CN103466721A - Cobalt molybdate hollow-ball powder material preparation method and cobalt molybdate hollow ball powder material - Google Patents
Cobalt molybdate hollow-ball powder material preparation method and cobalt molybdate hollow ball powder material Download PDFInfo
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Abstract
The invention relates to the field of molybdate and provides a preparation method of a cobalt molybdate powder material adopting a hollow ball structure. The preparation method comprises the following steps: using a dispersant to repeatedly wash yeast powder, and then using an activating agent to reactivate the yeast powder to obtain yeast cells; adding cobalt chloride hexahydrate and stirring for 2-4 h at the temeprature of 40-60 DEG C to enable the yeast cells to fully adsorb cobalt ions, and then adding sodium molybdate dihydrate, stirring at the constant temperature of 35-50 DEG C to obtain a purple sediment; seasoning the solution for 6-14 h at the temperature of 20-30 DEG C, centrifugally separating and drying the purple sediment; calcining the dried powder, and cooling to the room temperature to obtain cobalt molybdate micrometer-sized hollow balls. The hollow-ball powder has the average size of (2.0-4.5)*(1.5-4.0) mum, are about 100-400 nm in wall thickness, and is provided with a hollow part to accommodate a great amount of guest molecules to produce the wrapping effect, thereby achieving excellent physicochemical performance and wide application range.
Description
Technical field
The present invention relates to the molybdate field, especially relate to a kind of preparation method and cobalt molybdate hollow ball powder body material of cobalt molybdate hollow ball powder body material.
Background technology
At present, industry has obtained the cobalt molybdate micro Nano material of different dimensions and size by multiple preparation method, and these methods comprise: solid phase method has prepared the cobalt molybdate powder body material after solid precursors is mixed to also high-temperature calcination; Room temperature liquid phase ageing method has synthesized diameter 10～80nm, and length tens nm are to the cobalt molybdate nano rod of 1 μ m; Prepared diameter by hydrothermal method and be about 100nm, the cobalt molybdate nano rod of length 1 to 5 μ m; Utilize spray pyrolysis to prepare the cobalt molybdate thin-film material; Prepare the cobalt molybdate nano wire rod by chemical coprecipitation; Adopt sol-gel method, the citric acid of take is 60nm cobalt molybdate ultrafine particle etc. as complexing agent prepares particle diameter.
The pattern of the cobalt molybdate micro Nano material that above-mentioned method obtains is mainly the non-hollow structures such as nanometer rod, nano wire, ultrafine particle and film, they all do not possess by hollow space and hold a large amount of guest molecules and produce some peculiar parcel effects, and this has limited the excellent properties of cobalt molybdate micro Nano material and its application has also been caused to certain limitation.
Summary of the invention
The technical problem to be solved in the present invention is, above-mentioned defect for prior art, a kind of preparation method of cobalt molybdate powder body material is provided and makes cobalt molybdate hollow ball powder body material by the method, the cobalt molybdate powder body material that the method makes is hollow structure, there is hollow space, can hold a large amount of guest molecules and produce the parcel effect, thereby there is excellent physical and chemical performance, be widely used in various fields.
The technical solution adopted for the present invention to solve the technical problems is: a kind of cobalt molybdate powder body material preparation method of hollow ball structure is provided, yeast powder, after the repetitive scrubbing of dispersion agent, is carried out to activation treatment with activator to yeast powder, obtain yeast cell; Add cobalt chloride hexahydrate in the mixed solution of yeast cell and deionized water, the concentration that makes cobalt chloride hexahydrate is 0.05-0.1mol/L, and stirs 2～4h at 40～60 ℃ of temperature, makes the abundant adsorption of cobalt ion of yeast cell; Add two molybdic acid hydrate sodium in solution after, adding deionized water, to adjust the concentration of two molybdic acid hydrate sodium be 0.05-0.1mol/L, at 35-50 ℃ of lower constant temperature, is stirred to and obtains violet precipitate; By solution ageing 6～14h at 20～30 ℃ of temperature, centrifugation by the violet precipitate drying; Above-mentioned dried powder is calcined, then be cooled to room temperature, obtained the cobalt molybdate micrometre hollow sphere.
