CN102838165A - Method for preparing WO3 multiporous micro beads - Google Patents
Method for preparing WO3 multiporous micro beads Download PDFInfo
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- CN102838165A CN102838165A CN2012103747436A CN201210374743A CN102838165A CN 102838165 A CN102838165 A CN 102838165A CN 2012103747436 A CN2012103747436 A CN 2012103747436A CN 201210374743 A CN201210374743 A CN 201210374743A CN 102838165 A CN102838165 A CN 102838165A
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Abstract
The invention discloses a method for preparing WO3 multiporous micro beads, solving the technical problems that the WO3 multiporous micro beads prepared according to the conventional method are uneven in particle size and uncontrollable in form. The method for preparing the WO3 multiporous micro beads comprises the following steps of: adopting a microfluidics technology, and preparing large-pore micro beads by using PS nanospheres to fill WO3, namely using a template method to prepare the micro beads, then burning a template which is made of PS so as to obtain the WO3 multiporous micro beads. The WO3 multiporous micro beads, prepared according to the method disclosed by the invention, are controllable in form and even in particle size; the internal multiporous structures of the WO3 multiporous micro beads are arranged in order; and the WO3 multiporous micro beads can be applied to the field of gas sensitive materials, and also be applied to the aspects of adsorption, separation and selective catalysis.
Description
Technical field
The present invention relates to the preparation method of porous beads.
Background technology
WO
3Be a kind of have six sides, cube etc. the N-type semiconductor material of multiple symmetric form structure, WO
3Under light and electric field, demonstrate excellent photochromic and electrochromic property; It has fast-response speed and height variable color efficient; Make it be widely used in various light () and cause color-changing device, like display device, dexterous light modulation window, rear vision mirror, computingmachine memory storage elements, ornamental and protective packaging material etc.; While WO
3Highly sensitive aspect gas sensing property makes it have high selectivity to many gases, as: hydrogen, ammonia, hydrogen sulfide, nitrogen oxide (NO
X) etc.To WO
3Further scientific research, WO
3The gas sensing property of crystallization thin film is better, and response speed is fast, makes it stride forward a step in the gas sensitive field; Nanometer WO
3The preparation of material significantly makes its Application Areas continue to enlarge because of having huge specific surface area, volume effect, surface effects, quantum size effect and macro quanta tunnel effect; And the WO of other material that mixes
3Material also makes the performance of its each side be improved.Porous beads particle diameter heterogeneity, the form of existing method preparation are uncontrollable.
Summary of the invention
The present invention is porous beads particle diameter heterogeneity, the uncontrollable technical problem of form that will solve existing method preparation, thereby WO is provided
3The preparation method of porous beads.
WO of the present invention
3The preparation method of porous beads carries out according to the following steps:
One, deionized water is added in the there-necked flask; And loading tetrafluoroethylene stirring rake; Then there-necked flask is placed in-4 ℃ of ice baths; Add Glacial acetic acid min. 99.5 and volumn concentration and be 30% hydrogen peroxide, deionized water, Glacial acetic acid min. 99.5 and volumn concentration are that the volume ratio of 30% hydrogen peroxide is 1: (9～11): (9～11) obtain mixture;
Two, the temperature when mixture reaches-4 ℃, in mixture, adds 200 order tungsten powders, and the mass volume ratio of tungsten powder and deionized water be (16～17) g: (9～11) ml, and to keep the ice bath temperature be-4 ℃, reacts 23h～25h, the elimination solid, obtain filtrating;
