CN104071798A - Ultrathin montmorillonite nanosheet as well as preparation method and application thereof - Google Patents
Ultrathin montmorillonite nanosheet as well as preparation method and application thereof Download PDFInfo
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- CN104071798A CN104071798A CN201410315091.8A CN201410315091A CN104071798A CN 104071798 A CN104071798 A CN 104071798A CN 201410315091 A CN201410315091 A CN 201410315091A CN 104071798 A CN104071798 A CN 104071798A
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Abstract
The invention relates to an ultrathin montmorillonite nanosheet as well as a preparation method and application thereof. The preparation method comprises the following steps: 1) dispersing Na-montmorillonite in water so as to form a Na-montmorillonite first suspension liquid, and freezing the first suspension liquid at the temperature of minus 5 to minus 50 DEG C for 12-120 hours to obtain a Na-montmorillonite refrigerating fluid; 2) after unfreezing the Na-montmorillonite refrigerating fluid obtained in the step 1), carrying out ultrasonic treatment and centrifugalizing to remove Na-montmorillonite particles to obtain a Na-montmorillonite second suspension liquid; 3) freezing and drying the second suspension liquid prepared in the step 2) to obtain the ultrathin montmorillonite nanosheet.
Description
Technical field
The invention belongs to environment-friendly materials and photocatalysis technology field, be specifically related to a kind of ultra-thin montmorillonite-based nano sheet and its preparation method and application.
Background technology
Due to the environmental pollution day by day increasing the weight of, the research of Photocatalitic Technique of Semiconductor and application have caused people's extensive concern.Photocatalysis technology is the process of utilizing photocatalyst absorb light decomposing organic matter.Its mechanism is that semiconductor light-catalyst is subject to optical excitation to produce nonequilibrium carrier be light induced electron and hole, electronics and hole migration are after semiconductor surface, owing to thering is very strong oxidation and reducing power, can, with the organic pollutant generation redox reaction contacting with it, by organic substance decomposing, be that small molecules is also finally decomposed into CO
2and water.Because photochemical catalysis can utilize the luminous energy long term operation of occurring in nature, Shi Qi environmental pollution improvement field has broad application prospects.
Researching and developing new and effective visible light-responded property photocatalyst material, is the key of current photochemical catalysis environmental purification technology, is also that practical inexorable trend and developing direction further moved towards in photochemical catalysis.Bi
2wO
6photocatalyst is to study recently more a kind of novel semi-conductor visible light catalytic material, and band gap is about 2.74~2.90eV, and the threshold wave-length of its absorption is greater than 400nm, have active high, the advantages such as stability is strong, nontoxic and wide spectral response, become the visible light catalyst of at present tool potentiality.How further to improve Bi
2wO
6photocatalyst photocatalysis efficiency is to need at present the technical barrier of solution.
Summary of the invention
The present invention is intended to improve the performance of existing polynite aspect photochemical catalysis, the invention provides a kind of ultra-thin montmorillonite-based nano sheet and its preparation method and application.
The invention provides a kind of preparation method of ultra-thin montmorillonite-based nano sheet, described method comprises:
1) sodium-based montmorillonite is scattered in to sodium-based montmorillonite the first suspension forming in water, wherein the mass ratio of sodium-based montmorillonite and water is 1:(50-500), gained the first suspension obtains sodium-based montmorillonite refrigerating fulid for freezing 12~120 hours in-5~-50 ℃;
2) by step 1) after the sodium-based montmorillonite refrigerating fulid of gained thaws, carry out supersound process, centrifugal removal sodium-based montmorillonite particle, obtains sodium-based montmorillonite the second suspension;
3) by step 2) ultra-thin montmorillonite-based nano sheet described in described the second suspension obtained by freeze drying of preparing.
Preferably, step 1) in, by mass ratio, be (3-40): 1 polynite and soluble sodium salt are scattered in deionized water, at 40-100 ℃, stir 0.5-24 hour, through centrifugation, deionized water wash, obtains sodium-based montmorillonite after being dried, wherein the preferred sodium carbonate of soluble sodium salt, sodium-chlor and/or sodium bicarbonate.
