CN104860355A - Production method of large aperture of mesoporous tungsten trioxide microsphere - Google Patents
Production method of large aperture of mesoporous tungsten trioxide microsphere Download PDFInfo
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Abstract
The invention discloses a production method of a large aperture of mesoporous tungsten trioxide microsphere. Hexadecylamine serves as a template, isopropanol serves as a cosolvent, ethyl orthosilicate, ammonia water and deionized water serve as raw materials, stirring is performed after ultrasonic mixing is performed on the deionized water, the isopropanol and the hexadecylamine, the ammonia water and the ethyl orthosilicate are added in turn, stirring is performed until precipitation is produced in a solution, filtration, washing, drying and roasting are performed on the precipitation, an obtained silicon dioxide microsphere is soaked in a double salt solution to be reamed, an obtained reamed silicon dioxide microsphere serves as a hard template, a silicotungstic acid hydrate or a phosphotungstic acid hydrate is a precursor for producing the tungsten trioxide microsphere, the tungsten trioxide microsphere is introduced into a roamed silicon dioxide microsphere pore passage, the roasting is performed in the air atmosphere, and mesoporous silicon dioxide of an obtained mesoporous silicon dioxide microsphere for loading tungsten trioxide is removed through an HF (Hydrogen Fluoride) aqueous solution to obtain the large aperture of mesoporous tungsten trioxide microsphere. According to the production method of the large aperture of mesoporous tungsten trioxide microsphere, the production process is simple, the cycle is short, the production can be performed under the room temperature condition, and the aperture of the tungsten trioxide microsphere can be controlled in the production process.
Description
Technical field
A kind of wide-aperture mesoporous WO of the present invention
3the preparation method of microballoon, belongs to field of nanometer technology.
Background technology
Silicon dioxide microsphere to prepare the monodisperse silica microspheres of atresia in alcohol-water-ammoniacal liquor-tetraethoxy system by taking the lead in early than nineteen sixty-eight.1992, the scientist of Mobil company successfully prepared the mesoporous material of M41S series.In recent years, Chinese scholars is improved method, mainly through adding cats product or other swelling agents have synthesized mesoporous silicon dioxide micro-sphere.Wherein with tensio-active agents such as quaternary ammonium salts for the method for Template preparation mesoporous silicon dioxide micro-sphere is the most common.M.Grun etc. are at Advanced Materials, 1997, in 9:254-257, report utilizes hydrolysis of alkoxide to prepare on the basis of silicon dioxide microsphere technique, introduces hexadecyl trimethyl ammonium bromide (CTAB), has obtained the silicon dioxide microsphere of aperture 2-4 nanometer.Zhao is waiting Journal of Non-crystalline Solids, 2005, in 351:3593-3599, report utilizes organic amine as template, also be the catalyzer of silicon alkoxide hydrolysis, decrease the use of raw material during synthetic silica microballoon, but the pore size of silicon dioxide microsphere is unsatisfactory, and aperture increases, more be conducive to entering of macromolecular substance, for porous silica microballoon is in support of the catalyst, absorption creates convenience with the application be separated, the photocatalyst that active development has the adjustable meso-hole structure in aperture has become the important directions improving semi-conductor catalytic activity.
Research finds, W-Sn deposits has good catalytic performance, wherein WO
3advantage that is cheap due to it and that be easy to get is favored, WO
3can band gap narrower (2.4eV-2.8eV), can visible ray be made full use of, but its redox ability is more weak, by changing WO
3structure and other metals of load can further improve photoresponse scope and photocatalysis performance.The photocatalyst of meso-hole structure has the pore passage structure of high-crystallinity, bigger serface and rule, and these advantages can accelerate the transmission of photo-generated carrier, increases the active sites of catalyst surface, thus the effective catalytic activity improving photocatalyst.
As can be seen here, it is current problems faced that preparation has the larger tungstic oxide microballoon in aperture, and WO
3pattern, be also the factor affecting photocatalysis performance.Focus on that the silicon dioxide microsphere after utilizing reaming is as template in the present invention, synthesising mesoporous WO
3microballoon.
