CN101898749B - 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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- CN101898749B CN101898749B CN201010242079.0A CN201010242079A CN101898749B CN 101898749 B CN101898749 B CN 101898749B CN 201010242079 A CN201010242079 A CN 201010242079A CN 101898749 B CN101898749 B CN 101898749B
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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 the preparation method of a kind of metal oxide hollow particle, metal oxide hollow fiber, metal hollow particle or metal hollow fiber.
Background technology
Have micro-and nano-particles and the fiber of hollow structure, due to its low density, high-specific surface area and low thermal expansivity, be widely used in drug conveying, catalysis, sensing, Chu Qing, the 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-chamber hollow Nano particle and fiber) cause 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, nanotube etc.), multi-stage hollow nanoparticle and fiber have following characteristics: (1) has multilayer micro-nano hollow structure and multiple interface, likely causes new physicochemical property; (2) its complicated internal structure is conducive to control better the physical and chemical factor at the each position of particle; (3) there is multiple internal surface and high-specific surface area, there is higher activity than the solid of same size and individual layer hollow material, in drug conveying, catalysis, sensing, Chu Qing, the aspects such as lithium cell and microreactor show the better properties making 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) research discovery Cu
2the sensitivity to 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, the 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 PtC has the productive rate higher than 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 pre-synthesis micro nano structure as framework (as SiO
2or PS ball etc.), adopt successively coated method at its surface deposition multilayer second-phase material and transition layer, and remove subsequently template and transition layer and obtain the hollow and multi-stage hollow structure of the individual layer of second-phase material.But in the time preparing the hollow and multi-stage hollow micro-and nano-particles of individual layer, there is the solution of still needing of several problems: 1) sedimentation velocity is slow and can not large area deposition, is difficult to meet the needs of heavy industrialization; 2) preparation section is loaded down with trivial details, and the treatment process of template is more, requires template quality almost Perfect, disturbed by ambient conditions, causes deposition quality to decline, and settled layer intensity is low; 3) template used must removal, this has brought trouble to the hollow and multi-stage hollow micro-and nano-particles subsequent applications of individual layer, and hollow structure is easily subsided and is out of shape.Therefore hollow and multi-stage hollow micro-and nano-particles becomes the new direction that the skilled worker person of section explores in recent years for individual layer, to utilize non-template legal system.Wherein representative method is to prepare the method for hollow granule based on Kirkendall effect and Ostwald slaking mechanism.Kirkendall effect refers to a kind of phenomenon of atom two kinds of material interface diffusions, can obtain hollow Nano particle if the direction that atomic diffusion and cavity are assembled is controlled.Ostwald slaking mechanism refers to the one mechanism that constantly consumes little crystal grain in the process of growth of larger crystal grain, if the grain size distribution of particle agglomeration is controlled, so crystal grain during in subsequent growth hollow nanoparticle can form.But the hollow granule preparing based on Kirkendall effect and Ostwald slaking mechanism often, for comparatively simple individual layer is hollow or individual layer nucleocapsid hollow granule, also cannot be realized to the structure of product control (Yin, the Y.D. of system; Rioux, R.M.; Erdonmez, C.K.; Hughes, S.; Somorjai, G.A.; Alivisatos, A.P.Science 2004,304,711; Liu, B.; Zeng, H.C.Small2005,1,566).Patent CN101293192A utilizes 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 solvent thermal condition to prepare ferric oxide nucleocapsid hollow granule, but the method for utilizing the composite precursor particle that contains metallic compound and polymkeric substance or the non-homogeneous contractile mechanism of fiber under rapid heating condition to prepare various metals or poly-metal deoxide hollow granule and fiber there is not yet report.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of metal oxide hollow particle or fiber, the method is simple and easy, by regulating temperature rise rate can obtain having hollow granule or the hollow fiber of different boring structures.
To achieve these goals, the technical solution used in the present invention is: the preparation method of a kind of metal oxide hollow particle or fiber, it is characterized in that it comprises the steps: the composite particles that contains metallic compound and polymkeric substance or conjugated fibre to put in stove, temperature rise rate with 5-400 DEG C/min is processed 10min-48h to it at 300-1000 DEG C, obtains metal oxide hollow particle or metal oxide hollow fiber after furnace cooling.
Taking above-mentioned metal oxide hollow particle or metal oxide hollow fiber as raw material, carry out reduction reaction (through H
2or the reduction such as CO), can obtain metal hollow particle or metal hollow fiber.
