CN101898749A - Method for preparing metal oxide hollow particles or fibers - Google Patents
Method for preparing metal oxide hollow particles or fibers Download PDFInfo
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Abstract
The invention relates to a method for preparing metal oxide hollow particles, metal oxide hollow fibers, metal hollow particles or metal hollow fibers. The method for preparing the metal oxide hollow particles or the metal oxide hollow fibers is characterized by comprising the following steps of: putting composite particles or composite fibers containing a metal compound and a polymer into a furnace, treating the composite particles or the composite fibers at the temperature of between 300 and 1,000 DEG C for 10min to 48h at the temperature rate of 5 to 400 DEG C/min, and cooling the product along with the furnace to obtain the metal oxide hollow particles or the metal oxide hollow fibers. The method is simple; and the hollow particles or the hollow fibers with different internal hollow structures can be obtained by adjusting the temperature rate.
Description
Technical field
The present invention relates to a kind of metal oxide hollow particle, metal oxide hollow fiber, metal hollow particle or metal hollow fiber preparation method.
Background technology
Micro-and nano-particles and fiber with hollow structure, because its low density, high-specific surface area and low thermal expansivity are widely used in drug conveying, catalysis, sensing, Chu Qing, fields such as lithium cell and microreactor (Lou, X.W.; Archer, L.A.; Yang Z.C.Adv.Mater.2008,20,3987).Especially, be described as the multi-stage hollow nanoparticle with multistage internal structure and fiber (the Multilevel Hollow Nanoparticles and nanofibers of third generation nano material, MHNPs and MHNFs, comprise that nucleocapsid is hollow, multilayer hollow and multi-cavity chamber hollow Nano particle and fiber) caused extensive concern (Zhao, the Y. of various countries' researchers; Jiang, L.Adv.Mater.2009,21,1).With respect to the first-generation (as nanoparticle, nanometer rod etc.) and s-generation nano material (as hollow ball, nanotubes etc.), multi-stage hollow nanoparticle and fiber have following characteristics: (1) has multilayer micro-nano hollow structure and multiple interface, might cause new physicochemical property; (2) its complex inner structure helps controlling better the physics and the chemical environment at each position of particle; (3) have multiple internal surface and high-specific surface area, have higher activity than the solid of same size and individual layer hollow material, in drug conveying, catalysis, sensing, Chu Qing, the better properties that the performance of aspects such as lithium cell and microreactor makes new advances.As Q.S.Zhu seminar (Zhang, H.G.; Zhu, Q.S.; Zhang, Y.; Wang, Y.; Zhao, L.; Yu, B.Adv.Funct.Mater.2007,17,2766) discover Cu
2The sensitivity to the ethanol vapor detection (8.2) of O multilayer hollow particle is far above Cu
2The solid microparticle (1.5) of O nanocrystalline (2.7) and same size; (Ikeda, S. such as Ikeda; Ishino, S.; Harada, T.; N.Okamoto, N.; Sakata, T.; Mori, H.; Kuwabata, S.; Torimoto, T.; Matsumura, M.Angew.Chem.Int.Ed.2006,45,7063) find that the hud typed hollow Nano particle of Pt@C has than the higher productive rate of other forms of Pt catalyzer and better recycles characteristic on catalytic hydrogenation reaction.