Preferably, step 2) in, the time of supersound process is more than 1 minute.
Again, the ultra-thin montmorillonite-based nano sheet that the present invention also provides a kind of above-mentioned either method to prepare, in described ultra-thin montmorillonite-based nano sheet, the thickness of nanometer sheet is below 10nm, interlamellar spacing is 1-1.5nm.
And the present invention also provides a kind of method of preparing bismuth tungstate quantum dot intercalated montmorillonite matrix material, the preparation method of described matrix material comprises the preparation method of ultra-thin montmorillonite-based nano sheet claimed in claim 1; The preparation method of described matrix material also comprises:
A) soluble bismuth salt and sodium oleate are mixed in water, form emulsion form the first precursor liquid containing bismuth ion;
B) soluble tungstate salt and described ultra-thin montmorillonite-based nano sheet are scattered in water, dispersed formation is containing the second precursor liquid of tungstate ion and ultra-thin montmorillonite-based nano sheet;
C) by step a) in the first precursor liquid and the step b of preparation) in the second precursor liquid of preparation carry out Hydrothermal Synthesis after mixing, make described bismuth tungstate quantum dot intercalated montmorillonite matrix material.
Preferably, step a) in, soluble bismuth salt is Bismuth trinitrate and/or bismuth chloride.
Preferably, step a) in, in described the first precursor solution, the volumetric molar concentration of sodium oleate is 0.02-0.2mol/L, the volumetric molar concentration of bismuth ion is 0.01-0.04mol/L.
Preferably, described in mix by stirring and realize, the rotating speed of stirring is 100-1000rpm, churning time is more than 1 hour.
Preferably, step b) in, described soluble tungstate salt is sodium wolframate and/or ammonium tungstate.
Preferably, step b) in, in described the second precursor solution, the concentration of tungstate ion is 0.005-0.02mol/L, the content of polynite is 0.2-20g/L.
Preferably, step c) in, in the first precursor solution and step the second precursor solution mixing gained solution, the mol ratio of bismuth ion and tungstate ion is 2:1.
Preferably, step c) in, the processing parameter of Hydrothermal Synthesis is: the temperature of Hydrothermal Synthesis is 100-200 ℃, the time of Hydrothermal Synthesis is 2-72 hour.
Compared with prior art, the present invention has following beneficial effect:
1) the ultra-thin montmorillonite material even thickness being obtained by the inventive method is controlled at below 10nm, and interlamellar spacing increased 0.2nm left and right under the condition existing without any intercalator, becomes the good matrix material base material of preparing;
2) the ultra-thin montmorillonite composite material of the bismuth tungstate quantum dot intercalation being obtained by the inventive method, the bismuth tungstate quantum dot size between cheating engaging layer is in 1nm left and right.Due to the good light transmission of ultra-thin polynite, the efficiency of light energy utilization of interlayer quantum dot is not subject to the impact of intercalation configuration.And the existence of the negative charge between cheating engaging layer has promoted photohole in bismuth tungstate quantum dot to move to the probability on quantum dot surface.And the high photochemical catalytic oxidation ability of bismuth tungstate is mainly derived from the strong oxidation capacity of its photohole, therefore the bismuth tungstate quantum dot being positioned between cheating engaging layer shows the photocatalytic activity higher than simple quantum dot, and the life-span of its photo-generated carrier has been improved 6 times than simple bismuth tungstate quantum dot;
2) preparation method of the present invention is without specific installation and severe condition, and technique is simple, and controllability is strong, easily accomplishes scale production, and has practicality.
Accompanying drawing explanation
Fig. 1 is the contrast of the little angle XRD diffracting spectrum of the little angle of the ultra-thin polynite XRD diffracting spectrum that obtains in an embodiment of the invention and undressed bulk montmorillonite material;
Fig. 2 is the XRD diffracting spectrum of the ultra-thin montmorillonite composite material of bismuth tungstate quantum dot intercalation that obtains in an embodiment of the invention and the contrast of XRD diffracting spectrum after the ultra-thin polynite of intercalation is not processed under identical hydrothermal condition;
Fig. 3 is the transmission electron microscope photo of the ultra-thin montmorillonite composite material of bismuth tungstate quantum dot intercalation that obtains in an embodiment of the invention;
Fig. 4 be the bismuth tungstate quantum dot that obtains of the Graphene bismuth tungstate quantum dot composite material that obtains in an embodiment of the invention and comparative example 1 under sunlight to water in the contrast histogram of ammonia nitrogen degradation rate.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that following embodiment and/or accompanying drawing are only for the present invention is described, and unrestricted the present invention.