Summary of the invention
the object of the invention is to solve prior art intermediary hole WO
3mesoporous silicon dioxide micro-sphere (MS) pore size of template adopted in microballoon preparation process is less than 2nm, the mesoporous WO finally obtained
3the technical problem that microballoon aperture is little and a kind of wide-aperture mesoporous WO is provided
3the preparation method of microballoon, this preparation method with the silicon dioxide microsphere after reaming for template, the mesoporous WO finally obtained
3microballoon aperture is large, can reach about 4.5nm, and this preparation method is simple, room temperature condition.
technical scheme of the present invention
A kind of wide-aperture mesoporous WO
3the preparation method of microballoon, namely be template with cetylamine, Virahol is solubility promoter, tetraethoxy, concentration of volume percent is the ammoniacal liquor of 25-28% and deionized water is starting raw material, in water: Virahol: tetraethoxy: the volume ratio of ammoniacal liquor is that the ratio of 45:50:2.9:0.7 calculates;
First dried up, Virahol and cetylamine mixing will be gone, ultrasonic mix after, stir 10-30min, then ammoniacal liquor is added, add tetraethoxy after dissolving, continue to be stirred to appearance precipitation in reaction soln, by sedimentation and filtration, washing, drying, then controlling temperature rise rate is that 1 DEG C/min rises to 300-350 DEG C and carries out roasting 2-3h, obtains silicon dioxide microsphere;
Then will obtain silicon dioxide microsphere to be immersed in complex salt solution and to carry out reaming, obtain the silicon dioxide microsphere of reaming, described complex salt solution, by H
2o, NaCl, LiCl and KNO
3calculate in molar ratio, i.e. H
2o:NaCl:LiCl:KNO
3for the ratio of 39:3.4:1.2:0.5 mixes;
Then using the silicon dioxide microsphere of reaming as hard template, Silicotungstic acid hydrate or phosphotungstic acid hydrate are the presoma preparing tungstic oxide microballoon, tungstic oxide microballoon is introduced in mesoporous silicon dioxide micro-sphere duct, in air atmosphere, control temperature rise rate 1 DEG C/min is warming up to 350-600 DEG C and carries out roasting 3-5h, obtained a kind of load WO
3mesoporous silicon dioxide micro-sphere;
After reaming, the consumption of silicon dioxide microsphere and Silicotungstic acid hydrate or phosphotungstic acid hydrate, calculates in mass ratio, i.e. silicon dioxide microsphere: Silicotungstic acid hydrate or phosphotungstic acid hydrate are 1:1-3, is preferably 1:2.25;
Be finally the HF aqueous solution removing mesoporous silicon oxide of 10% with mass percent concentration, obtain wide-aperture mesoporous WO
3microballoon.
Above-mentioned wide-aperture mesoporous WO
3the preparation method of microballoon, specifically comprises the steps:
(1), the preparation of silicon dioxide microsphere
By deionized water and Virahol mixing, then cetylamine is added, be 50-100KHz in ultrasonic frequency, ultrasonic time is add the ammoniacal liquor that concentration of volume percent is 25-28% after 10-30min mixes, under room temperature, controlling mixing speed is that 600-800r/min stirs 10-30min, then tetraethoxy is added, stop stirring after continuing to stir 30-40s, precipitation is there is in left at room temperature 1d to reaction soln, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid uses alcohol flushing 3 times after neutrality again, then control temperature is that 60-80 carries out drying, then controlling temperature rise rate is that 1 DEG C/min rises to 300-350 DEG C and carries out roasting 2-3h, obtain silicon dioxide microsphere,
(2), the preparation of the silicon dioxide microsphere of reaming
