid, filters and does after magnetic agitation 36h
It is dry, obtain product.
Products therefrom is detected according to the characterization test method of embodiment 1, as a result shown, products therefrom is still yellow tungsten
Acid.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.To these embodiments
A variety of modifications will be apparent for those skilled in the art, generic principles defined herein can be with
Without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to the most wide model consistent with features of novelty with principles disclosed herein
Enclose.
Claims (10)
1. a kind of individual layer is hydrated tungstic trioxide nano-slice, it is characterised in that the length of the nanometer sheet is 0.1~2 μm, width is
0.1~2 μm, thickness is 0.5~0.7nm.
2. nanometer sheet according to claim 1, it is characterised in that the length-width ratio of the nanometer sheet is (1~20): 1.
3. nanometer sheet according to claim 1, it is characterised in that the hydration tungstic trioxide nano-slice is orthorhombic phase.
4. according to nanometer sheet according to any one of claims 1 to 3, it is characterised in that the hydration tungstic trioxide nano-slice
For two hydration tungstic trioxide nano-slices.
5. a kind of individual layer according to any one of claims 1 to 4 is hydrated the preparation method of tungstic trioxide nano-slice, its feature exists
In comprising the following steps：
A) yellow wolframic acid is mixed with up-stripping agent, it is ultrasonically treated, obtain the first tungstate-base nonwoven fabric from filaments；
The up-stripping agent is selected from the organic polar solvent of carbon chain lengths≤4；
B) the first tungstate-base nonwoven fabric from filaments is mixed with main remover, heating response, obtain the second tungstate-base nonwoven fabric from filaments；
The main remover is selected from the organic amine that carbon chain lengths are 10~18；
C) the second tungstate-base nonwoven fabric from filaments is mixed with nitric acid liquid, filtered, obtain individual layer hydration tungstic trioxide nano-slice.
6. preparation method according to claim 5, it is characterised in that in the step a), up-stripping agent be selected from methanol,
One or more in ethanol, ether, butyraldehyde, formic acid, butyric acid and acetone.
7. the preparation method according to claim 5 or 6, it is characterised in that in the step a), the yellow wolframic acid and auxiliary
The mol ratio of remover is 1: (5~30).
8. preparation method according to claim 5, it is characterised in that in the step b), main remover is selected from ten amine, ten
One or more in diamines, tetradecy lamine, cetylamine and oleyl amine.
9. the preparation method according to claim 5 or 8, it is characterised in that the mol ratio of the yellow wolframic acid and main remover
For 1: (10~75).
10. preparation method according to claim 5, it is characterised in that in the step b), the temperature of the heating response
For 120~220 DEG C；
After the heating response, in addition to precipitating reagent will be added into gained reaction solution and be precipitated, and filtered, obtain the second tungsten
Acidic group nonwoven fabric from filaments；
In the step c), the mass ratio of the second tungstate-base nonwoven fabric from filaments and nitric acid liquid is 1: (25~75)；
The concentration of the nitric acid liquid is 2~8mol/L.
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