The invention discloses a kind of ultra-thin montmorillonite-based nano sheet and Bi thereof
2wO
6the preparation method of intercalation material, comprising: frost heave legal system is for ultra-thin montmorillonite-based nano sheet and use hydro-thermal legal system for its metal oxide intercalation material.By the inventive method, can obtain the ultra-thin montmorillonite-based nano sheet below thickness 10nm, its interlamellar spacing increases 0.2nm left and right than unstripped bulk polynite, makes it more easily prepare intercalation composite material.The saturating visible ray of ultra-thin montmorillonite material, can be used as the good carrier of visible light catalytic material.The present invention is with common visible light catalyst Bi
2wO
6for example, adopt hydrothermal method will there is highly active Bi
2wO
6quantum dot is intercalation in ultra-thin montmorillonite-based nano sheet and has obtained Bi
2wO
6the composite photocatalyst material of quantum dot intercalation.Due to the effect of polynite interlayer charge, this matrix material can greatly improve separation and the transmission efficiency in light induced electron hole, has than simple Bi
2wO
6the photocatalytic activity that quantum dot is higher, all kinds of organic pollutants that can difficult degradation under fast degradation natural condition under sunlight and inorganic ammonia nitrogen etc., have application prospect.Preparation method of the present invention is without specific installation and severe condition, and technique is simple, and controllability is strong, easily accomplishes scale production, and has practicality.
The invention provides a kind of preparation method of ultra-thin montmorillonite-based nano sheet, is frost heave method, comprising:
Steps A: the soluble sodium salts such as polynite and sodium carbonate are scattered in deionized water by a certain percentage, and constant temperature obtains sodium-based montmorillonite after stirring certain hour, through centrifugation, deionized water wash, dry rear standby;
Step B: the sodium-based montmorillonite obtaining in step B is dispersed in to deionized water for stirring and forms suspension after for some time, be placed on freeze overnight in home freezer, thaw under physical environment after taking out standby;
Step C: the montmorillonite suspension liquid thawing in step B was placed in supersonic cleaning machine after ultrasonic for some time, with centrifugal separation method, unstripped large size polynite is removed, the light yellow transperent suspension liquid in upper strata after collection centrifugation obtains ultra-thin montmorillonite-based nano sheet after lyophilize.
In described steps A, the mass ratio of polynite and sodium carbonate is 3:1~40:1, and constant temperature whipping temp is 40~100 ℃, and churning time is 0.5~24h.
In described step B, the mass ratio of polynite and deionized water is 1:50~1:500.
In described step C, ultrasonic time is more than 1min, and the rotating speed of centrifugation is 1000~10000 to turn, and centrifugation time is 1~3min.
In described steps A, sodium carbonate used can use other soluble sodium salts such as sodium-chlor, sodium bicarbonate to replace, and the size that corresponding consumption can its molecular weight adjusts.
The present invention also provides a kind of method of preparing bismuth tungstate quantum dot intercalated montmorillonite matrix material, comprise: by soluble bismuth salt and 1 hour above emulsion form the first precursor solution forming containing bismuth ion of sodium oleate stirring soluble in water, soluble tungstate salt and polynite are scattered in water, the second precursor solution stir, the ultrasonic formation that is uniformly dispersed containing tungstate ion and polynite, mix described the first precursor solution and the second precursor solution, 100 ℃ of above Hydrothermal Synthesiss are more than 2 hours.
In described the first precursor solution, the volumetric molar concentration of sodium oleate is 0.02~0.2mol/L, and in described the first precursor solution, the volumetric molar concentration of bismuth ion is 0.01~0.04mol/L.
