CN107324391B - A kind of single layer hydration tungstic trioxide nano-slice and preparation method thereof - Google Patents
A kind of single layer hydration tungstic trioxide nano-slice and preparation method thereof Download PDFInfo
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- CN107324391B CN107324391B CN201710702469.3A CN201710702469A CN107324391B CN 107324391 B CN107324391 B CN 107324391B CN 201710702469 A CN201710702469 A CN 201710702469A CN 107324391 B CN107324391 B CN 107324391B
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Abstract
The present invention provides a kind of single layers to be hydrated tungstic trioxide nano-slice, provides hydration tungstic trioxide nano-slice thickness and substantially reduces, is individual layer nanometer sheet, and better crystallinity degree, pattern are uniform.The present invention also provides the preparation methods of single layer hydration tungstic trioxide nano-slice, and preparation process is simple and easy, low for equipment requirements, are convenient for large-scale production.
Description
Technical field
The present invention relates to technical field of nano material, in particular to a kind of single layer hydration tungstic trioxide nano-slice and its preparation
Method.
Background technique
Tungstic acid (WO3) it is a kind of N-shaped wide bandgap semiconductor oxide, the WO of ordered nano-structure3Or hydration WO3Tool
There are the characteristics such as quantum effect, skin effect specific to nano material, has in fields such as gas sensing, photocatalysis, energy storage devices
Wide application prospect.It is well known that the performance of semiconductor material and application have very big association with its microstructure and pattern,
In, the two-dimensional nano WO with high specific surface area3Or hydration WO3With unique photoelectric characteristic, more and more closed
Note.
Currently, the tungstic acid of two-dimensional nanostructure or the preparation method of hydration tungstic acid are 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. is
It is (100~800) nm × (100~800) nm that 200710054544.6 Chinese patent application, which discloses a kind of area, apparent thick
Degree is the WO of 5~40nm3Nanometer sheet and preparation method thereof；Application No. is 2012103776091 Chinese patent applications to disclose
It is a kind of to prepare WO using thermal oxidation method3The method of nanometer sheet, WO made from the method3Nanometer sheet with a thickness of 0.2~2 μm；There is document
(Chem.Mater.2010,22,5660-5666) a kind of concentrated nitric acid chemical stripping tungsten foil preparation WO is reported3The 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 preparation WO3The method of nanometer sheet, WO made from the method3Nanometer sheet thickness is also only 1.4nm or so.
The resulting prior art is all to have certain thickness multilayer WO3Nanometer sheet or hydration WO3Nanometer sheet, however, WO3
Nanometer sheet or hydration WO3Nanometer sheet thickness is smaller, and flexibility is more preferable, specific surface area is bigger, moreover, its band gap is wider, work content
Number is smaller, has better electric conductivity.Therefore, how to reduce its thickness or obtain individual layer nanometer sheet and be of great significance.
Summary of the invention
In view of this, the present invention mentions the present invention provides a kind of single layer hydration tungstic trioxide nano-slice and preparation method thereof
The hydration tungstic trioxide nano-slice of confession is individual layer nanometer sheet, and thickness substantially reduces.
The present invention provides a kind of single layers to be hydrated tungstic trioxide nano-slice, and the length of the nanometer sheet is 0.1~2 μm, wide
Degree is 0.1~2 μm, with a thickness of 0.5~0.7nm.
Preferably, the length-width ratio of the nanometer sheet is (1~20): 1.
Preferably, the hydration tungstic trioxide nano-slice is orthorhombic phase.
Preferably, the hydration tungstic trioxide nano-slice is two hydration tungstic trioxide nano-slices.
The present invention provides a kind of preparation method of the hydration tungstic trioxide nano-slice of single layer described in above-mentioned technical proposal, packets
Include following steps:
A) yellow wolframic acid mixed with up-stripping agent, be 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 mixed with main remover, heat and reacts, 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 mixed with nitric acid liquid, filtered, obtain single layer hydration tungstic trioxide nano-slice.
Preferably, in the step a), up-stripping agent is selected from methanol, ethyl alcohol, ether, butyraldehyde, formic acid, butyric acid and acetone
One or more of.
Preferably, in the step a), the molar ratio of the Huang wolframic acid and up-stripping agent is 1: (5~30).
Preferably, in the step b), main remover in ten amine, lauryl amine, tetradecy lamine, cetylamine and oleyl amine one
Kind is several.
Preferably, the molar ratio of the yellow wolframic acid and main remover is 1: (10~75).
Preferably, in the step b), the temperature of the heating reaction is 120~220 DEG C；
After heating reaction, further includes that precipitating reagent will be added into gained reaction solution precipitate, filter, 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.