The further preferred version of the present invention is: described dispersion agent is deionized water or physiological saline, and the washing times of yeast powder is 2～5 times; Described activator is dehydrated alcohol.
The further preferred version of the present invention is: described activation treatment is that after dissolving by absolute ethyl alcohol and stirring, the speed with 2500～3500r/min in whizzer is carried out centrifugal 3～8min, removes supernatant liquor.
The further preferred version of the present invention is: described drying temperature is 60-90 ℃, time 4-14h.
The further preferred version of the present invention is: described calcining temperature is 400-600 ℃, and calcination time is 3-6h.
The further preferred version of the present invention is: described centrifugation is the process of with the speed of 2500～3500r/min, solid-liquid being separated in whizzer.
The further preferred version of the present invention is: when in described system, the quality of yeast cell template is 500-1500g, the two molybdic acid hydrate sodium that are added in solution are 2.5-10mol.
The further preferred version of the present invention is: described stirring is to utilize magnetic stirring apparatus to be stirred.
The further preferred version of the present invention is: described yeast cell is bread yeast dry powder or commodity yeast cell dry powder.
The invention provides a kind of cobalt molybdate hollow ball powder body material made by aforesaid method, the mean sizes of described hollow ball is 2.0～4.5*1.5～4.0 μ m, and wall thickness is about 100～400nm.
Beneficial effect of the present invention is, compared with prior art, the present invention is main raw material by adopting two molybdic acid hydrate sodium, cobalt chloride hexahydrate, utilize eco-friendly reaction conditions, and adopt cheap yeast cell to make cobalt molybdate micrometre hollow sphere powder body material, the mean sizes of gained hollow ball powder is 2.0～4.5*1.5～4.0 μ m, wall thickness is about 100～400nm, having hollow space holds a large amount of guest molecules and produces the parcel effect, thereby there is excellent physical and chemical performance, applied range.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
The X-ray diffractogram of the cobalt molybdate hollow ball of Fig. 1 embodiment 1 preparation;
The scanning electron microscope (SEM) photograph of the cobalt molybdate hollow ball of Fig. 2 embodiment 1 preparation;
The X-ray diffractogram of the cobalt molybdate hollow ball of Fig. 3 embodiment 2 preparations;
The scanning electron microscope (SEM) photograph of the cobalt molybdate hollow ball of Fig. 4 embodiment 2 preparations;
The energy spectrogram of the cobalt molybdate hollow ball of Fig. 5 embodiment 2 preparations;
The X-ray diffractogram of the cobalt molybdate hollow ball of Fig. 6 embodiment 3 preparations;
The scanning electron microscope (SEM) photograph of the cobalt molybdate hollow ball of Fig. 7 embodiment 3 preparations;
The X-ray diffractogram of the cobalt molybdate hollow ball of Fig. 8 embodiment 4 preparations;
The scanning electron microscope (SEM) photograph of the cobalt molybdate hollow ball of Fig. 9 embodiment 4 preparations.
Embodiment
Now by reference to the accompanying drawings, preferred embodiment of the present invention is elaborated.
The step of embodiments of the invention is as follows:
1, the washing of yeast cell and activation
Take yeast dry powder and mix in container with the ratio that dispersion agent adds the 3000mL dispersion agent in every 500g yeast powder, described dispersion agent is deionized water or 0.9% physiological saline.Mixed solution is stirring and dissolving after 30 minutes at room temperature, the centrifugal 5min of 3000r/s in whizzer, and after centrifugal end, abandoning supernatant, disperse with dispersion agent and centrifugal again, repeats this operation three times, realizes the abundant cleaning of dispersion agent to yeast cell surface.For the third time after centrifugal end, abandoning supernatant, yeast sedimentation after cleaning is carried out to activation treatment with activator, and activator is dehydrated alcohol, then carries out stirring and dissolving, the centrifugal 5min of 3000r/s in whizzer, after centrifugal end, abandoning supernatant, repeat twice of this operation, the yeast cell throw out proceeds in container, obtains the biological template yeast cell of surface active.