In described the second precursor solution, the concentration of tungstate ion is 0.005~0.02mol/L, and in described the second precursor solution, the content of polynite is 0.2~20g/L.
Hydrothermal Synthesis temperature is at 100~200 ℃.The Hydrothermal Synthesis time is at 2~72h.
The mol ratio of described bismuth ion and tungstate ion is 2:1.
Described soluble bismuth salt is Bismuth trinitrate and/or bismuth chloride.
Described soluble tungstate salt is sodium wolframate and/or ammonium tungstate.
Photocatalysis efficiency height one is the impact that is subject to the separated transmission efficiency in light induced electron hole.The 2nd, be subject to the impact of catalyzer on the absorption property of pollutent.Therefore, fundamentally increase photocatalysis performance, must improve the separated transmission efficiency of photo-generated carrier and improve the adsorptive power of catalyzer to pollutent.This can be from regulating the microtexture aspect of material to realize.For example, synthesize the minimum photocatalyst material of size as quantum dot.Because carrier transport is directly related with its particle size to the surface time, size is less, and carrier transport is shorter to the surface time, thus the reduction compound probability of current carrier and improve photocatalysis performance.And undersized quantum dot surface can be high, also high than massive material to the adsorptive power of pollutent.But the agglomeration traits between the quantum dot being brought by its high surface energy makes the high catalytic performance of quantum dot be difficult to performance, in practical application, quantum dot must be fixed in other materials.
Polynite is the natural silicate material with interlayer charge, using it as Bi
2wO
6the substrate material of quantum dot, can solve the easy agglomeration traits of quantum dot on the one hand.On the other hand, if quantum dot is inserted between cheating engaging layer, photohole will move to faster quantum dot surface and participate in photocatalysis oxidation reaction under the effect of interlayer negative charge, and this process can further improve the separated transmission efficiency in light induced electron hole, thereby increase Bi
2wO
6the photocatalysis performance of quantum dot.And polynite rich content on earth, each pollutant is had to good absorption property.In conjunction with these advantages of polynite, the low material of base using polynite as quantum dot, the compound photocatalyst material of preparation polynite and quantum dot can greatly improve the efficiency of existing photocatalyst, compares and uses simple Bi
2wO
6photocatalyst material has lower cost.
Yet natural montmorillonite is because particle is larger, interlamellar spacing is less, by Bi
2wO
6technical difficulty between quantum dot interposed layer is larger.And oarse-grained polynite light transmission is poor, affect the Bi that interlayer inserts
2wO
6the efficiency of light energy utilization of quantum dot, is unfavorable for obtaining highly active visible light catalytic material.The technology of inventing a kind of ultra-thin polynite that can be mass-produced cheaply becomes possibility using the excellent carrier that makes polynite as quantum point type photocatalyst material.Therefore, realize low-cost preparation and and the Bi thereof in batches of ultra-thin polynite
2wO
6the intercalation compounding technology of quantum dot, not only has higher scientific value but also have the practical significance that environmental pollution is administered.
Compared with prior art, the present invention has following beneficial effect:
1) the ultra-thin montmorillonite material even thickness being obtained by the inventive method is controlled at below 10nm, and interlamellar spacing increased 0.2nm left and right under the condition existing without any intercalator, becomes the good matrix material base material of preparing;
2) the ultra-thin montmorillonite composite material of the bismuth tungstate quantum dot intercalation being obtained by the inventive method, the bismuth tungstate quantum dot size between cheating engaging layer is in 1nm left and right.Due to the good light transmission of ultra-thin polynite, the efficiency of light energy utilization of interlayer quantum dot is not subject to the impact of intercalation configuration.And the existence of the negative charge between cheating engaging layer has promoted photohole in bismuth tungstate quantum dot to move to the probability on quantum dot surface.And the high photochemical catalytic oxidation ability of bismuth tungstate is mainly derived from the strong oxidation capacity of its photohole, therefore the bismuth tungstate quantum dot being positioned between cheating engaging layer shows the photocatalytic activity higher than simple quantum dot, and the life-span of its photo-generated carrier has been improved 6 times than simple bismuth tungstate quantum dot;
2) preparation method of the present invention is without specific installation and severe condition, and technique is simple, and controllability is strong, easily accomplishes scale production, and has practicality.