Step (1) silicon dioxide microsphere that obtains is immersed in complex salt solution and carries out reaming 40-60min, then control temperature is 60-80 DEG C and dries, then controlling temperature rise rate is roasting 2h at 1 DEG C/min rises to 350 DEG C, naturally cools to room temperature, then washes with water and use AgNO to effluent liquid
3detect without C1
? exist, obtain the silicon dioxide microsphere of reaming;
(3), load WO
3the preparation of mesoporous silicon dioxide micro-sphere
Using the silicon dioxide microsphere of the reaming of step (2) gained as hard template, Silicotungstic acid hydrate or phosphotungstic acid hydrate are the presoma preparing tungstic oxide microballoon, and introduced in mesoporous silicon dioxide micro-sphere duct by tungstic oxide microballoon, concrete steps are as follows:
First Silicotungstic acid hydrate is got or phosphotungstic acid hydrate is placed in dehydrated alcohol, stir under the rotating speed of 600rpm and make all to dissolve in dehydrated alcohol, slowly add the silicon dioxide microsphere of the reaming of step (2) gained, after 12h is stirred in sealing, in 50 DEG C of water-baths, solvent dehydrated alcohol evaporate to dryness is obtained white powder, white powder is placed in corundum crucible, then corundum crucible is put into retort furnace to control temperature rise rate 1 DEG C/min and be warming up to 350 DEG C and carry out annealing reaction 5h, be warming up to 600 DEG C again, temperature rise rate 1 DEG C/min, carry out annealing reaction 4h, then room temperature is naturally cooled to, obtain load WO
3mesoporous silicon dioxide micro-sphere,
The amount of above-mentioned dehydrated alcohol used, in dehydrated alcohol: the silicon dioxide microsphere of reaming is the ratio calculating of 100-250ml:1g; In various embodiments of the present invention, this step is only introduced for Silicotungstic acid hydrate, but does not limit phosphotungstic acid hydrate at preparation load WO
3mesoporous silicon dioxide micro-sphere in application;
(4), by the load WO of step (3) gained
3mesoporous silicon dioxide micro-sphere mass percent concentration be 10% HF aqueous acid soak 30min to remove silicon-dioxide, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid is neutral, and then with alcohol flushing 3 times, then control temperature is 50-80 DEG C and carries out dry 12-24h, obtains wide-aperture mesoporous WO
3microballoon.
beneficial effect of the present invention
Wide-aperture mesoporous WO of the present invention
3the preparation method of microballoon, due to utilize the silicon dioxide microsphere of complex salt solution reaming as template, the presoma of tungstic oxide microballoon, as the presoma preparing tungstic oxide, is introduced in mesoporous silicon dioxide micro-sphere duct, is obtained load WO by silicotungstic acid or phospho-wolframic acid
3mesoporous silicon dioxide micro-sphere, then obtain to remove silicon-dioxide the mesoporous WO that aperture is about 4.5nm
3microballoon.Its preparation technology is simple, under room temperature condition.
Accompanying drawing explanation
The field emission scanning electron microscope figure of the silicon dioxide microsphere of the reaming of Fig. 1 a, embodiment 1 step (2) gained;
The wide-aperture mesoporous WO of Fig. 1 b, embodiment 1 gained
3the electron diffraction scanning electron microscope (SEM) photograph of microballoon;
The wide-aperture mesoporous WO of Fig. 2 a, embodiment 2 gained
3n2 adsorption-the desorption isotherm of microballoon;
The wide-aperture mesoporous WO of Fig. 2 b, embodiment 2 gained
3the graph of pore diameter distribution of microballoon;
The wide-aperture mesoporous WO of Fig. 3 a, embodiment 3 gained
3the little angle XRD figure of microballoon;
The wide-aperture mesoporous WO of Fig. 3 b, embodiment 3 gained
3the big angle XRD figure of microballoon.