At present, template is as a kind of method with high controllability, is widely used in preparation (Xu, the H.L. of individual layer hollow and multi-stage hollow micro-and nano-particles and fiber; Wang, W.Z.Angew.Chem.Int.Ed.2007,46,1489).Template be utilize in advance the synthetic micro nano structure as framework (as SiO
2Or PS ball etc.), adopts the method that successively coats, and remove template subsequently and obtain the second hollow and multi-stage hollow structure of individual layer of material mutually with transition layer at its surface deposition multilayer second phase material and transition layer.But solutions of still needing of several problems arranged when the hollow and multi-stage hollow micro-and nano-particles of preparation individual layer: 1) sedimentation velocity slowly and can not large area deposition be difficult to satisfy the needs of heavy industrialization; 2) preparation section is loaded down with trivial details, and the treatment process of template is more, and it is perfect to require template quality to be close to, and disturbed by ambient conditions, causes deposition quality to descend, and settled layer intensity is low; 3) template used must the removal, this has brought trouble for the hollow and multi-stage hollow micro-and nano-particles subsequent applications of individual layer, and hollow structure is subsided easily and is out of shape.Therefore, utilize the non-template legal system to be equipped with the hollow and multi-stage hollow micro-and nano-particles of individual layer and become the new direction that the skilled worker person of section explores in recent years.Wherein representative method is based on Kirkendall effect and the machine-processed method for preparing hollow granule of Ostwald slaking.The Kirkendall effect is meant a kind of phenomenon of atom two kinds of material interface diffusions, can obtain the hollow Nano particle if atomic diffusion and cavity accumulative direction are controlled.Ostwald slaking mechanism is meant a kind of mechanism that constantly consumes little crystal grain in the process of growth of big crystal grain, if the grain size distribution of particle agglomeration is controlled, so crystal grain during in subsequent growth hollow nanoparticle can form.But often be the comparatively simple hollow or individual layer nucleocapsid hollow granule of individual layer based on the hollow granule that Kirkendall effect and Ostwald slaking mechanism prepare, also can't be to control (Yin, the Y.D. of the structure realization system of product; Rioux, R.M.; Erdonmez, C.K.; Hughes, S.; Somorjai, G.A.; Alivisatos, A.P.Science 2004,304, and 711; Liu, B.; Zeng, H.C.Small2005,1,566).Patent CN101293192A utilizes the tensio-active agent vesica to prepare individual layer and multiple layer metal oxide compound hollow granule as template, patent CN101318710A adopts the Ostwald slaking mechanism under the solvent thermal condition to prepare ferric oxide nucleocapsid hollow granule, contains the composite precursor particle of metallic compound and polymkeric substance or method that the non-homogeneous contractile mechanism of fiber under the rapid heating condition prepares various metals or poly-metal deoxide hollow granule and fiber does not see that as yet report is arranged but utilize.
Summary of the invention
The purpose of this invention is to provide a kind of metal oxide hollow particle or fiber preparation method, this method is simple and easy, can obtain having different boring structure of hollow particles or hollow fiber by regulating temperature rise rate.
To achieve these goals, the technical solution used in the present invention is: a kind of metal oxide hollow particle or fiber preparation method, it is characterized in that it comprises the steps: the composite particles or the conjugated fibre that contain metallic compound and polymkeric substance are put in the stove, temperature rise rate with 5-400 ℃/min is handled 10min-48h to it under 300-1000 ℃, obtain metal oxide hollow particle or metal oxide hollow fiber behind the furnace cooling.
With above-mentioned metal oxide hollow particle or metal oxide hollow fiber is raw material, carries out reduction reaction (through H
2Or reduction such as CO), can obtain metal hollow particle or metal hollow fiber.
The described preparation (spray method) that contains the composite particles of metallic compound and polymkeric substance: the mass ratio of pressing metal compound and polymkeric substance is (0.1-10): 1, and choose metallic compound and polymkeric substance and dissolving and be mixed with concentration (the quality sum of metallic compound and polymkeric substance and the ratio of solution quality) and be the electrostatic spray precursor solution of 20-40wt.%; The electrostatic spray precursor solution placed the electrostatic spray feeding device that diameter is the 0.6mm syringe needle is housed, the feed speed of solution is 0.02-0.2mL/h, adopt the operating voltage of 7-30kV under 25 ℃ of room temperatures, to carry out electrostatic spray, at distance syringe needle 4-15cm place, collect the electrostatic spray product with aluminium flake, obtain containing the composite particles of metallic compound and polymkeric substance.