Fig. 1 is the contrast of the little angle XRD diffracting spectrum of the little angle of the ultra-thin polynite XRD diffracting spectrum that obtains in an embodiment of the invention and undressed bulk montmorillonite material;
Fig. 2 is the XRD diffracting spectrum of the ultra-thin montmorillonite composite material of bismuth tungstate quantum dot intercalation that obtains in an embodiment of the invention and the contrast of XRD diffracting spectrum after the ultra-thin polynite of intercalation is not processed under identical hydrothermal condition;
Fig. 3 is the transmission electron microscope photo of the ultra-thin montmorillonite composite material of bismuth tungstate quantum dot intercalation that obtains in an embodiment of the invention;
Fig. 4 be the bismuth tungstate quantum dot that obtains of the Graphene bismuth tungstate quantum dot composite material that obtains in an embodiment of the invention and comparative example 1 under sunlight to water in the contrast histogram of ammonia nitrogen degradation rate.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameter that following example is concrete etc. is only also an example in OK range, and those skilled in the art can be done in suitable scope and be selected by explanation herein, and do not really want to be defined in the below concrete numerical value of example.
" the Bi that hydrothermal method makes described in embodiment
2wO
6nano material " be to obtain with reference to processing condition preparation described in embodiment 2 in Chinese patent ZL200610117981.3.
Embodiment 1
Ultra-thin polynite preparation
1g polynite is dispersed in 100mL water, after stirring certain hour, obtains the suspension of polynite.This suspension is put into refrigerator and cooled freeze more than 12 hours after standing for some time, the temperature of freezing treatment is-18 ℃.Then freezing polynite is placed under physical environment and is thawed, add the rear supersound process several minutes of certain water gaging dilution, the suspension obtaining leaves the heart through 8000, and unstripped bulk polynite is removed, and upper strata suspension obtain ultra-thin montmorillonite-based nano sheet after lyophilize;
Fig. 1 is the XRD diffracting spectrum of the ultra-thin montmorillonite-based nano sheet of the present embodiment acquisition, from XRD, can see, compare with unstripped bulk polynite, the diffraction peak of (001) crystal face of ultra-thin polynite obviously moves to little angular direction, illustrates that (001) spacing of ultra-thin montmorillonite-based nano sheet is that interlamellar spacing obviously increases;
In described ultra-thin montmorillonite-based nano sheet, the thickness of nanometer sheet is below 10nm, and interlamellar spacing is 1.26nm.
Embodiment 2
Bi
2wO
6the ultra-thin montmorillonite composite material preparation of quantum dot intercalation
2.2mmoL sodium oleate is dissolved in 20mL deionized water, after dissolving, adds 0.194g Bi (NO
3)
35H
2o, magnetic agitation 1.5 hours, the rotating speed of stirring is 800rpm, forms emulsion form precursor solution;
Ultra-thin montmorillonite-based nano sheet and 0.066g sodium wolframate that 120mg embodiment 1 is obtained are dissolved in 20mL deionized water, stir 1 hour also ultrasonic making be uniformly dispersed;
Two groups of solution mix and blends are transferred to after 1 hour in the water heating kettle of 50mL, 160 ℃ of hydro-thermal reactions 18 hours, naturally cooled to room temperature;
Through normal hexane, after the washing such as ethanol, use Vacuum Freezing & Drying Technology to obtain Bi solid sample in water heating kettle
2wO
6the ultra-thin montmorillonite composite material of quantum dot intercalation.
Fig. 2 is the Bi that the present embodiment obtains
2wO
6xRD diffracting spectrum after the ultra-thin montmorillonite composite material of quantum dot intercalation and pure polynite hydrothermal treatment consists, thanks through XRD composition analysis and debye and strangles formula and calculate known: the about 3nm of bismuth tungstate average grain size in the matrix material obtaining, Bi
2wO
6quantum dot further increases the interlamellar spacing of its (001) crystal face after inserting polynite.Pure polynite interlamellar spacing after hydrothermal treatment consists does not change.