The present invention provides a kind of single layers to be hydrated tungstic trioxide nano-slice, and it is big to provide hydration tungstic trioxide nano-slice thickness
It is big to reduce, it is individual layer nanometer sheet, and better crystallinity degree, pattern are uniform.The present invention also provides the single layers to be hydrated tungsten trioxide nano
The preparation method of piece, preparation process is simple and easy, low for equipment requirements, is convenient for large-scale production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the X-ray diffractogram of 1 products therefrom of embodiment；
Fig. 2 is the transmission electron microscope of 1 products therefrom of embodiment；Wherein, Fig. 2 a and Fig. 2 b is the transmission electron microscope under different multiples
Figure；
Fig. 3 is that the atomic force microscopy of 1 products therefrom of embodiment characterizes analysis diagram；Wherein, Fig. 3 a is atomic force microscopy characterization
Figure, Fig. 3 b are the pattern analysis diagram in Fig. 3 a at difference；
Fig. 4 is the uv-visible absorption spectroscopy figure of 1 products therefrom of embodiment；
Fig. 5 is the Raman spectrogram of 1 products therefrom of embodiment.
Specific embodiment
The present invention provides a kind of single layers to be hydrated tungstic trioxide nano-slice, and the length of the nanometer sheet is 0.1~2 μm, wide
Degree is 0.1~2 μm, with a thickness of 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 crystal form is
JCPDS#18-1420。
The present invention also provides the preparation methods of above-mentioned single layer hydration tungstic trioxide nano-slice, comprising the following steps:
A) yellow wolframic acid mixed with up-stripping agent, be 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 mixed with main remover, heat and reacts, 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 mixed with nitric acid liquid, filtered, obtain single layer hydration tungstic trioxide nano-slice.
According to the present invention, yellow wolframic acid is mixed with up-stripping agent first, is ultrasonically treated, obtains the first tungstate-base stratiform
Object.
In the present invention, it is general commercially available product, molecular formula is that the source of the Huang wolframic acid, which is not particularly limited,
WO3·H2O.In the present invention, the up-stripping agent is the organic polar solvent of carbon chain lengths≤4；Carbon chain lengths are too long, it is difficult to
Intercalation stripping forms layer structure；In some embodiments, specially methanol, ethyl alcohol, ether, butyraldehyde, formic acid, butyric acid and acetone
One or more of.In the present invention, the molar ratio of yellow wolframic acid and up-stripping agent is preferably 1: (5~30).Yellow wolframic acid with it is auxiliary
Remover is helped to mix and be ultrasonically treated, in the present invention, the power of the ultrasonic treatment is preferably 90~110W, in some realities
It applies in example as 100W.In the present invention, the time of the ultrasonic treatment is preferably 5~60min.After the ultrasonic treatment, obtain
First tungstate-base nonwoven fabric from filaments.
According to the present invention, after obtaining the first tungstate-base nonwoven fabric from filaments, by the first tungstate-base nonwoven fabric from filaments and main remover
Mixing, heating reaction, 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 too long or too short,
It is difficult to obtain single layer hydration tungstic trioxide nano-slice；In some embodiments, specially ten amine, lauryl amine, tetradecy lamine, 16
One or more of amine and oleyl amine.In the present invention, when the first tungstate-base nonwoven fabric from filaments is mixed with main remover, the molar ratio of the two
Preferably 1: (10~75).After mixing, heating reaction is carried out, in the present invention, the temperature of the heating reaction is preferably 120~
220℃；The time of the heating reaction is preferably 5~for 24 hours, it is reacted using solvent-thermal method, forms the second tungstate-base stratiform
Object.
In the present invention, the heating reaction after, it is also preferable to include into gained reaction solution be added precipitating reagent precipitated,
Filtering, obtains the second tungstate-base nonwoven fabric from filaments.In the present invention, the type of the precipitating reagent is not particularly limited, and can sufficiently be dissolved
The main remover, preferably one or more of methanol, ethyl alcohol, ether, butyraldehyde, formic acid, butyric acid and acetone；It is more excellent
It is selected as acetone.The dosage of the precipitating reagent is not particularly limited, and reactant can be precipitated by introducing enough precipitating reagents.?
It after the precipitating, is filtered, obtains the second tungstate-base nonwoven fabric from filaments.