Three, filtrating joining had in the container of cooling and reflux device, being heated to temperature is 50 ℃～60 ℃ backflow 16h～20h, under temperature is 30 ℃～50 ℃, the condition of vacuum tightness 0.5MPa～0.6MPa, is dried to powder then;
Four, the powder that step 3 is obtained is (9～11) g with absolute ethyl alcohol by mass volume ratio: (45～55) ml mixes, and carries out filtration under diminished pressure then, obtains peroxide wolframic acid verivate;
Five, peroxide wolframic acid verivate and ethanol are pressed mass volume ratio (30～32) g: (68～73) ml mixed dissolution obtains peroxide wolframic acid verivate colloidal sol;
Six, in the PS colloidal nanoparticles, add deionized water; Pack into behind the ultra-sonic dispersion in the centrifuge tube; Centrifugal 8～12min under the condition of 6500～7500r/min collects supernatant liquid, then with the supernatant liquid centrifugal 8～12min under the condition of 11000～13000r/min that collects; Remove upper solution, obtain sedimentary PS colloidal particle;
Seven, repeating step is 65 times, obtains irised colloidal nanoparticles;
Eight, the peroxide wolframic acid verivate colloidal sol that irised colloidal nanoparticles that step 6 is obtained and step 5 obtain is (73～74) by volume: mix (25～27), obtains WO
3-PS colloidal sol;
Nine, connect micro fluidic device: micro fluidic device comprises 10mL syringe, 50mL syringe, micro-injection pump, threeway, polypropylene container; Said 10mL syringe is parallel with the 50mL syringe to be placed in the micro-injection pump; The 10mL syringe links to each other with the vertical end of threeway through conduit; The 50mL syringe links to each other with the horizontal ends of threeway through conduit, and another horizontal ends of threeway links to each other with polypropylene container with conduit;
Ten, the 10mL syringe is drawn 2mL WO
3-PS colloidal sol, the 50mL syringe is drawn 50mL silicone oil, starts micro-injection pump, and WO is regulated in the control threeway
3At 50ml/h～80ml/h, obtain particle diameter is 100 μ m～1mmWO to the flow velocity of-PS colloidal sol at the flow velocity of 0.5ml/h～0.7ml/h and silicone oil
3-PS microballon is collected WO with the polypropylene container that the thick silicone oil of 1cm is housed
3-PS microballon;
11, WO will be housed
3The container of-PS microballon is placed on 7h～9h in 50～70 ℃ of baking ovens, then oven temperature is elevated to 40～60 ℃ and continues heating 11h～13h, is cooled to room temperature then;
12, with container at the middle and upper levels silicone oil outwell, add the normal hexane washing, after washing silicone oil fully off, with WO
3-PS microballon places room temperature to bead surface normal hexane to volatilize fully, then with WO
3-PS microballon is put in the crucible, crucible is put in the retort furnace again, at heat-up rate is to be warming up to 500～600 ℃ of calcining 0.5h～1.5h under the condition of 30～50 ℃/10min, naturally cools to room temperature, obtains WO
3Porous beads.
The present invention utilizes microflow control technique, fills WO with the PS nanometer ball
3Prepare the macropore microballon, promptly use template to prepare microballon, the template that is prepared into of burning-off PS can obtain WO then
3Porous beads, the specific surface area of this microballon are 15～18m
2/ g makes it in air-sensitive sense field of materials very big potential value arranged;
The present invention is through regulating WO
3The flow velocity of-PS colloidal sol and silicone oil and the microballon that obtains, its particle diameter can be at micron to the mm size regulation and control, and gained porous beads uniform particle diameter, inner vesicular structure ordered arrangement, and the internal surface area of this ordered porous microballon is 11～14m
2/ g, with make its in absorption, separate and select and will show a lot of special functions aspect the capable catalysis.