Embodiment
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
embodiment 1
A kind of wide-aperture mesoporous WO
3the preparation method of microballoon, specifically comprises the steps:
(1), the preparation of silicon dioxide microsphere
By 45mL water and the mixing of 50 mL Virahols, then 0.5g cetylamine is added, after under the ultrasound condition of 50KHz, ultrasonic 10-30min mixes, adding 0.7 mL concentration of volume percent is the ammoniacal liquor of 25-28%, under room temperature, controlling mixing speed is that 600r/min stirs 30min, then 2.9mL tetraethoxy is added, stop stirring after continuing to stir 30s, precipitation is there is in left at room temperature 1d to reaction soln, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid uses alcohol flushing 3 times after neutrality again, then control temperature is 60 DEG C and carries out drying, then controlling temperature rise rate is that 1 DEG C/min rises to 300 DEG C and carries out roasting 2h, obtain silicon dioxide microsphere,
(2), the preparation of the silicon dioxide microsphere of reaming
Step (1) silicon dioxide microsphere that obtains is immersed in complex salt solution and carries out reaming 40min; Then control temperature is 60 DEG C and dries, then roasting 2h(temperature rise rate 1 DEG C/min at 350 DEG C), naturally cool to room temperature.Then wash with water to effluent liquid without C1
? (use AgNO
3detect), obtain the silicon dioxide microsphere of reaming;
Above-mentioned complex salt solution used, by H
2o, NaCl, LiCl and KNO
3calculate in molar ratio, i.e. H
2o:NaCl:LiCl:KNO
3for the ratio of 39:3.4:1.2:0.5 mixes;
(3), load WO
3the preparation of mesoporous silicon dioxide micro-sphere
Using the silicon dioxide microsphere of the reaming of step (2) gained as hard template, Silicotungstic acid hydrate is the presoma preparing tungstic oxide microballoon, and introduced in mesoporous silicon dioxide micro-sphere duct by tungstic oxide microballoon, concrete steps are as follows:
First get 0.45g Silicotungstic acid hydrate and be placed in 50mL dehydrated alcohol, stir under the rotating speed of 600rpm and make all to dissolve in dehydrated alcohol, slowly add the silicon dioxide microsphere of the reaming of 0.2g step (2) gained, after 12h is stirred in sealing, in 50 DEG C of water-baths, solvent dehydrated alcohol evaporate to dryness is obtained white powder, white powder is placed in corundum crucible, then corundum crucible is put into retort furnace to control temperature rise rate 1 DEG C/min and be warming up to 350 DEG C and carry out annealing reaction 5h, be warming up to 600 DEG C again, temperature rise rate 1 DEG C/min, carry out annealing reaction 4h, then room temperature is naturally cooled to, obtain load WO
3mesoporous silicon dioxide micro-sphere,
The amount of the silicon dioxide microsphere of the reaming of above-mentioned Silicotungstic acid hydrate used, dehydrated alcohol, step (2) gained, in Silicotungstic acid hydrate: dehydrated alcohol: the silicon dioxide microsphere of the reaming of step (2) gained is the ratio calculating of 0.45g:50ml:0.2g;
(4), by the load WO of step (3) gained
3mesoporous silicon dioxide micro-sphere mass percent concentration be 10% HF aqueous acid soak 30min to remove silicon-dioxide, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid is neutral, and then with alcohol flushing 3 times, then control temperature is 60 DEG C and carries out dry 24h, obtains wide-aperture mesoporous WO
3microballoon.
Adopt scanning electronic microscope (S-4800, Hitachi) silicon dioxide microsphere of the reaming of above-mentioned steps (2) gained is measured, as shown in Figure 1a, as can be seen from Fig. 1 a, the silicon dioxide microsphere size uniform of the reaming of gained distributes the field emission scanning electron microscope figure of gained.
Adopt scanning electronic microscope (S-3400N, Hitachi) to the wide-aperture mesoporous WO of above-mentioned gained
3microballoon measures, the electron diffraction scanning electron microscope (SEM) photograph of gained as shown in Figure 1 b, as can be seen from Fig. 1 b, the mesoporous WO of gained
3microsphere Size is uniformly distributed.