2, the absorption of yeast cell to cobalt ion
Take the cobalt chloride hexahydrate of 1.25-5mol in container with analytical balance, add a small amount of deionized water that it is dissolved fully and join in the yeast cell solution of step 1 preparation, add the deionized water constant volume, the concentration that makes cobalt chloride hexahydrate is 0.05-0.1mol/L.Utilize magnetic stirring apparatus to stir 1-4h to solution at 40-60 ℃ of temperature, thereby promote the absorption of yeast cell to cobalt ion.
3, cobalt molybdate generates and grows in the ageing of yeast cell surface
Take the two molybdic acid hydrate sodium of 1.25-5mol with analytical balance, with in interpolation system after a small amount of deionized water dissolving, and system is settled to 15000-60000mL, the concentration that makes two molybdic acid hydrate sodium is 0.05-0.1mol/L, after question response liquid mixes, with magnetic stirring apparatus, at 35-50 ℃ of temperature, stir until obtain a large amount of purple precipitations, then solution left standstill ageing, Aging Temperature 20-30 ℃, digestion time 6-14h.
4, the acquisition of hybrid material and drying
The system of step 3 gained is once centrifugal at the 3000r/s whizzer, centrifugal 5min, after centrifugal end, abandoning supernatant, then with dehydrated alcohol, throw out is washed 3 times, all centrifugal at the 3000r/s whizzer after each washing, centrifugal 5min, will be deposited in baking oven and obtain yeast-cobalt molybdate hydridization particle purple powder after dry a few hours.Above-mentioned oven drying temperature is 60-90 ℃, time 4-14h.
5. template is removed in high-temperature calcination
The dried powder that step 4 is obtained moves to high-temperature calcination in muffle furnace with key, after calcining finishes, after the taking-up sample, naturally cools to room temperature, and above-mentioned calcining temperature is 400-600 ℃, and calcination time is 3-6h.
The cobalt molybdate that the method for the embodiment of the present invention makes is X-ray diffraction (XRD) for powder body material, the means such as scanning electron microscope (SEM) and ultimate analysis (EDX) are studied the cobalt molybdate tiny balloon of preparation, result shows, the composition of the cobalt molybdate micrometre hollow sphere of making under these conditions is the cobalt molybdate material, the hollow ball mean sizes is 2.0～4.5*1.5～4.0 μ m, and wall thickness is about 100～400nm.
The reaction mechanism that the present invention prepares the cobalt molybdate micrometre hollow sphere is: in the preparation technology of cobalt molybdate hollow ball powder body material, yeast through repeatedly the washing and activation treatment after, at first with a certain amount of cobalt chloride hexahydrate, in system, mix, and with magnetic stirring apparatus, solution is mixed at a certain temperature, in this process, the functional group of yeast cell surface can interact with the cobalt ion in solution that dissociates, cell progressively is adsorbed in cell surface by cobalt ion, thereby has formed the hydration cobalt-iron layer at cell surface.Added two molybdic acid hydrate sodium in system after, under certain system temperature condition, solution neutralization is adsorbed in the molybdenum acid ion that the yeast cell surface cobalt ion all can dissociate with Sodium orthomolybdate and reacts, and in the yeast cell surface of adsorption of cobalt ion and the aqueous solution, starts to form cobalt molybdate molecule nano bundle simultaneously.According to slaking and gathering theory, under certain concentration conditions, in system, formed cobalt molybdate nano bundle can be realized by mutual Fast Collision the growth of particle.In this process, because system remains on higher temperature, the cobalt molybdate nano bundle that in addition is incorporated into yeast cell surface has very large surface-area, thereby has guaranteed efficiency that cobalt molybdate nano Shu Yougeng on the yeast template is high and cobalt molybdate molecule nano Shu Jinhang Collision coagulation the combination in solution.So, in ageing process, the cobalt molybdate nano particle growth progressively formed on cell walls, the cobalt molybdate wall thickness constantly increases, and has finally formed the hydridization particle of the nucleocapsid structure of yeast-cobalt molybdate.Through centrifugal, clean, dry and calcining, the biological template-yeast cell of hydridization granule interior is ashed removal, thereby has formed the structure of the consistent cobalt molybdate micrometre hollow sphere of pattern height.