Description of drawings
Fig. 1 is the micro fluidic device synoptic diagram described in embodiment one step 9; 1 is the 10mL syringe among the figure, and 2 is the 50mL syringe, and 3 is micro-injection pump, and 4 are threeway, and 5 is polypropylene container;
Fig. 2 is the WO of test one preparation
3The opticmicroscope projection photo of-PS microballon;
Fig. 3 is the WO of test one preparation
3Sem photograph behind the-PS microballon burning-off PS;
Fig. 4 is the WO of test two preparations
3Surface tissue low power sem photograph behind the-PS microballon burning-off PS;
Fig. 5 is the WO of test one preparation
3Surface tissue high power sem photograph behind the-PS microballon burning-off PS;
Fig. 6 is the WO of test one preparation
3Internal structure low power sem photograph behind the-PS microballon burning-off PS;
Fig. 7 is the WO of test two preparations
3Internal structure high power sem photograph behind the-PS microballon burning-off PS
Embodiment
Embodiment one: WO in this embodiment
3The preparation method of porous beads carries out according to the following steps:
One, deionized water is added in the there-necked flask; And loading tetrafluoroethylene stirring rake; Then there-necked flask is placed in-4 ℃ of ice baths; Add Glacial acetic acid min. 99.5 and volumn concentration and be 30% hydrogen peroxide, deionized water, Glacial acetic acid min. 99.5 and volumn concentration are that the volume ratio of 30% hydrogen peroxide is 1: (9～11): (9～11) obtain mixture;
Two, the temperature when mixture reaches-4 ℃, in mixture, adds 200 order tungsten powders, and the mass volume ratio of tungsten powder and deionized water be (16～17) g: (9～11) ml, and to keep the ice bath temperature be-4 ℃, reacts 23h～25h, the elimination solid, obtain filtrating;
Three, filtrating joining had in the container of cooling and reflux device, being heated to temperature is 50 ℃～60 ℃ backflow 16h～20h, under temperature is 30 ℃～50 ℃, the condition of vacuum tightness 0.5MPa～0.6MPa, is dried to powder then;
Four, the powder that step 3 is obtained is (9～11) g with absolute ethyl alcohol by mass volume ratio: (45～55) ml mixes, and carries out filtration under diminished pressure then, obtains peroxide wolframic acid verivate;
Five, peroxide wolframic acid verivate and ethanol are pressed mass volume ratio (30～32) g: (68～73) ml mixed dissolution obtains peroxide wolframic acid verivate colloidal sol;
Six, in the PS colloidal nanoparticles, add deionized water; Pack into behind the ultra-sonic dispersion in the centrifuge tube; Centrifugal 8～12min under the condition of 6500～7500r/min collects supernatant liquid, then with the supernatant liquid centrifugal 8～12min under the condition of 11000～13000r/min that collects; Remove upper solution, obtain sedimentary PS colloidal particle;
Seven, repeating step is 65 times, obtains irised colloidal nanoparticles;
Eight, the peroxide wolframic acid verivate colloidal sol that irised colloidal nanoparticles that step 6 is obtained and step 5 obtain is (73～74) by volume: mix (25～27), obtains WO
3-PS colloidal sol;
Nine, connect micro fluidic device: micro fluidic device comprises 10mL syringe 1,50mL syringe 2, micro-injection pump 3, threeway 4, polypropylene container 5; Said 10mL syringe 1 and 50mL syringe 2 parallel being placed in the micro-injection pump 3; 10mL syringe 1 links to each other with the vertical end of threeway 4 through conduit; 50mL syringe 2 links to each other with the horizontal ends of threeway 4 through conduit, and another horizontal ends of threeway 4 links to each other with polypropylene container 5 with conduit;
Ten, 10mL syringe 1 is drawn 2mL WO
3-PS colloidal sol, 50mL syringe 2 is drawn 50mL silicone oil, starts micro-injection pump 3, and WO is regulated in control threeway 4
3At 50ml/h～80ml/h, obtain particle diameter is 100 μ m～1mmWO to the flow velocity of-PS colloidal sol at the flow velocity of 0.5ml/h～0.7ml/h and silicone oil
3-PS microballon is collected WO with the polypropylene container that the thick silicone oil of 1cm is housed
3-PS microballon;
11, WO will be housed
3The container of-PS microballon is placed on 7h～9h in 50～70 ℃ of baking ovens, then oven temperature is elevated to 40～60 ℃ and continues heating 11h～13h, is cooled to room temperature then;
12, with container at the middle and upper levels silicone oil outwell, add the normal hexane washing, after washing silicone oil fully off, with WO
3-PS microballon places room temperature to bead surface normal hexane to volatilize fully, then with WO
3-PS microballon is put in the crucible, crucible is put in the retort furnace again, at heat-up rate is to be warming up to 500～600 ℃ of calcining 0.5h～1.5h under the condition of 30～50 ℃/10min, naturally cools to room temperature, obtains WO
3Porous beads.