embodiment 2
A kind of wide-aperture mesoporous WO
3the preparation method of microballoon, specifically comprises the steps:
(1), the preparation of silicon dioxide microsphere
By 45mL water and the mixing of 50 mL Virahols, then 1g cetylamine is added, after under the ultrasound condition of 75KHz, ultrasonic 10-30min mixes, add the ammoniacal liquor that 1.4mL concentration of volume percent is 25-28%, under room temperature, controlling mixing speed is that 600r/min stirs 30min, then 5.8mL tetraethoxy is added, stop stirring after continuing to stir 30s, precipitation is there is in left at room temperature 2d to reaction soln, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid uses alcohol flushing 3 times after neutrality again, then control temperature is 60 DEG C and carries out drying, then controlling temperature rise rate is that 1 DEG C/min rises to 320 DEG C and carries out roasting 2.5h, obtain silicon dioxide microsphere,
(2), the preparation of the silicon dioxide microsphere of reaming
Step (1) silicon dioxide microsphere that obtains is immersed in complex salt solution and carries out reaming 40min; Then control temperature is 60 DEG C and dries, then control temperature rise rate 1 DEG C/min be warming up to 350 DEG C at roasting 2h, naturally cool to room temperature, then wash with water and use AgNO to effluent liquid
3detect without C1
? exist, obtain the silicon dioxide microsphere of reaming;
Above-mentioned complex salt solution used, by H
2o, NaCl, LiCl and KNO
3calculate in molar ratio, i.e. H
2o:NaCl:LiCl:KNO
3for the ratio of 39:3.4:1.2:0.5 mixes;
(3), load WO
3the preparation of mesoporous silicon dioxide micro-sphere
Using the silicon dioxide microsphere of the reaming of step (2) gained as hard template, Silicotungstic acid hydrate is the presoma preparing tungstic oxide microballoon, and introduced in mesoporous silicon dioxide micro-sphere duct by tungstic oxide microballoon, concrete steps are as follows:
First get 0.9g Silicotungstic acid hydrate and be placed in 60mL dehydrated alcohol, stir under the rotating speed of 800rpm and make all to dissolve in dehydrated alcohol, slowly add the silicon dioxide microsphere of the reaming of 0.4g step (2) gained, after 15h is stirred in sealing, in 60 DEG C of water-baths, solvent dehydrated alcohol evaporate to dryness is obtained white powder, white powder is placed in corundum crucible, then corundum crucible is put into retort furnace to control temperature rise rate 1 DEG C/min and be warming up to 350 DEG C and carry out annealing reaction 5h, control temperature rise rate 1 DEG C/min to be again warming up to 600 DEG C and to carry out annealing reaction 4h, then room temperature is naturally cooled to, obtain load WO
3mesoporous silicon dioxide micro-sphere,
The amount of the silicon dioxide microsphere of the reaming of above-mentioned Silicotungstic acid hydrate used, dehydrated alcohol, step (2) gained, in Silicotungstic acid hydrate: dehydrated alcohol: the silicon dioxide microsphere of the reaming of step (2) gained is the ratio calculating of 0.45g:30ml:0.2g;
(4), by the load WO of step (3) gained
3mesoporous silicon dioxide micro-sphere mass percent concentration be 10% HF aqueous acid soak 30min to remove silicon-dioxide, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid is neutral, and then with alcohol flushing 3 times, then control temperature is 70 DEG C and carries out dry 18h, obtains wide-aperture mesoporous WO
3microballoon.
Adopt ratio surface area instrument (Micromeritics, ASAP 2020) to the wide-aperture mesoporous WO of above-mentioned gained
3microballoon carries out specific surface area and pore distribution test.Test result is as shown in Fig. 2 a, 2b, and Fig. 2 a, 2b are respectively mesoporous WO
3n2 adsorption-the desorption isotherm of microballoon, graph of pore diameter distribution; Can find out that from Fig. 2 a there is mesoporous WO
3microsphere sample there is typical Langmuir-IV type adsorption-desorption isothermal and H clearly
ihysteresis loop, this is the feature adsorpting type of typical mesoporous material, indicates this wide-aperture mesoporous WO thus
3microballoon has the feature of mesoporous material, can find out wide-aperture mesoporous WO from Fig. 2 b
3microballoon has single aperture distribution pattern, and pore size distribution is about about 4.5nm, indicates this wide-aperture mesoporous WO thus
3microballoon has pore passage structure.