According to the present invention, after obtaining the second tungstate-base nonwoven fabric from filaments, the second tungstate-base nonwoven fabric from filaments is mixed with nitric acid liquid, mistake
Filter obtains single 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 nitric acid 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；It is filtered later, by the sediment mistake in mixed liquor
It filters out and；It in the present invention, after the filtering, is preferably also dried, after the drying, obtains single layer hydration tungstic acid
Nanometer sheet.The feature that gained single layer is hydrated tungstic trioxide nano-slice is consistent with above-mentioned technical proposal, and details are not described herein.
The present invention provides a kind of preparation methods of single layer hydration tungstic trioxide nano-slice, by yellow wolframic acid and specific auxiliary
Remover mixing, up-stripping agent function simultaneously as solvent and remover, are mixed again with specific main remover later, make to lead
Removing is easier to be inserted into and strut yellow wolframic acid layer structure, under the cooperation of successive specific release effect, realizes single layer hydration
The preparation of tungstic trioxide nano-slice.Preparation method provided by the invention not only successfully prepares single layer hydration tungstic trioxide nano-slice,
And its preparation process is simple and easy, at low cost, is convenient for large-scale production.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation 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
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 0.5mL methanol (12mmol) and is ultrasonically treated 5min at 100W,
Be added 10mL tetradecy lamine (38mmol), at 120 DEG C solvent thermal reaction for 24 hours, it is backward obtained by enough acetone is added in mixed liquor,
It is formed and precipitates and filter；Gained white precipitate is mixed with the nitric acid liquid that 50mL concentration is 4mol/L, mistake after magnetic agitation 36h
Filter, the yellow mercury oxide that will filter out is dry, obtains single layer two and is hydrated tungstic trioxide nano-slice.
The characterization 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
Map corresponds to standard card JCPDS#18-1420, is two water tungstic acid of orthorhombic phase, has (010) high preferred orientation of 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 is different multiples as shown in Figure 2
Under transmission electron microscope picture)；As can be seen that products therefrom is crystallinity height, transparent single sheet structure, area is (0.1~2)
μ m (0.1~2) μm, length-width ratio are (1~20): 1.
(3) atomic force microscopy characterization test is carried out to products therefrom, as a result (wherein, Fig. 3 a is aobvious for atomic force as shown in Figure 3
Micro- phenogram, Fig. 3 b are the pattern analysis diagram in Fig. 3 a at difference)；As can be seen that nanometer sheet with a thickness of 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 single 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 single layer is hydrated tungstic trioxide nano-slice shown in Fig. 5；Fig. 5 is that single layer is hydrated three oxygen
Change the Raman spectrogram of tungsten nanometer sheet)；As seen from Figure 4, products therefrom can absorb 520nm visible light below.It can by Fig. 5
To find out, 275cm-1And 315cm-1The peak at place belongs to O-W-O bending vibration, 720cm-1And 810cm-1The peak at place belongs to O-W-O and stretches
Contracting vibration；Different from traditional WO3Nano material, single layer produced by the present invention hydration tungstic trioxide nano-slice key-for no reason at 950
W=O illustrates that the W in the hydration tungstic trioxide nano-slice of single layer obtained by the present invention is connect with O with singly-bound.
Embodiment 2
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 6mL ether (58mmol) and is ultrasonically treated 60min at 100W,
Be added ten amine of 20mL (100mmol), the solvent thermal reaction 12h at 140 DEG C, it is backward obtained by enough acetone is added in mixed liquor,
It is formed and precipitates and filter；Gained white precipitate is mixed with the nitric acid liquid that 75mL concentration is 2mol/L, mistake after magnetic agitation 72h
Filter, the yellow mercury oxide that will filter out is dry, obtains single layer two and is hydrated tungstic trioxide nano-slice.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that the X-ray of products therefrom
Diffracting spectrum corresponds to standard card JCPDS#18-1420, is that the single layer two of orthorhombic phase is hydrated tungstic trioxide nano-slice, area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, nanometer sheet with a thickness of 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 3
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 3mL butyraldehyde (33mmol) and is ultrasonically treated 45min at 100W,
Be added 45mL cetylamine (150mmol), the solvent thermal reaction 5h at 220 DEG C, it is backward obtained by enough acetone is added in mixed liquor,
It is formed and precipitates and filter；The nitric acid liquid that gained white precipitate and 75mL concentration are 8mol/L is mixed, magnetic agitation mistake afterwards for 24 hours
Filter, the yellow mercury oxide that will filter out is dry, obtains single layer two and is hydrated tungstic trioxide nano-slice.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that the X-ray of products therefrom