This embodiment utilizes microflow control technique, fills WO with the PS nanometer ball
3Prepare the macropore microballon, promptly use template to prepare microballon, the template that is prepared into of burning-off PS can obtain WO then
3Porous beads, the specific surface area of this microballon are 15～18m
2/ g makes it in air-sensitive sense field of materials very big potential value arranged;
This embodiment is through regulating WO
3The flow velocity of-PS colloidal sol and silicone oil and the microballon that obtains, its particle diameter can be at micron to the mm size regulation and control, and gained porous beads uniform particle diameter, inner vesicular structure ordered arrangement, and the internal surface area of this ordered porous microballon is 11～14m
2/ g, with make its in absorption, separate and select and will show a lot of special functions aspect the capable catalysis.
Embodiment two: what this embodiment and embodiment one were different is: deionized water, Glacial acetic acid min. 99.5 and volumn concentration are that the volume ratio of 30% hydrogen peroxide is 1: 10: 10 in the step 1.Other is identical with embodiment one.
Embodiment three: what this embodiment was different with practical implementation one or two is: the mass volume ratio of tungsten powder and deionized water is 16.25g: 10ml in the step 2.Other is identical with practical implementation one or two.
Embodiment four: what this embodiment was different with one of embodiment one to three is: reflux temperature is 55 ℃ in the step 3, and return time is 18h.Other identical with one of embodiment one to three.
Embodiment five: what this embodiment was different with one of embodiment one to four is: the mass volume ratio of powder and absolute ethyl alcohol is 10g: 50ml in the step 4.Other identical with one of embodiment one to five.
Embodiment six: what this embodiment was different with one of embodiment one to five is: the mass volume ratio 31g of peroxide wolframic acid verivate and absolute ethyl alcohol: 70ml in the step 5.Other identical with one of embodiment one to five.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: PS colloidal nanoparticles particle diameter is 197～296nm in the step 6.Other identical with one of embodiment one to six.
Embodiment eight: what this embodiment was different with one of embodiment one to seven is: PS colloidal nanoparticles particle diameter is 234～256nm in the step 6.Other identical with one of embodiment one to seven.
Embodiment nine: what this embodiment was different with one of embodiment one to eight is: in the step 11 container is placed on 8h in 50 ℃ of baking ovens.Other identical with one of embodiment one to eight.
Embodiment ten: what this embodiment was different with one of embodiment one to nine is: temperature is elevated to 60 ℃ of continuation heating 12h in the step 11.Other identical with one of embodiment one to nine.
Embodiment 11: what this embodiment was different with one of embodiment one to ten is: under heat-up rate is the condition of 40 ℃/10min, be warming up to 500 ℃ of calcining 1h in the step 12.Other identical with one of embodiment one to nine.
Through following verification experimental verification beneficial effect of the present invention:
Test one: the WO of this test
3The preparation method of porous beads realizes by following method:
One, the 10mL deionized water is added in the 500mL there-necked flask, and load the tetrafluoroethylene stirring rake, then there-necked flask is placed in-4 ℃ of ice baths, the Glacial acetic acid min. 99.5 of adding 100ml and the volumn concentration of 100ml are 30% hydrogen peroxide;
Two, the temperature when mixture reaches-4 ℃, in mixture, adds 200 order tungsten powder 16.25g, and to keep the ice bath temperature be-4 ℃, and reaction 24h crosses the elimination solid, obtains filtrating;