embodiment 3
A kind of wide-aperture mesoporous WO
3the preparation method of microballoon, specifically comprises the steps:
(1), the preparation of silicon dioxide microsphere
By 45mL water and the mixing of 50mL Virahol, then 1g cetylamine is added, after under the ultrasound condition of 100KHz, ultrasonic 10-30min mixes, add the ammoniacal liquor that 1.4mL concentration of volume percent is 25-28%, under room temperature, controlling mixing speed is that 600r/min stirs 30min, then 5.8mL tetraethoxy is added, stop stirring after continuing to stir 30s, precipitation is there is in left at room temperature 2d to reaction soln, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid uses alcohol flushing 3 times after neutrality again, then control temperature is 60 DEG C and carries out drying, then controlling temperature rise rate is that 1 DEG C/min rises to 320 DEG C and carries out roasting 2.5h, obtain silicon dioxide microsphere,
(2), the preparation of the silicon dioxide microsphere of reaming
Step (1) silicon dioxide microsphere that obtains is immersed in complex salt solution and carries out reaming 40min; Then control temperature is 60 DEG C and dries, then control temperature rise rate 1 DEG C/min be warming up to 350 DEG C at roasting 2h, naturally cool to room temperature, then wash with water and use AgNO to effluent liquid
3detect without C1
? exist, obtain the silicon dioxide microsphere of reaming;
Above-mentioned complex salt solution used, by H
2o, NaCl, LiCl and KNO
3calculate in molar ratio, i.e. H
2o:NaCl:LiCl:KNO
3for the ratio of 39:3.4:1.2:0.5 mixes;
(3), load WO
3the preparation of mesoporous silicon dioxide micro-sphere
Using the silicon dioxide microsphere of the reaming of step (2) gained as hard template, Silicotungstic acid hydrate is the presoma preparing tungstic oxide microballoon, and introduced in mesoporous silicon dioxide micro-sphere duct by tungstic oxide microballoon, concrete steps are as follows:
First get 1.35g Silicotungstic acid hydrate and be placed in 60mL dehydrated alcohol, stir under the rotating speed of 800rpm and make all to dissolve in dehydrated alcohol, slowly add the silicon dioxide microsphere of the reaming of 0.6g step (2) gained, after 15h is stirred in sealing, in 60 DEG C of water-baths, solvent dehydrated alcohol evaporate to dryness is obtained white powder, white powder is placed in corundum crucible, then corundum crucible is put into retort furnace to control temperature rise rate 1 DEG C/min and be warming up to 350 DEG C and carry out annealing reaction 5h, control temperature rise rate 1 DEG C/min to be again warming up to 600 DEG C and to carry out annealing reaction 4h, then room temperature is naturally cooled to, obtain load WO
3mesoporous silicon dioxide micro-sphere,
The amount of the silicon dioxide microsphere of the reaming of above-mentioned Silicotungstic acid hydrate used, dehydrated alcohol, step (2) gained, in Silicotungstic acid hydrate: dehydrated alcohol: the silicon dioxide microsphere of the reaming of step (2) gained is the ratio calculating of 0.45g:20ml:0.2g;
(4), by the load WO of step (3) gained
3mesoporous silicon dioxide micro-sphere mass percent concentration be 10% HF aqueous acid soak 30min to remove silicon-dioxide, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid is neutral, and then with alcohol flushing 3 times, then control temperature is 80 DEG C and carries out dry 12h, obtains wide-aperture mesoporous WO
3microballoon.
Adopt X-ray diffractometer (X
,pert PW3040/60, PANalytical, Holland) to the wide-aperture mesoporous WO of above-mentioned gained
3microballoon powder carries out material phase analysis, and the little angle XRD figure spectrum of gained as shown in Figure 3 a, can be found out to have diffraction peak between 1-2 ° from Fig. 3 a, indicate this wide-aperture mesoporous WO thus
3microballoon powder has pore passage structure, has namely synthesized mesoporous tungsten trioxide; The big angle XRD figure of gained as shown in Figure 3 b, can find out with Silicotungstic acid hydrate to be the wide-aperture mesoporous WO of tungstic oxide presoma gained from Fig. 3 b
3microballoon is monoclinic phase, thus the product demonstrating gained is further mesoporous tungsten trioxide.