Diffracting spectrum corresponds to standard card JCPDS#18-1420, is that the single layer two of orthorhombic phase is hydrated tungstic trioxide nano-slice, area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, nanometer sheet with a thickness of 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 4
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 2mL formic acid (53mmol) and is ultrasonically treated 30min at 100W,
Be added 30mL oleyl amine (93mmol), the solvent thermal reaction 10h at 160 DEG C, it is backward obtained by enough acetone, shape is added in mixed liquor
At precipitating and filter；Gained white precipitate is mixed with the nitric acid liquid that 50mL concentration is 5mol/L, is filtered after magnetic agitation 36h,
The yellow mercury oxide that will filter out is dry, obtains single layer two and is hydrated tungstic trioxide nano-slice.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that the X-ray of products therefrom
Diffracting spectrum corresponds to standard card JCPDS#18-1420, is that the single layer two of orthorhombic phase is hydrated tungstic trioxide nano-slice, area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, nanometer sheet with a thickness of 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 5
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 5mL butyric acid (54mmol) and is ultrasonically treated 45min at 100W,
Be added 25mL lauryl amine (108mmol), the solvent thermal reaction 8h at 180 DEG C, it is backward obtained by enough acetone is added in mixed liquor,
It is formed and precipitates and filter；Gained white precipitate is mixed with the nitric acid liquid that 30mL concentration is 6mol/L, mistake after magnetic agitation 48h
Filter, the yellow mercury oxide that will filter out is dry, obtains single layer two and is hydrated tungstic trioxide nano-slice.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that the X-ray of products therefrom
Diffracting spectrum corresponds to standard card JCPDS#18-1420, is that the single layer two of orthorhombic phase is hydrated tungstic trioxide nano-slice, area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, nanometer sheet with a thickness of 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 6
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 4mL acetone (54mmol) and is ultrasonically treated 60min at 100W,
Be added 40mL oleyl amine (124mmol), the solvent thermal reaction 6h at 140 DEG C, it is backward obtained by enough acetone, shape is added in mixed liquor
At precipitating and filter；Gained white precipitate is mixed with the nitric acid liquid that 75mL concentration is 3mol/L, is filtered after magnetic agitation 48h,
The yellow mercury oxide that will filter out is dry, obtains single layer two and is hydrated tungstic trioxide nano-slice.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that the X-ray of products therefrom
Diffracting spectrum corresponds to standard card JCPDS#18-1420, is that the single layer two of orthorhombic phase is hydrated tungstic trioxide nano-slice, area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, nanometer sheet with a thickness of 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 7
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 3mL ethyl alcohol (53mmol) and is ultrasonically treated 60min at 100W,
Be added 25mL oleyl amine (78mmol), the solvent thermal reaction 10h at 150 DEG C, it is backward obtained by enough acetone, shape is added in mixed liquor
At precipitating and filter；Gained white precipitate is mixed with the nitric acid liquid that 50mL concentration is 4mol/L, is filtered after magnetic agitation 72h,
The yellow mercury oxide that will filter out is dry, obtains single layer two and is hydrated tungstic trioxide nano-slice.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that the X-ray of products therefrom
Diffracting spectrum corresponds to standard card JCPDS#18-1420, is that the single layer two of orthorhombic phase is hydrated tungstic trioxide nano-slice, area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, nanometer sheet with a thickness of 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Embodiment 8
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 2mL methanol (48mmol) and is ultrasonically treated 60min at 100W,
Be added 20mL oleyl amine (62mmol), the solvent thermal reaction 10h at 150 DEG C, it is backward obtained by enough acetone, shape is added in mixed liquor
At precipitating and filter；Gained white precipitate is mixed with the nitric acid liquid that 50mL concentration is 6mol/L, is filtered after magnetic agitation 72h,
The yellow mercury oxide that will filter out is dry, obtains single layer two and is hydrated tungstic trioxide nano-slice.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that the X-ray of products therefrom
Diffracting spectrum corresponds to standard card JCPDS#18-1420, is that the single layer two of orthorhombic phase is hydrated tungstic trioxide nano-slice, area
For (0.1~2) μ m (0.1~2) μm, length-width ratio is (1~20): 1, nanometer sheet with a thickness of 0.5~0.7nm, average thickness
ForThat is 0.6nm.
Comparative example 1
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 3mL octanol (19mmol) and is ultrasonically treated 5min at 100W, add
Enter 10mL tetradecy lamine (38mmol), at 120 DEG C solvent thermal reaction for 24 hours, it is backward gained mixed liquor in enough acetone, shape is added
At precipitating and filter；Gained precipitating is mixed with the nitric acid liquid that 50mL concentration is 4mol/L, 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, the results show that products therefrom is still yellow tungsten
Acid.