The described preparation that contains the composite particles of metallic compound and polymkeric substance also can be adopted the emulsion polymerisation process preparation.
The described preparation (utilizing spinning processes) that contains the conjugated fibre of metallic compound and polymkeric substance: the mass ratio of pressing metal compound and polymkeric substance is (0.1-10): 1, and choose metallic compound and polymkeric substance and dissolving and be mixed with concentration (the quality sum of metallic compound and polymkeric substance and the ratio of solution quality) and be the electrostatic spinning precursor solution of 45-60wt.%; The electrostatic spinning precursor solution placed the electrostatic spinning feeding device that diameter is the 0.6mm syringe needle is housed, the feed speed of solution is 0.1-1mL/h, adopt the operating voltage of 10-30kV under 25 ℃ of room temperatures, to carry out electrostatic spinning, at distance syringe needle 4-20cm place, collect the electrostatic spinning product with copper mesh, obtain containing the conjugated fibre of metallic compound and polymkeric substance.
Described metallic compound is any one or any mixture that (contains any two kinds) more than two kinds in metal organic acid salt, metal inorganic salt, the organometallic complex etc., and any is any proportioning when (containing any two kinds) more than two kinds and mixing.
Described metal organic acid salt is the mixing of any one or two kinds in acetate, the Citrate trianion etc., and two kinds is any proportioning when mixing; Described metal inorganic salt is any one or any mixing that (contains any two kinds) more than two kinds in halogen, nitrate, the vitriol etc., and any is any proportioning when (containing any two kinds) more than two kinds and mixing.
Described organometallic complex is the carbonyl compound of metal Fe, Co or Ni, perhaps is butyl (tetra) titanate, aluminum isopropylate or ethanol tantalum etc.
Acetate is the acetate of the metal ion of Fe, Co, Ni, Zn, Cu, Ba or Sr etc.; Citrate trianion is the Citrate trianion of the metal ion of Fe, Co, Ni, Zn, Cu, Ba or Sr etc.; Halogen is the halogen of the metal ion of Fe, Co, Ni, Zn, Cu, Ba or Sr etc., nitrate is the nitrate of the metal ion of Fe, Co, Ni, Zn, Cu, Ba or Sr etc., and carbonate is the carbonate of the metal ion of Fe, Co, Ni, Zn, Cu, Ba or Sr etc.
Described polymkeric substance is any one or any mixing that (contains any two kinds) more than two kinds in polyvinylpyrrolidone (PVP), polystyrene (PS), polyethylene (PE), polyoxyethylene (PEO), the polyacrylonitrile (PANI) etc., and any is any proportioning when (containing any two kinds) more than two kinds and mixing.
Described metal oxide hollow particle is: the metal oxide hollow particle that individual layer is hollow, nucleocapsid is hollow, multilayer is hollow or multi-layer core-shell is hollow.
Described metal oxide hollow fiber is: the metal oxide hollow fiber that individual layer is hollow, nucleocapsid is hollow, multilayer is hollow or multi-layer core-shell is hollow.
Metal oxide hollow particle or fiber with the inventive method preparation comprise: M
xFe
yO
z, M
xO
y(M=Fe, Co, Ni, Zn, Cu, Ba, Sr, metal ions such as Ti).
The invention has the beneficial effects as follows: the present invention utilizes the composite particles of metallic compound and polymkeric substance or metal oxide hollow particle and the fiber that the non-homogeneous contraction of fiber under the rapid heating condition prepares various boring structures, can obtain having different boring structure of hollow particles or fiber [temperature rise rate is 5-400 ℃/min by regulating temperature rise rate, from low paramount, can obtain successively that individual layer is hollow, nucleocapsid is hollow, multilayer (nucleocapsid) hollow granule or fiber].
It is simple that present method and template relatively have technology, and the time is short, and large-scale production is convenient in control easily; Compare with hollow granule (fiber) preparation method based on Kirkendall effect and Ostwald slaking mechanism, present method can realize product structure hollow hollow to nucleocapsid by individual layer simply by the adjusting to temperature rise rate, again to multilayer (nucleocapsid) hollow granule or fiber.