Take 250g Angel Yeast powder and add in 15000ml physiological saline, fully stir 30min with magnetic stirring apparatus under room temperature, then centrifugal 5min under the 3000r/m condition, abandoning supernatant, disperse after washing centrifugal with physiological saline again, repeatedly carry out three times, again the yeast after cleaning is dissolved by absolute ethyl alcohol and stirring, under the 3000r/m condition after centrifugal 5min, abandoning supernatant, again with dehydrated alcohol, disperse activation, repeat twice of this operation; The precipitation obtained is mixed with deionized water, and add the 1.25mol cobalt chloride hexahydrate in mixed solution, the concentration that makes cobalt chloride hexahydrate is 0.083mol/L, at 50 ℃ of temperature, stirs 3h, makes the abundant adsorption of cobalt ion of yeast cell; Then slowly add 1.25mol bis-molybdic acid hydrate sodium and deionized waters in system, in the adjustment system, the concentration of two molybdic acid hydrate sodium is 0.083mol/L, stir above-mentioned solution until obtain a large amount of purples precipitations with magnetic stirring apparatus at 35 ℃, by solution at 30 ℃ of still aging 8h; Then to gained solution centrifugal 5min under the 3000r/m condition, and by throw out, put into 70 ℃ of dry 14h of baking oven; Dried powder is moved to crucible, and high-temperature calcination 6h in 400 ℃ of muffle furnaces, naturally cool to room temperature after the taking-up sample.Can obtain cobalt molybdate micrometre hollow sphere material, Fig. 1 confirms the powder body material that resulting materials is cobalt molybdate micrometre hollow sphere structure, and shown in Fig. 2, the hollow ball mean sizes is 4.1*3.8 μ m, and wall thickness is about 360nm.
Take 500g Angel Yeast powder and add in the 30000ml deionized water, fully stir 30min with magnetic stirring apparatus under room temperature, then centrifugal 5min under the 3000r/m condition, abandoning supernatant, disperse after washing centrifugal with deionized water again, repeatedly carry out three times, again the yeast after cleaning is dissolved by absolute ethyl alcohol and stirring, under the 3000r/m condition after centrifugal 5min, abandoning supernatant, again with dehydrated alcohol, disperse activation, repeat twice of this operation; The precipitation obtained is mixed with deionized water, and add the 2.5mol cobalt chloride hexahydrate in mixed solution, the concentration that makes cobalt chloride hexahydrate is 0.083mol/L, at 50 ℃ of temperature, stirs 3h, makes the abundant adsorption of cobalt ion of yeast cell; Then slowly add 2.5mol bis-molybdic acid hydrate sodium and deionized waters in system, in the adjustment system, the concentration of two molybdic acid hydrate sodium is 0.083mol/L, stir above-mentioned solution until obtain a large amount of purples precipitations with magnetic stirring apparatus at 40 ℃, by solution at 25 ℃ of still aging 12h; Then to gained solution centrifugal 5min under the 3000r/m condition, and by throw out, put into 80 ℃ of dry 8h of baking oven; Dried powder is moved to crucible, and high-temperature calcination 5h in 500 ℃ of muffle furnaces, naturally cool to room temperature after the taking-up sample.Can obtain cobalt molybdate micron hollow microspheres, Fig. 3 and Fig. 5 confirm the powder body material that resulting materials is cobalt molybdate micrometre hollow sphere structure, and Fig. 4 illustrates that the hollow ball mean sizes is 3.4*3.1 μ m, and wall thickness is about 320nm.