Comparative example 2
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 0.5mL methanol (12mmol) and is ultrasonically treated 5min at 100W,
Be added 15mL hexylamine (114mmol), at 120 DEG C solvent thermal reaction for 24 hours, it is backward obtained by enough acetone is added in mixed liquor,
It is formed and precipitates and filter；Gained precipitating is mixed with the nitric acid liquid that 50mL concentration is 4mol/L, 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, the results show that products therefrom is orthorhombic phase
Two hydration tungstic acids, nanometer sheet thickness 2.8nm.
Comparative example 3
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 0.5mL methanol (12mmol) and is ultrasonically treated 5min at 100W,
Be added the bis- cetylamines of 40mL (71mmol), at 120 DEG C solvent thermal reaction for 24 hours, it is backward obtained by be added enough third in mixed liquor
Ketone forms and precipitates and filter；Gained precipitating is mixed with the nitric acid liquid that 50mL concentration is 4mol/L, is filtered after magnetic agitation 36h
And it is dry, obtain product.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that products therefrom is orthorhombic phase
Two hydration tungstic acids, nanometer sheet thickness 5.6nm.
Comparative example 4
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 5mL octanol (32mmol) and is ultrasonically treated 5min at 100W, add
Enter 30mL hexylamine (53mmol), at 120 DEG C solvent thermal reaction for 24 hours, it is backward gained mixed liquor in enough acetone is added, formed
It precipitates and filters；Gained precipitating is mixed with the nitric acid liquid that 50mL concentration is 4mol/L, is filtered after magnetic agitation 36h and dry,
Obtain product.
Products therefrom is detected according to the characterization test method of embodiment 1, the results show that products therefrom is still yellow tungsten
Acid.
Comparative example 5
After 0.5g Huang wolframic acid (about 2mmol) is mixed with 5mL octanol (32mmol) and is ultrasonically treated 5min at 100W, add
Enter the bis- cetylamines of 20mL (36mmol), at 120 DEG C solvent thermal reaction for 24 hours, it is backward gained mixed liquor in enough acetone is added,
It is formed and precipitates and filter；Gained precipitating is mixed with the nitric acid liquid that 50mL concentration is 4mol/L, 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, the results show that products therefrom is still yellow tungsten
Acid.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.To these embodiments
A variety of modifications will be readily apparent to those skilled in the art, the general principles defined herein can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to widest model consistent with the principles and novel features disclosed in this article
It encloses.
Claims (10)
1. a kind of single layer is hydrated tungstic trioxide nano-slice, which is characterized in that the length of the nanometer sheet is 0.1~2 μm, and width is
0.1~2 μm, with a thickness of 0.5~0.7nm；
The single layer hydration tungstic trioxide nano-slice is made by following preparation method:
A) yellow wolframic acid mixed with up-stripping agent, be 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 mixed with main remover, heat and reacts, 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 mixed with nitric acid liquid, filtered, obtain single layer hydration tungstic trioxide nano-slice.
2. nanometer sheet according to claim 1, which is characterized in that the length-width ratio of the nanometer sheet is (1~20): 1.
3. nanometer sheet according to claim 1, which is characterized in that the hydration tungstic trioxide nano-slice is orthorhombic phase.
4. nanometer sheet described in any one of claim 1 to 3, which is characterized in that the hydration tungstic trioxide nano-slice
For two hydration tungstic trioxide nano-slices.
5. a kind of preparation method of single layer hydration tungstic trioxide nano-slice according to any one of claims 1 to 4, feature exist
In, comprising the following steps:
A) yellow wolframic acid mixed with up-stripping agent, be 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 mixed with main remover, heat and reacts, 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 mixed with nitric acid liquid, filtered, obtain single layer hydration tungstic trioxide nano-slice.
6. preparation method according to claim 5, which is characterized in that in the step a), up-stripping agent be selected from methanol,
One or more of ethyl alcohol, ether, butyraldehyde, formic acid, butyric acid and acetone.
7. preparation method according to claim 5 or 6, which is characterized in that in the step a), the Huang wolframic acid and auxiliary
The molar ratio of remover is 1: (5~30).
8. preparation method according to claim 5, which is characterized in that in the step b), main remover is selected from ten amine, ten
One or more of diamines, tetradecy lamine, cetylamine and oleyl amine.
9. the preparation method according to claim 5 or 8, which is characterized in that the molar ratio of the Huang wolframic acid and main remover
It is 1: (10~75).
10. preparation method according to claim 5, which is characterized in that in the step b), the temperature of the heating reaction
It is 120~220 DEG C；
After heating reaction, further includes that precipitating reagent will be added into gained reaction solution to precipitate, filter, 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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