Description of drawings
Fig. 1 is prepared γ-Fe
2O
3(A) individual layer is hollow, and (B) nucleocapsid is hollow, (C) double-layer hollow, (D) the transmission electron microscope figure of double-deck nucleocapsid hollow granule.
Fig. 2 is prepared γ-Fe
2O
3(A) nucleocapsid is hollow, (B) scanning electron microscope diagram of double-layer hollow fiber.
Fig. 3 is prepared α-Fe
2O
3(A) nucleocapsid is hollow, (B) scanning electron microscope diagram of double-layer hollow fiber.
Fig. 4 is prepared CoFe
2O
4(A) nucleocapsid is hollow, (B) the transmission electron microscope figure of double-layer hollow particle.
Fig. 5 is prepared NiFe
2O
4(A) nucleocapsid is hollow, (B) the transmission electron microscope figure of double-layer hollow particle.
Fig. 6 is prepared BaFe
12O
19The scanning electron microscope diagram of double-layer hollow fiber.
Fig. 7 is the γ-Fe of preparation
2O
3, α-Fe
2O
3, CoFe
2O
4, NiFe
2O
4, and BaFe
12O
19The XRD figure of hollow structure material.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but do not limit the present invention.
Embodiment 1: γ-Fe
2O
3Individual layer is hollow, nucleocapsid is hollow, the preparation of double-layer hollow, double-deck nucleocapsid hollow granule:
1) polyvinylpyrrolidone (PVP) being dissolved in the concentration that 30mL prepares in advance is in the ironic citrate solution of 0.1g/mL, the mass ratio of ironic citrate and polyvinylpyrrolidone (PVP) is 5: 4, heats the magnetic agitation dehydration down at 60 ℃ and makes the concentration of solute (ironic citrate and PVP) reach 40wt.% formation electrostatic spray precursor solution; The electrostatic spray precursor solution placed the electrostatic spray feeding device that diameter is the 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV under 25 ℃ of room temperatures, to carry out electrostatic spray, at distance syringe needle 15cm place, collect electrostatic spray product---PVP/ ironic citrate composite particles with aluminium flake.
2) above-mentioned PVP/ ironic citrate composite particles is placed the tube furnace of temperature programmed control together with aluminium flake, temperature rise rate with 10 ℃/min rises to 500 ℃, continue calcining 2h then under this temperature, PVP and ironic citrate are decomposed, furnace cooling can prepare γ-Fe
2O
3The individual layer hollow granule;
Temperature rise rate is heightened to 20 ℃/min, repeated above-mentioned thermal treatment process and can obtain γ-Fe
2O
3The nucleocapsid hollow granule;
Temperature rise rate is heightened to 50 ℃/min, repeated above-mentioned thermal treatment process and can obtain γ-Fe
2O
3The double-layer hollow particle;
Temperature rise rate is heightened to 250 ℃/min, repeated above-mentioned thermal treatment process and can obtain γ-Fe
2O
3Double-deck nucleocapsid hollow granule; γ-Fe
2O
3The XRD figure of double-deck nucleocapsid hollow granule product is shown in the A among Fig. 4.
Utilize transmission electron microscope (TEM, JEM-2100F, JEOL Co., Ltd., Japan) and field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan) structure and the pattern to product characterizes, the structure of the individual layer hollow granule for preparing, nucleocapsid hollow granule, double-layer hollow particle and double-deck nucleocapsid hollow granule and pattern are shown in the A among Fig. 1, B, C and D, and the A among Fig. 1, B, C and D have illustrated that the product that obtains is individual layer hollow granule, nucleocapsid hollow granule, double-layer hollow particle and double-deck nucleocapsid hollow granule.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd. is Japan) to γ-Fe
2O
3The thing of double-deck nucleocapsid hollow granule product characterizes mutually, shows that preparing product is γ-Fe
2O
3, shown in the A among Fig. 7.