Three, the 55 ℃ of refluxed 18h that will filtrate are dried to powder then under temperature is 40 ℃, vacuum tightness 0.5MPa～0.6MPa;
Four, the powder 10g and the absolute ethyl alcohol 50ml hybrid reaction that step 3 are obtained are carried out filtration under diminished pressure then, obtain peroxide wolframic acid verivate;
Five, peroxide wolframic acid verivate 3.1g and ethanol 7ml mixed dissolution obtain peroxide wolframic acid verivate colloidal sol;
Six, pack into after in particle diameter is the PS colloidal nanoparticles of 242nm, adding deionized water, ultra-sonic dispersion in the centrifuge tube; Centrifugal 10min under the condition of 7000rpm; Collect supernatant liquid; With the supernatant liquid centrifugal 10min under the condition of 12000rpm that collects, remove upper solution then, obtain sedimentary PS colloidal particle;
Seven, repeating step is 65 times, obtains irised colloidal nanoparticles;
Eight, the peroxide wolframic acid verivate colloidal sol 13ml mixed preparing that irised colloidal nanoparticles 37m that step 6 is obtained and step 5 obtain obtains WO
3-PS colloidal sol;
Nine, connect micro fluidic device: micro fluidic device comprises 10mL syringe 1,50mL syringe 2, micro-injection pump 3, threeway 4, polypropylene container 5; Said 10mL syringe 1 and 50mL syringe 2 parallel being placed in the micro-injection pump 3; 10mL syringe 1 links to each other with the vertical end of threeway 4 through conduit; 50mL syringe 2 links to each other with the horizontal ends of threeway 4 through conduit, and another horizontal ends of threeway 4 links to each other with polypropylene container 5 with conduit;
Ten, 10mL syringe 1 is drawn 2mL WO
3-PS colloidal sol, 50mL syringe 2 is drawn 50mL silicone oil, starts micro-injection pump 3, and WO is regulated in control threeway 4
3The flow velocity of-PS colloidal sol at 50ml/h, obtains the WO that particle diameter is 200 μ m at the flow velocity of 0.5ml/h and silicone oil
3-PS microballon is collected WO with the polypropylene container that the thick silicone oil of 1cm is housed
3-PS microballon;
11, WO will be housed
3The container of-PS microballon is placed on 8h in 50 ℃ of baking ovens, then oven temperature is elevated to 60 ℃ and continues heating 12h, is cooled to room temperature then;
12, with container at the middle and upper levels silicone oil outwell, add the normal hexane washing, after washing silicone oil fully off, with WO
3-PS microballon places room temperature to bead surface normal hexane to volatilize fully, then with WO
3-PS microballon is put in the crucible, crucible is put in the retort furnace again, and heat-up rate is to be warming up to 500 ℃ of calcining 1h under the condition of 40 ℃/10min, naturally cools to room temperature, obtains WO
3Porous beads.
This tests employed micro fluidic device figure with reference to figure 1.
The WO of this test one preparation
3The opticmicroscope projection photo of-PS microballon is as shown in Figure 2, as can beappreciated from fig. 2 the WO of microflow control technique preparation
3The spherical perfection of porous beads, uniform particle diameter.
The WO of this test preparation
3Sem photograph behind the-PS microballon burning-off PS is as shown in Figure 3, as can beappreciated from fig. 3 the WO of the present invention's preparation
3The microspherulite diameter of porous beads is even, smooth surface.
The WO of this test one preparation
3Surface tissue high power sem photograph behind the-PS microballon burning-off PS is as shown in Figure 5, as can beappreciated from fig. 5 WO
3Porous beads is the photonic crystal of counter opal structure, and porous size homogeneous.
The WO of this test one preparation
3Internal structure low power sem photograph behind the-PS microballon burning-off PS is as shown in Figure 6, as can beappreciated from fig. 6 WO
3The inner vesicular structure ordered arrangement of microballon.