Fig. 3 is the Bi that the present embodiment obtains
2wO
6the transmission electron microscope photo of the ultra-thin montmorillonite composite material of quantum dot intercalation, as seen from Figure 3: the Bi that is dispersed in polynite surface in the matrix material obtaining
2wO
6about 3nm left and right, the Bi of interlayer
2wO
6quantum dot is in 1nm left and right.
For the photocatalysis performance of institute system for composite sample, the experiment of ammonia nitrogen in degradation water under simulation sunlight.In water, ammonia nitrogen hard degradation under field conditions (factors), is to cause body eutrophication, causes breaking out the principal pollutant of blue-green algae.Therefore in degradation water, ammonia nitrogen can be weighed the actual application ability of catalyzer.In the present embodiment, by distillation nitriding, characterize ammonia nitrogen in solution concentration, and then draw degradation rate.
By 0.05g Bi
2wO
6it is in the ammonia nitrogen solution of 100mg/L that the ultra-thin montmorillonite composite material of quantum dot intercalation adds 200mL concentration, and with NaOH solution, regulating pH is 10.5 left and right,, be then placed under 500W xenon lamp and irradiate, after 1.5 hours, detect and in solution, remain ammonia nitrogen concentration.Detected result shows, after 1.5 hours, ammonia nitrogen in solution concentration is reduced to 30mg/L, nearly 70% ammonia nitrogen in 1.5 hours by Bi
2wO
6the ultra-thin montmorillonite composite material degraded of quantum dot intercalation.
Embodiment 3
The difference of the present embodiment and embodiment 2 is only: containing bismuth ion emulsion form precursor solution, be by 0.4mmoL BiCl
3be dissolved in 2.2mmoL sodium oleate that 20mL deionized water forms;
All the other contents are all with identical described in embodiment 2;
Analyze and learn after testing: the Bi that the present embodiment obtains
2wO
6the ultra-thin montmorillonite composite material of quantum dot intercalation is the approximately quadrature phase Bi of 5~6nm left and right of grain-size
2wO
6quantum dot is attached to polynite sheet surface.Bi between interposed layer
2wO
6quantum dot obviously reduces;
The Bi that the present embodiment obtains
2wO
6the ultra-thin montmorillonite composite material of quantum dot intercalation with embodiment 2 the same terms under to water in ammonia nitrogen degradation rate be 45%.
Comparative example 1
The difference of the present embodiment and embodiment 2 is only: in preparation process, do not add ultra-thin montmorillonite-based nano sheet;
All the other contents are all with identical described in embodiment 2;
The present embodiment obtain bismuth tungstate quantum dot under the matrix material the same terms obtaining with embodiment 2 to water in the degradation rate of ammonia nitrogen be 24%, than the performance of matrix material, obviously decline.
Comparative example 2
The difference of the present embodiment and embodiment 2 is only: the churning time that contains the emulsion form precursor solution of bismuth ion and sodium oleate shortens to 0.5h;
All the other contents are all with identical described in embodiment 2;
Analyze and learn after testing: the present embodiment product is defined as Bi through XRD composition analysis
2o
3, WO
3and a small amount of Bi
2wO
6mixed phase, illustrate that the too short meeting of churning time causes oleic acid radical ion and fully complexing of bismuth ion, the Bismuth trinitrate after direct hydrolysis reacts and generates Bi in follow-up water-heat process
2o
3;
And described product with embodiment 2 the same terms under to the degradation rate of ammonia nitrogen, be only 15%, photocatalysis performance is poor.
Comparative example 3
The difference of the present embodiment and embodiment 2 is only: sodium oleate consumption is increased to 0.3mol/L;
All the other contents are all with identical described in embodiment 2;
Analyze and learn after testing: the present embodiment product is defined as Bi through XRD composition analysis
2o
3, WO
3, illustrate that sodium oleate consumption too much can cause precursor solution alkalescence to strengthen and can not get Bi
2wO
6phase;
And described product with embodiment 2 the same terms under to the degradation rate of ammonia nitrogen, be only 15% left and right, photocatalysis performance is poor.