Embodiment 2: γ-Fe
2O
3Nucleocapsid is hollow, the double-layer hollow fiber production:
1): it is in the ironic citrate solution of 0.1g/mL that polyvinylpyrrolidone (PVP) is dissolved in the concentration that 30mL prepares in advance, the mass ratio of ironic citrate and PVP is 4: 1, heats the magnetic agitation dehydration down at 60 ℃ and makes the concentration of solute (ironic citrate and PVP) reach 50wt.% formation electrostatic spinning precursor solution; Precursor solution placed the electrostatic spinning feeding device that diameter is the 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV under 25 ℃ of room temperatures, to carry out electrostatic spinning, at distance syringe needle 15cm place, collect electrostatic spray product P VP/ ironic citrate conjugated fibre with copper mesh.
2) above-mentioned PVP/ ironic citrate conjugated fibre is transferred to the porcelain boat and with it from copper mesh placed the tube furnace of temperature programmed control together, temperature rise rate with 100 ℃/min rises to 500 ℃, under this temperature, continue calcining 2h then, PVP and ironic citrate are decomposed, and furnace cooling can prepare γ-Fe
2O
3The nucleocapsid hollow fiber is shown in the A among Fig. 2;
Temperature rise rate is heightened to 250 ℃/min, repeated above-mentioned thermal treatment process and can obtain γ-Fe
2O
3The double-layer hollow fiber is shown in the B among Fig. 1.
Utilize field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan) structure and the pattern to product characterizes, the nucleocapsid hollow fiber for preparing, the structure of double-layer hollow fiber and pattern are shown in A and B among Fig. 2, and the A among Fig. 2 has illustrated that the product that obtains is the nucleocapsid hollow fiber, and the B among Fig. 2 has illustrated that the product that obtains is the double-layer hollow fiber.
Embodiment 3 α-Fe
2O
3Nucleocapsid is hollow, the double-layer hollow fiber production:
1) polyvinylpyrrolidone (PVP) being dissolved in the concentration that 30mL prepares in advance is in the ironic citrate solution of 0.1g/mL, the mass ratio of ironic citrate and PVP is 4: 1, heats the magnetic agitation dehydration down at 60 ℃ and makes the concentration of solute (ironic citrate and PVP) reach 55wt.% formation static spray spinning precursor solution; Precursor solution placed the electrostatic spinning feeding device that diameter is the 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV under 25 ℃ of room temperatures, to carry out electrostatic spinning, at distance syringe needle 15cm place, collect electrostatic spray product---PVP/ ironic citrate conjugated fibre with copper mesh.
2) above-mentioned PVP/ ironic citrate conjugated fibre is transferred to the porcelain boat and with it from copper mesh placed the tube furnace of temperature programmed control together, after rising to 400 ℃ of pre-treatment 30min with the temperature rise rate of 100 ℃/min, temperature rise rate with 10 ℃/min rises to 800 ℃, under this temperature, continue calcining 2h then, PVP and ironic citrate are decomposed fully, and furnace cooling can prepare α-Fe
2O
3The nucleocapsid hollow fiber.
The pre-treatment temperature rise rate is heightened to 200 ℃/min, repeated above-mentioned thermal treatment process and can obtain α-Fe
2O
3The double-layer hollow fiber.
Utilize field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan) structure and the pattern to product characterizes, the nucleocapsid hollow fiber for preparing and the structure and morphology of double-layer hollow fiber are shown in A and B among Fig. 3.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd., Japan) thing to product characterizes mutually, shows that preparing the double-layer hollow fiber product is α-Fe
2O
3, shown in the B among Fig. 7.