Test two: the WO of this test
3The preparation method of porous beads realizes by following method:
One, the 10mL deionized water is added in the 500mL there-necked flask, and load the tetrafluoroethylene stirring rake, then there-necked flask is placed in-4 ℃ of ice baths, the Glacial acetic acid min. 99.5 of adding 100ml and the volumn concentration of 100ml are 30% hydrogen peroxide;
Two, the temperature when mixture reaches-4 ℃, in mixture, adds 200 order tungsten powder 16.25g, and to keep the ice bath temperature be-4 ℃, and reaction 24h crosses the elimination solid, obtains filtrating;
Three, the 55 ℃ of refluxed 18h that will filtrate are dried to powder then under temperature is 40 ℃, vacuum tightness 0.5MPa～0.6MPa;
Four, the powder 10g and the absolute ethyl alcohol 50ml hybrid reaction that step 3 are obtained are carried out filtration under diminished pressure then, obtain peroxide wolframic acid verivate;
Five, peroxide wolframic acid verivate 3.1g and ethanol 7ml mixed dissolution obtain peroxide wolframic acid verivate colloidal sol;
Six, pack into after in particle diameter is the PS colloidal nanoparticles of 242nm, adding deionized water, ultra-sonic dispersion in the centrifuge tube; Centrifugal 10min under the condition of 7000rpm; Collect supernatant liquid; With the supernatant liquid centrifugal 10min under the condition of 12000rpm that collects, remove upper solution then, obtain sedimentary PS colloidal particle;
Seven, repeating step is 65 times, obtains irised colloidal nanoparticles;
Eight, the peroxide wolframic acid verivate colloidal sol 13ml mixed preparing that irised colloidal nanoparticles 37m that step 6 is obtained and step 5 obtain obtains WO
3-PS colloidal sol;
Nine, connect micro fluidic device: micro fluidic device comprises 10mL syringe 1,50mL syringe 2, micro-injection pump 3, threeway 4, polypropylene container 5; Said 10mL syringe 1 and 50mL syringe 2 parallel being placed in the micro-injection pump 3; 10mL syringe 1 links to each other with the vertical end of threeway 4 through conduit; 50mL syringe 2 links to each other with the horizontal ends of threeway 4 through conduit, and another horizontal ends of threeway 4 links to each other with polypropylene container 5 with conduit;
Ten, 10mL syringe 1 is drawn 2mL WO
3-PS colloidal sol, 50mL syringe 2 is drawn 50mL silicone oil, starts micro-injection pump 3, and WO is regulated in control threeway 4
3The flow velocity of-PS colloidal sol at the flow velocity of 0.7ml/h and silicone oil at 80ml/h, to obtain the WO that particle diameter is 500 μ m
3-PS microballon is collected WO with the polypropylene container that the thick silicone oil of 1cm is housed
3-PS microballon;
11, WO will be housed
3The container of-PS microballon is placed on 8h in 50 ℃ of baking ovens, then oven temperature is elevated to 60 ℃ and continues heating 12h, is cooled to room temperature then;
12, with container at the middle and upper levels silicone oil outwell, add the normal hexane washing, after washing silicone oil fully off, with WO
3-PS microballon places room temperature to bead surface normal hexane to volatilize fully, then with WO
3-PS microballon is put in the crucible, crucible is put in the retort furnace again, and heat-up rate is to be warming up to 500 ℃ of calcining 1h under the condition of 40 ℃/10min, naturally cools to room temperature, obtains WO
3Porous beads.
This tests employed micro fluidic device figure with reference to figure 1.
The WO of this test preparation
3Sem photograph behind the-PS microballon burning-off PS is as shown in Figure 3, as can beappreciated from fig. 3 the WO of the present invention's preparation
3The microspherulite diameter of porous beads is even, smooth surface.
The WO of this test two preparations
3Surface tissue low power sem photograph behind the-PS microballon burning-off PS is as shown in Figure 4, as can beappreciated from fig. 4 WO
3The structurally ordered arrangement of porous beads porous surface.
The WO of this test two preparations
3Internal structure high power sem photograph behind the-PS microballon burning-off PS is as shown in Figure 7, as can beappreciated from fig. 7 WO
3The inner porous size of microballon homogeneous.
Can know by test one and test two contrasts, through regulating WO
3The flow velocity of-PS colloidal sol and silicone oil can obtain the different WO of size
3-PS microballon, its particle diameter can be at micron to the mm size regulation and control, and form is controlled.