Take 450g Angel Yeast powder and add in 9000ml physiological saline, fully stir 30min with magnetic stirring apparatus under room temperature, then centrifugal 5min under the 3000r/m condition, abandoning supernatant, disperse after washing centrifugal with physiological saline again, repeatedly carry out three times, again the yeast after cleaning is dissolved by absolute ethyl alcohol and stirring, under the 3000r/m condition after centrifugal 5min, abandoning supernatant, again with dehydrated alcohol, disperse activation, repeat twice of this operation; The precipitation obtained is mixed with deionized water, and add the 0.75mol cobalt chloride hexahydrate in mixed solution, the concentration that makes cobalt chloride hexahydrate is 0.083mol/L, at 55 ℃ of temperature, stirs 2h, makes the abundant adsorption of cobalt ion of yeast cell; Then slowly add 0.75mol bis-molybdic acid hydrate sodium and deionized waters in system, in the adjustment system, the concentration of two molybdic acid hydrate sodium is 0.083mol/L, stir above-mentioned solution until obtain a large amount of purples precipitations with magnetic stirring apparatus at 45 ℃, by solution at 30 ℃ of still aging 6h; Then to gained solution centrifugal 5min under the 3000r/m condition, and by throw out, put into 70 ℃ of dry 12h of baking oven; Dried powder is moved to crucible, and high-temperature calcination 4h in 600 ℃ of muffle furnaces, naturally cool to room temperature after the taking-up sample.Can obtain cobalt molybdate micron hollow microspheres, Fig. 6 confirms the powder body material that resulting materials is cobalt molybdate micrometre hollow sphere structure, and Fig. 7 illustrates that the hollow ball mean sizes is 2.9*2.7 μ m, and wall thickness is about 200nm.
Take 600g Angel Yeast powder and add in the 12000ml deionized water, fully stir 30min with magnetic stirring apparatus under room temperature, then centrifugal 5min under the 3000r/m condition, abandoning supernatant, disperse after washing centrifugal with deionized water again, repeatedly carry out three times, again the yeast after cleaning is dissolved by absolute ethyl alcohol and stirring, under the 3000r/m condition after centrifugal 5min, abandoning supernatant, again with dehydrated alcohol, disperse activation, repeat twice of this operation; The precipitation obtained is mixed with deionized water, and add the 1mol cobalt chloride hexahydrate in mixed solution, the concentration that makes cobalt chloride hexahydrate is 0.083mol/L, at 50 ℃ of temperature, stirs 4h, makes the abundant adsorption of cobalt ion of yeast cell; Then slowly add 1mol bis-molybdic acid hydrate sodium and deionized waters in system, in the adjustment system, the concentration of two molybdic acid hydrate sodium is 0.083mol/L, stir above-mentioned solution until obtain a large amount of purples precipitations with magnetic stirring apparatus at 45 ℃, by solution at 25 ℃ of still aging 14h; Then to gained solution centrifugal 5min under the 3000r/m condition, and by throw out, put into 80 ℃ of dry 10h of baking oven; Dried powder is moved to crucible, and high-temperature calcination 3h in 600 ℃ of muffle furnaces, naturally cool to room temperature after the taking-up sample.Can obtain cobalt molybdate micron hollow microspheres, Fig. 8 confirms the powder body material that resulting materials is cobalt molybdate micrometre hollow sphere structure, and Fig. 9 illustrates that the hollow ball mean sizes is 2.6*2.5 μ m, and wall thickness is about 200nm.
In the preparation technology of the embodiment of the present invention, focus on the one hand the strength of solution in reaction process is strictly controlled, effectively reduced the impact on liquor capacity and material concentration of absorption and heat-processed; On the other hand, the technology utilization heated and stirred realizes the generation step of cobalt molybdate, the solution system that the innovation of technique has overcome lower concentration preferably at room temperature is difficult to realize a large amount of problems that generate of yeast-cobalt molybdate hydridization particle, in the successful preparation of yeast in realizing the solution system of lower concentration-cobalt molybdate hydridization particle, effectively by the free cobalt molybdate impurity generated in solution, be down to minimum, prepared cobalt molybdate powder body material surface is long-pending larger, impurity particle is few, and physical and chemical performance is good.