Embodiment 4:CoFe
2O
4Nucleocapsid is hollow, the double-layer hollow particle preparation:
1) polyvinylpyrrolidone (PVP) and cobaltous acetate being dissolved in the concentration that 30mL prepares in advance is in the ironic citrate solution of 0.1g/mL, the mass ratio of ironic citrate and PVP is 5: 4, the mol ratio of ironic citrate and cobaltous acetate is 2: 1, heating the magnetic agitation dehydration down at 60 ℃ makes the concentration of solute (ironic citrate, cobaltous acetate and PVP) reach 40wt.% formation electrostatic spray precursor solution; Precursor solution placed the electrostatic spray feeding device that diameter is the 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV under 25 ℃ of room temperatures, to carry out electrostatic spray, at distance syringe needle 15cm place, collect electrostatic spray product---metallic compound composite particles with aluminium flake.
2) above-mentioned electrostatic spray product is placed the tube furnace of temperature programmed control together with aluminium flake, rise to 500 ℃ with the temperature rise rate of 50 ℃/min, continue calcining 2h then under this temperature, PVP and ironic citrate are decomposed, furnace cooling can prepare CoFe
2O
4The nucleocapsid hollow granule;
Temperature rise rate is heightened to 100 ℃/min, repeated above-mentioned thermal treatment process and can obtain CoFe
2O
4The double-layer hollow particle.
Utilize transmission electron microscope (TEM, JEM-2100F, JEOL Co., Ltd., Japan) structure and the pattern to product characterizes, nucleocapsid hollow granule for preparing and double-layer hollow morphology of particles and pattern are shown in A and B among Fig. 4.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd., Japan) thing to product characterizes mutually, shows that preparing product is CoFe
2O
4Shown in the C among Fig. 7.
Embodiment 5NiFe
2O
4Nucleocapsid is hollow, the double-layer hollow particle preparation:
1) polyvinylpyrrolidone (PVP) and nickelous acetate being dissolved in the concentration that 30mL prepares in advance is in the ironic citrate solution of 0.1g/mL, the mass ratio of ironic citrate and PVP is 5: 4, the mol ratio of ironic citrate and nickelous acetate is 2: 1, heating the magnetic agitation dehydration down at 60 ℃ makes the concentration of solute (ironic citrate, nickelous acetate and PVP) reach 40wt.% formation electrostatic spray precursor solution; Precursor solution placed the electrostatic spray feeding device that diameter is the 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV under 25 ℃ of room temperatures, to carry out electrostatic spray,, collect the electrostatic spray product with aluminium flake at distance syringe needle 15cm place.
2) above-mentioned electrostatic spray product is placed the tube furnace of temperature programmed control together with the aluminium flake substrate, rise to 500 ℃ with the temperature rise rate of 50 ℃/min, continue calcining 2h then under this temperature, PVP and ironic citrate are decomposed, furnace cooling can prepare CoFe
2O
4The nucleocapsid hollow granule.
Temperature rise rate is heightened to 100 ℃/min, repeated above-mentioned thermal treatment process and can obtain CoFe
2O
4The double-layer hollow particle.
Utilize transmission electron microscope (TEM, JEM-2100F, JEOL Co., Ltd., Japan) structure and the pattern to product characterizes, nucleocapsid hollow granule for preparing and double-layer hollow morphology of particles and pattern are shown in A and B among Fig. 5.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd., Japan) thing to product characterizes mutually, shows that the thing for preparing product is mutually for NiFe
2O
4, shown in the D among Fig. 7.
Embodiment 6BaFe
12O
19The double-layer hollow fiber production
1) polyvinylpyrrolidone (PVP) and barium acetate being dissolved in the concentration that 30mL prepares in advance is in the ironic citrate solution of 0.1g/mL, the mass ratio of ironic citrate and PVP is 4: 1, the mol ratio of ironic citrate and nickelous acetate is 12: 1, heating the magnetic agitation dehydration down at 60 ℃ makes the concentration of solute (ironic citrate, barium acetate and PVP) reach 50wt.% formation electrostatic spinning precursor solution; Precursor solution placed the electrostatic spinning feeding device that diameter is the 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV under 25 ℃ of room temperatures, to carry out electrostatic spinning,, collect the electrostatic spinning conjugated fibre with copper mesh at distance syringe needle 15cm place.