Claims (10)
1.WO
3The preparation method of porous beads is characterized in that WO
3The preparation method of porous beads carries out according to the following steps:
One, deionized water is added in the there-necked flask; And loading tetrafluoroethylene stirring rake; Then there-necked flask is placed in-4 ℃ of ice baths; Add Glacial acetic acid min. 99.5 and volumn concentration and be 30% hydrogen peroxide, deionized water, Glacial acetic acid min. 99.5 and volumn concentration are that the volume ratio of 30% hydrogen peroxide is 1: (9～11): (9～11) obtain mixture;
Two, the temperature when mixture reaches-4 ℃, in mixture, adds 200 order tungsten powders, and the mass volume ratio of tungsten powder and deionized water be (16～17) g: (9～11) ml, and to keep the ice bath temperature be-4 ℃, reacts 23h～25h, the elimination solid, obtain filtrating;
Three, filtrating joining had in the container of cooling and reflux device, being heated to temperature is 50 ℃～60 ℃ backflow 16h～20h, under temperature is 30 ℃～50 ℃, the condition of vacuum tightness 0.5MPa～0.6MPa, is dried to powder then;
Four, the powder that step 3 is obtained is (9～11) g with absolute ethyl alcohol by mass volume ratio: (45～55) ml mixes, and carries out filtration under diminished pressure then, obtains peroxide wolframic acid verivate;
Five, peroxide wolframic acid verivate and ethanol are pressed mass volume ratio (30～32) g: (68～73) ml mixed dissolution obtains peroxide wolframic acid verivate colloidal sol;
Six, in the PS colloidal nanoparticles, add deionized water; Pack into behind the ultra-sonic dispersion in the centrifuge tube; Centrifugal 8～12min under the condition of 6500～7500r/min collects supernatant liquid, then with the supernatant liquid centrifugal 8～12min under the condition of 11000～13000r/min that collects; Remove upper solution, obtain sedimentary PS colloidal particle;
Seven, repeating step is 65 times, obtains irised colloidal nanoparticles;
Eight, the peroxide wolframic acid verivate colloidal sol that irised colloidal nanoparticles that step 6 is obtained and step 5 obtain is (73～74) by volume: mix (25～27), obtains WO
3-PS colloidal sol;
Nine, connect micro fluidic device: micro fluidic device comprises 10mL syringe (1), 50mL syringe (2), micro-injection pump (3), threeway (4), polypropylene container (5); Said 10mL syringe (1) is parallel with 50mL syringe (2) to be placed in the micro-injection pump (3); 10mL syringe (1) links to each other with the vertical end of threeway (4) through conduit; 50mL syringe (2) links to each other with the horizontal ends of threeway (4) through conduit, and another horizontal ends of threeway (4) links to each other with polypropylene container (5) with conduit;
Ten, 10mL syringe (1) is drawn 2mL WO
3-PS colloidal sol, 50mL syringe (2) is drawn 50mL silicone oil, starts micro-injection pump (3), and WO is regulated in control threeway (4)
3At 50ml/h～80ml/h, obtain particle diameter is 100 μ m～1mmWO to the flow velocity of-PS colloidal sol at the flow velocity of 0.5ml/h～0.7ml/h and silicone oil
3-PS microballon is collected WO with the polypropylene container that the thick silicone oil of 1cm is housed
3-PS microballon;
11, WO will be housed
3The container of-PS microballon is placed on 7h～9h in 50～70 ℃ of baking ovens, then oven temperature is elevated to 40～60 ℃ and continues heating 11h～13h, is cooled to room temperature then;
12, with container at the middle and upper levels silicone oil outwell, add the normal hexane washing, after washing silicone oil fully off, with WO
3-PS microballon places room temperature to bead surface normal hexane to volatilize fully, then with WO
3-PS microballon is put in the crucible, crucible is put in the retort furnace again, at heat-up rate is to be warming up to 500～600 ℃ of calcining 0.5h～1.5h under the condition of 30～50 ℃/10min, naturally cools to room temperature, obtains WO
3Porous beads.
2. WO according to claim 1
3The preparation method of porous beads is characterized in that deionized water in the step 1, Glacial acetic acid min. 99.5 and volumn concentration are that the volume ratio of 30% hydrogen peroxide is 1: 10: 10.
3. WO according to claim 1
3The preparation method of porous beads is characterized in that the mass volume ratio of tungsten powder and deionized water is 16.25g: 10ml in the step 2.