In sum, the wide-aperture mesoporous WO of one of the present invention
3the preparation method of microballoon, solves prior art intermediary hole WO
3mesoporous silicon dioxide micro-sphere (MS) pore size of template adopted in microballoon preparation process is less than 2nm, the mesoporous WO finally obtained
3the technical problem that microballoon aperture is little and a kind of wide-aperture mesoporous WO is provided
3the preparation method of microballoon, this preparation method with the silicon dioxide microsphere after reaming for template, the mesoporous WO finally obtained
3microballoon aperture is large, can reach about 4.5nm.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (3)
1. one kind
wide-aperturemesoporous WO
3the preparation method of microballoon, it is characterized in that this preparation method take cetylamine as template, Virahol is solubility promoter, tetraethoxy, concentration of volume percent are the ammoniacal liquor of 25-28% and deionized water is starting raw material, in water: Virahol: tetraethoxy: the volume ratio of ammoniacal liquor is that the ratio of 45:50:2.9:0.7 calculates;
First by after ultrasonic to water, Virahol and cetylamine mixing, stir 10-30min, then ammoniacal liquor, tetraethoxy is added successively, continue to be stirred in solution and occur precipitation, by sedimentation and filtration, washing, drying, then controlling temperature rise rate is that 1 DEG C/min rises to 300-350 DEG C and carries out roasting 2-3h, obtains silicon dioxide microsphere;
Then will obtain silicon dioxide microsphere to be immersed in complex salt solution and to carry out reaming, obtain the silicon dioxide microsphere of reaming;
Described complex salt solution, by H
2o, NaCl, LiCl and KNO
3calculate in molar ratio, i.e. H
2o:NaCl:LiCl:KNO
3for the ratio of 39:3.4:1.2:0.5 mixes;
Then using the silicon dioxide microsphere of reaming as hard template, Silicotungstic acid hydrate or phosphotungstic acid hydrate are the presoma preparing tungstic oxide microballoon, tungstic oxide microballoon is introduced in mesoporous silicon dioxide micro-sphere duct, in air atmosphere, control temperature rise rate 1 DEG C/min is warming up to 350-600 DEG C and carries out roasting 3-5h, obtained a kind of load WO
3mesoporous silicon dioxide micro-sphere;
After reaming, the consumption of silicon dioxide microsphere and Silicotungstic acid hydrate or phosphotungstic acid hydrate, calculates in mass ratio, i.e. silicon dioxide microsphere: Silicotungstic acid hydrate or phosphotungstic acid hydrate are 1:1-3;
Be finally the HF aqueous solution removing mesoporous silicon oxide of 10% with mass percent concentration, obtain
wide-aperturemesoporous WO
3microballoon.
2. as claimed in claim 1 a kind of
wide-aperturemesoporous WO
3the preparation method of microballoon, silicon dioxide microsphere and prepare the consumption of presoma of tungstic oxide after it is characterized in that reaming, calculates, i.e. silicon dioxide microsphere: Silicotungstic acid hydrate or phosphotungstic acid hydrate are 1:2.25 in mass ratio.