2) above-mentioned electrostatic spinning conjugated fibre is transferred to the porcelain boat and with it from copper mesh placed the tube furnace of temperature programmed control together, after rising to 400 ℃ of pre-treatment 30min with the temperature rise rate of 200 ℃/min, temperature rise rate with 10 ℃/min rises to 800 ℃, under this temperature, continue calcining 2h then, PVP and ironic citrate are decomposed fully, and furnace cooling can prepare BaFe
12O
19The double-layer hollow fiber.
Utilize field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan) structure and the pattern to product characterizes, the structure and morphology for preparing the double-layer hollow fiber as shown in Figure 6.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd., Japan) thing to product characterizes mutually, shows that the thing for preparing product is mutually for BaFe
12O
19, shown in the E among Fig. 7.
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can both realize the present invention's (can both reach the effect of embodiment 1-6), do not enumerate embodiment one by one at this.
Claims (8)
1. metal oxide hollow particle or fiber preparation method, it is characterized in that it comprises the steps: the composite particles or the conjugated fibre that contain metallic compound and polymkeric substance are put in the stove, temperature rise rate with 5-400 ℃/min is handled 10min-48h to it under 300-1000 ℃, obtain metal oxide hollow particle or metal oxide hollow fiber behind the furnace cooling.
2. a kind of metal oxide hollow particle according to claim 1 or fiber preparation method, it is characterized in that: described composite particles or long and slender by containing metallic compound and polymkeric substance constitutes, the mass ratio of metallic compound and polymkeric substance is (0.1-10): 1.
3. a kind of metal oxide hollow particle according to claim 1 and 2 or fiber preparation method is characterized in that: described metallic compound is any one or any mixture more than two kinds in metal organic acid salt, metal inorganic salt, the organometallic complex.
4. a kind of metal oxide hollow particle according to claim 3 or fiber preparation method is characterized in that: described metal organic acid salt is the mixing of any one or two kinds in acetate, the Citrate trianion, and two kinds is any proportioning when mixing; Described metal inorganic salt is any one or any mixing more than two kinds in halogen, nitrate, the vitriol, and any is any proportioning when mixing more than two kinds.
5. a kind of metal oxide hollow particle according to claim 3 or fiber preparation method is characterized in that: described organometallic complex is the carbonyl compound of metal Fe, Co or Ni, perhaps is butyl (tetra) titanate, aluminum isopropylate or ethanol tantalum.
6. a kind of metal oxide hollow particle according to claim 1 and 2 or fiber preparation method, it is characterized in that: described polymkeric substance is any one or any mixing more than two kinds in polyvinylpyrrolidone, polystyrene, polyethylene, polyoxyethylene, the polyacrylonitrile, and any is any proportioning when mixing more than two kinds.
7. a kind of metal oxide hollow particle according to claim 1 or fiber preparation method is characterized in that: described metal oxide hollow particle is: the metal oxide hollow particle that individual layer is hollow, nucleocapsid is hollow, multilayer is hollow or multi-layer core-shell is hollow.
8. a kind of metal oxide hollow particle according to claim 1 or fiber preparation method is characterized in that: described metal oxide hollow fiber is: the metal oxide hollow fiber that individual layer is hollow, nucleocapsid is hollow, multilayer is hollow or multi-layer core-shell is hollow.
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| CN105776348A (en) * | 2016-05-03 | 2016-07-20 | 陕西理工学院 | Simple preparation method for micron-order magnetic alpha-iron trioxide particles |
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| CN1761003A (en) * | 2005-11-22 | 2006-04-19 | 武汉理工大学 | Method for fabricating magnetic hollow ball |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1761003A (en) * | 2005-11-22 | 2006-04-19 | 武汉理工大学 | Method for fabricating magnetic hollow ball |
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