4. WO according to claim 1
3The preparation method of porous beads is characterized in that reflux temperature is 55 ℃ in the step 3, and return time is 18h.
5. WO according to claim 1
3The preparation method of porous beads is characterized in that the mass volume ratio of powder and absolute ethyl alcohol is 10g: 50ml in the step 4.
6. WO according to claim 1
3The preparation method of porous beads is characterized in that the mass volume ratio 31g of peroxide wolframic acid verivate and absolute ethyl alcohol in the step 5: 70ml.
7. WO according to claim 1
3The preparation method of porous beads is characterized in that PS colloidal nanoparticles particle diameter is 197～296nm in the step 6.
8. WO according to claim 1
3The preparation method of porous beads is characterized in that in the step 11 container being placed on 8h in 50 ℃ of baking ovens.
9. WO according to claim 1
3The preparation method of porous beads is characterized in that temperature is elevated to 60 ℃ of continuation heating 12h in the step 11.
10. WO according to claim 1
3The preparation method of porous beads is characterized in that in the step 12 under heat-up rate is the condition of 40 ℃/10min, being warming up to 500 ℃ of calcining 1h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210374743.6A CN102838165B (en) | 2012-09-29 | 2012-09-29 | Method for preparing WO3 multiporous micro beads |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210374743.6A CN102838165B (en) | 2012-09-29 | 2012-09-29 | Method for preparing WO3 multiporous micro beads |
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| CN105565386A (en) * | 2016-01-14 | 2016-05-11 | 北京交通大学 | Method for preparing tungsten oxide with three-dimensional ordered macroporous structure |
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| JPH0437610A (en) * | 1990-05-30 | 1992-02-07 | Ricoh Co Ltd | Hyperfine tungsten oxide particles |
| CN101417819A (en) * | 2008-11-21 | 2009-04-29 | 中国地质大学（武汉） | Photochromic WO3 film with hollow microsphere as micro-morphology and preparation method thereof |
| CN102500298A (en) * | 2011-11-24 | 2012-06-20 | 武汉大学 | Preparation method of metal oxides and composite microspheres of metal oxides |
| CN202410630U (en) * | 2012-01-19 | 2012-09-05 | 黑龙江大学 | Simple microfluidic device for laboratory |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0437610A (en) * | 1990-05-30 | 1992-02-07 | Ricoh Co Ltd | Hyperfine tungsten oxide particles |
| CN101417819A (en) * | 2008-11-21 | 2009-04-29 | 中国地质大学（武汉） | Photochromic WO3 film with hollow microsphere as micro-morphology and preparation method thereof |
| CN102500298A (en) * | 2011-11-24 | 2012-06-20 | 武汉大学 | Preparation method of metal oxides and composite microspheres of metal oxides |
| CN202410630U (en) * | 2012-01-19 | 2012-09-05 | 黑龙江大学 | Simple microfluidic device for laboratory |
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| 《Adv. Funct. Mater.》 20081231 Di Chen，et al. "Hierarchical WO3 Hollow Shells：Dendrite，Sphere，Dumbbell，and Their Photocatalytic Properties" 1922-1928 1-10 第18卷, * |
| 《J. Phys. Chem. C》 20090330 Zhi-Gang Zhao，et al. "Shape Modulation of Tungstic Acid and Tungsten Oxide Hollow Structures" 6539-6546 1-10 第113卷, 第16期 * |
| DI CHEN，ET AL.: ""Hierarchical WO3 Hollow Shells：Dendrite，Sphere，Dumbbell，and Their Photocatalytic Properties"", 《ADV. FUNCT. MATER.》 * |
| ZHI-GANG ZHAO，ET AL.: ""Shape Modulation of Tungstic Acid and Tungsten Oxide Hollow Structures"", 《J. PHYS. CHEM. C》 * |
Cited By (1)
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|---|---|---|---|---|
| CN105565386A (en) * | 2016-01-14 | 2016-05-11 | 北京交通大学 | Method for preparing tungsten oxide with three-dimensional ordered macroporous structure |
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