Visible in sum: by the inventive method, can to obtain a kind of Bi
2wO
6the ultra-thin montmorillonite Composite photocatalyst material of quantum dot intercalation, therefore this matrix material can increase light induced electron hole separated transmission efficiency, has significant photocatalytic activity, and under the natural condition that can be used for degrading, the pollutent of difficult degradation, has application prospect; And described preparation method is without specific installation and severe condition, and technique is simple, and controllability is strong, easily accomplishes scale production, and has practicality.
Claims (10)
1. a preparation method for ultra-thin montmorillonite-based nano sheet, is characterized in that, described method comprises:
1) sodium-based montmorillonite is scattered in to sodium-based montmorillonite the first suspension forming in water, wherein the mass ratio of sodium-based montmorillonite and water is 1:(50-500), gained the first suspension obtains sodium-based montmorillonite refrigerating fulid for freezing 12~120 hours in-5~-50 ℃;
2) after the sodium-based montmorillonite refrigerating fulid of step 1) gained is thawed, carry out supersound process, centrifugal removal sodium-based montmorillonite particle, obtains sodium-based montmorillonite the second suspension;
3) by step 2) ultra-thin montmorillonite-based nano sheet described in described the second suspension obtained by freeze drying of preparing.
2. preparation method according to claim 1, it is characterized in that, in step 1), by mass ratio, be (3-40): 1 polynite and soluble sodium salt are scattered in deionized water, at 40-100 ℃, stir 0.5-24 hour, through centrifugation, deionized water wash, after dry, obtain sodium-based montmorillonite, wherein the preferred sodium carbonate of soluble sodium salt, sodium-chlor and/or sodium bicarbonate.
3. the ultra-thin montmorillonite-based nano sheet that prepared by preparation method according to claim 1 and 2, is characterized in that, in described ultra-thin montmorillonite-based nano sheet, the thickness of nanometer sheet is below 10 nm, and interlamellar spacing is 1~1.5 nm.
4. a preparation method for bismuth tungstate quantum dot intercalated montmorillonite matrix material, is characterized in that, the preparation method of described matrix material comprises the preparation method of ultra-thin montmorillonite-based nano sheet claimed in claim 1; The preparation method of described matrix material also comprises:
A) soluble bismuth salt and sodium oleate are mixed in water, form emulsion form the first precursor liquid containing bismuth ion;
B) soluble tungstate salt and described ultra-thin montmorillonite-based nano sheet are scattered in water, dispersed formation is containing the second precursor liquid of tungstate ion and ultra-thin montmorillonite-based nano sheet;
C) by carrying out Hydrothermal Synthesis after the second precursor liquid mixing of preparing in the first precursor liquid of preparing in step a) and step b), make described bismuth tungstate quantum dot intercalated montmorillonite matrix material.
5. method according to claim 4, is characterized in that, in step a), soluble bismuth salt is Bismuth trinitrate and/or bismuth chloride.
6. according to the method described in claim 4 or 5, it is characterized in that, in step a), in described the first precursor liquid, the volumetric molar concentration of sodium oleate is 0.02-0.2 mol/L, and the volumetric molar concentration of bismuth ion is 0.01-0.04 mol/L.
7. according to arbitrary described method in claim 4-6, it is characterized in that, in step a), described in mix by stirring and realize, the rotating speed of stirring is 100-1000 rpm, churning time is more than 1 hour.
8. according to arbitrary described method in claim 4-7, it is characterized in that, in step b), in described the second precursor liquid, the concentration of tungstate ion is 0.005-0.02mol/L, and the content of ultra-thin montmorillonite-based nano sheet is 0.2-20 g/L.
9. according to arbitrary described method in claim 4-8, it is characterized in that, in step c), in the first precursor liquid and step the second precursor liquid mixing gained solution, the mol ratio of bismuth ion and tungstate ion is 2:1.
10. according to arbitrary described method in claim 4-9, it is characterized in that, in step c), the processing parameter of Hydrothermal Synthesis is: the temperature of Hydrothermal Synthesis is 100-200 ℃, and the time of Hydrothermal Synthesis is 2-72 hour.
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