3. as claimed in claim 1 a kind of
wide-aperturemesoporous WO
3the preparation method of microballoon, is characterized in that specifically comprising the steps:
(1), the preparation of silicon dioxide microsphere
By deionized water and Virahol mixing, then cetylamine is added, be 50-100KHz in ultrasonic frequency, ultrasonic time is add the ammoniacal liquor that concentration of volume percent is 25-28% after 10-30min mixes, under room temperature, controlling mixing speed is that 600-800r/min stirs 10-30min, then tetraethoxy is added, stop stirring after continuing to stir 30-40s, precipitation is there is in left at room temperature 1d to reaction soln, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid uses alcohol flushing 3 times after neutrality again, then control temperature is that 60-80 carries out drying, then controlling temperature rise rate is that 1 DEG C/min rises to 300-350 DEG C and carries out roasting 2-3h, obtain silicon dioxide microsphere,
(2), the preparation of the silicon dioxide microsphere of reaming
Step (1) silicon dioxide microsphere that obtains is immersed in complex salt solution and carries out reaming 40-60min, then control temperature is 60-80 DEG C and dries, then controlling temperature rise rate is roasting 2h at 1 DEG C/min rises to 350 DEG C, naturally cools to room temperature, then washes with water and use AgNO to effluent liquid
3detect without C1
? exist, obtain the silicon dioxide microsphere of reaming;
(3), load WO
3the preparation of mesoporous silicon dioxide micro-sphere
Using the silicon dioxide microsphere of the reaming of step (2) gained as hard template, Silicotungstic acid hydrate or phosphotungstic acid hydrate are the presoma preparing tungstic oxide microballoon, and introduced in mesoporous silicon dioxide micro-sphere duct by tungstic oxide microballoon, concrete steps are as follows:
First Silicotungstic acid hydrate is got or phosphotungstic acid hydrate is placed in dehydrated alcohol, stir under the rotating speed of 600rpm and make all to dissolve in dehydrated alcohol, slowly add the silicon dioxide microsphere of the reaming of step (2) gained, after 12h is stirred in sealing, in 50 DEG C of water-baths, solvent dehydrated alcohol evaporate to dryness is obtained white powder, white powder is placed in corundum crucible, then corundum crucible is put into retort furnace to control temperature rise rate 1 DEG C/min and be warming up to 350 DEG C and carry out annealing reaction 5h, be warming up to 600 DEG C again, temperature rise rate 1 DEG C/min, carry out annealing reaction 4h, then room temperature is naturally cooled to, obtain load WO
3mesoporous silicon dioxide micro-sphere,
The amount of above-mentioned dehydrated alcohol used, in dehydrated alcohol: the silicon dioxide microsphere of reaming is the ratio calculating of 100-250ml:1g;
(4), by the load WO of step (3) gained
3mesoporous silicon dioxide micro-sphere mass percent concentration be 10% HF aqueous acid soak 30min to remove silicon-dioxide, then filter, the filter cake distilled water of gained cleans, until the pH of effluent liquid is neutral, and then with alcohol flushing 3 times, then control temperature is 50-80 DEG C and carries out dry 12-24h, to obtain final product
wide-aperturemesoporous WO
3microballoon.
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| CN113975454A (en) * | 2021-11-12 | 2022-01-28 | 延边大学 | Preparation and application of mesoporous silica/tannic acid composite hydrogel hemostatic material |
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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 |
| CN105948127A (en) * | 2016-05-03 | 2016-09-21 | 吉林大学 | Method for preparing white tungsten oxide |
| CN105948127B (en) * | 2016-05-03 | 2017-04-12 | 吉林大学 | Method for preparing white tungsten oxide |
| CN109115834A (en) * | 2018-08-01 | 2019-01-01 | 华东师范大学 | A kind of ppb grades of NO2Gas sheet type sensor and preparation method |
| CN112892522A (en) * | 2021-01-21 | 2021-06-04 | 华东理工大学 | Porous microsphere, Z-type photocatalyst, preparation method and application thereof |
| CN112892522B (en) * | 2021-01-21 | 2022-09-06 | 华东理工大学 | Porous microsphere, Z-type photocatalyst, preparation method and application thereof |
| CN113975454A (en) * | 2021-11-12 | 2022-01-28 | 延边大学 | Preparation and application of mesoporous silica/tannic acid composite hydrogel hemostatic material |
| CN114804747A (en) * | 2022-04-27 | 2022-07-29 | 西安德润九州新材料有限公司 | Ceramic tile binder and preparation method thereof |
| CN117089157A (en) * | 2023-09-19 | 2023-11-21 | 南通惟怡新材料科技有限公司 | Preparation method of quantum dot composite material |
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