Should be understood that; for those of ordinary skills, can be improved according to the above description described yeast cell conversion; and the replacement of molybdate material, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (10)
1. the preparation method of cobalt molybdate hollow ball powder body material, is characterized in that: yeast powder, after the repetitive scrubbing of dispersion agent, is carried out to activation treatment with activator to yeast powder, obtain yeast cell; Add cobalt chloride hexahydrate in the mixed solution of yeast cell and deionized water, the concentration that makes cobalt chloride hexahydrate is 0.05-0.1mol/L, and stirs 2～4h at 40～60 ℃ of temperature, makes the abundant adsorption of cobalt ion of yeast cell; Add two molybdic acid hydrate sodium in solution after, adding deionized water, to adjust the concentration of two molybdic acid hydrate sodium be 0.05-0.1mol/L, at 35-50 ℃ of lower constant temperature, is stirred to and obtains violet precipitate; By solution ageing 6～14h at 20～30 ℃ of temperature, centrifugation by the violet precipitate drying; Above-mentioned dried powder is calcined, then be cooled to room temperature, obtained the cobalt molybdate micrometre hollow sphere.
2. preparation method according to claim 1, it is characterized in that: described dispersion agent is deionized water or physiological saline, the washing times of yeast powder is 2～5 times; Described activator is dehydrated alcohol.
3. preparation method according to claim 1, it is characterized in that: described activation treatment is that after dissolving by absolute ethyl alcohol and stirring, the speed with 2500～3500r/min in whizzer is carried out centrifugal 3～8min, removes supernatant liquor.
4. preparation method according to claim 1, it is characterized in that: described drying temperature is 60-90 ℃, time 4-14h.
5. preparation method according to claim 1, it is characterized in that: described calcining temperature is 400-600 ℃, calcination time is 3-6h.
6. preparation method according to claim 1, it is characterized in that: described centrifugation is the process of with the speed of 2500～3500r/min, solid-liquid being separated in whizzer.
7. preparation method according to claim 1, it is characterized in that: when in described system, the quality of yeast cell is 500-1500g, the two molybdic acid hydrate sodium that are added in solution are 2.5-10mol.
8. preparation method according to claim 1, it is characterized in that: described stirring is to utilize magnetic stirring apparatus to be stirred.
9. preparation method according to claim 1, it is characterized in that: described yeast cell is bread yeast dry powder or commodity yeast cell dry powder.
10. the cobalt molybdate hollow ball powder body material made by the described method of claim 1, it is characterized in that: the mean sizes of described hollow ball is 2.0～4.5*1.5～4.0 μ m, and wall thickness is about 100～400nm.
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| CN115465898A (en) * | 2022-09-19 | 2022-12-13 | 陕西红马科技有限公司 | Method for preparing hollow sphere cobaltosic oxide by bionic method |
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Cited By (7)
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| CN107970944A (en) * | 2017-12-05 | 2018-05-01 | 惠州学院 | A kind of preparation method and applications of compound molybdate tiny balloon |
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| CN109012683A (en) * | 2018-08-09 | 2018-12-18 | 扬州大学 | A kind of preparation method of cobalt molybdate tiny balloon elctro-catalyst |
| CN109012683B (en) * | 2018-08-09 | 2021-05-14 | 扬州大学 | Preparation method of cobalt molybdate hollow microsphere electrocatalyst |
| CN115465898A (en) * | 2022-09-19 | 2022-12-13 | 陕西红马科技有限公司 | Method for preparing hollow sphere cobaltosic oxide by bionic method |
| CN115465898B (en) * | 2022-09-19 | 2024-01-30 | 陕西红马科技有限公司 | Method for preparing hollow sphere cobaltosic oxide by using bionic method |
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