The preparation (spray method) of the described composite particles that contains metallic compound and polymkeric substance: be (0.1-10) by the mass ratio of metallic compound and polymkeric substance: 1, choose metallic compound and polymkeric substance dissolving and be mixed with the electrostatic spray precursor solution that concentration (the quality sum of metallic compound and polymkeric substance and the ratio of solution quality) is 20-40wt.%; Electrostatic spray precursor solution is placed in the electrostatic spray feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.02-0.2mL/h, adopt the operating voltage of 7-30kV to carry out electrostatic spray under 25 DEG C of room temperatures, apart from syringe needle 4-15cm place, collect electrostatic spray product with aluminium flake, obtain the composite particles that contains metallic compound and polymkeric substance.
The preparation of the described composite particles that contains metallic compound and polymkeric substance also can adopt emulsion polymerisation process preparation.
The preparation (utilizing spinning processes) of the described conjugated fibre that contains metallic compound and polymkeric substance: be (0.1-10) by the mass ratio of metallic compound and polymkeric substance: 1, choose metallic compound and polymkeric substance dissolving and be mixed with the electrostatic spinning precursor solution that concentration (the quality sum of metallic compound and polymkeric substance and the ratio of solution quality) is 45-60wt.%; Electrostatic spinning precursor solution is placed in the electrostatic spinning feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.1-1mL/h, adopt the operating voltage of 10-30kV to carry out electrostatic spinning under 25 DEG C of room temperatures, apart from syringe needle 4-20cm place, collect electrostatic spinning product with copper mesh, obtain the conjugated fibre that contains metallic compound and polymkeric substance.
Described metallic compound is the mixture of any one or any two or more (containing any two) in metal organic acid salt, metal inorganic salt, organometallic complex etc., and any two above (containing any two) is any proportioning while mixing.
Described metal organic acid salt is the mixing of any one or two kinds in acetate, Citrate trianion etc., and two kinds is any proportioning while mixing; Described metal inorganic salt is the mixing of any one or any two or more (containing any two) in halogen, nitrate, vitriol etc., and any two above (containing any two) is any proportioning while mixing.
Described organometallic complex is the carbonyl compound of metal Fe, Co or Ni, or 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 the mixing of any one or any two or more (containing any two) in polyvinylpyrrolidone (PVP), polystyrene (PS), polyethylene (PE), polyoxyethylene (PEO), polyacrylonitrile (PANI) etc., and any two above (containing any two) is any proportioning while 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 the fiber prepared by the inventive method comprise: M
xfe
yo
z, M
xo
y(M=Fe, Co, Ni, Zn, Cu, Ba, Sr, the 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 the non-homogeneous contraction of fiber under rapid heating condition to prepare metal oxide hollow particle and the fiber of various boring structures, by regulating temperature rise rate can obtain having the hollow granule of different boring structures or fiber, [temperature rise rate is 5-400 DEG C/min, from low paramount, can obtain successively that individual layer is hollow, nucleocapsid is hollow, multilayer (nucleocapsid) hollow granule or fiber].
Present method and template relatively have that technique is simple, and the time is short, easily control, and are convenient to large-scale production; With hollow granule (fiber) the preparation method comparison based on Kirkendall effect and Ostwald slaking mechanism, present method can be hollow hollow to nucleocapsid by individual layer by realizing product structure the adjusting of temperature rise rate simply, then to multilayer (nucleocapsid) hollow granule or fiber.
Brief description of the 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
Below in conjunction with specific embodiment, the invention will be further described, 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) is dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and polyvinylpyrrolidone (PVP) is 5: 4, heats magnetic agitation dehydration and make the concentration of solute (ironic citrate and PVP) reach 40wt.% formation electrostatic spray precursor solution at 60 DEG C; Electrostatic spray precursor solution is placed in the electrostatic spray feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV to carry out electrostatic spray under 25 DEG C of room temperatures, apart from 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 in to the tube furnace of temperature programmed control together with aluminium flake, rise to 500 DEG C with the temperature rise rate of 10 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed, furnace cooling can prepare γ-Fe
2o
3individual layer hollow granule;
Temperature rise rate is heightened to 20 DEG C/min, repeated above-mentioned thermal treatment process and can obtain γ-Fe
2o
3nucleocapsid hollow granule;
Temperature rise rate is heightened to 50 DEG C/min, repeated above-mentioned thermal treatment process and can obtain γ-Fe
2o
3double-layer hollow particle;
Temperature rise rate is heightened to 250 DEG C/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 as shown in the A in Fig. 4.
Utilize transmission electron microscope (TEM, JEM-2100F, JEOL Co., Ltd., and field emission scanning electron microscope (SEM Japan), S-4800, Hitachi Co., Ltd., Japan) structure to product and pattern characterize, the structure of individual layer hollow granule, nucleocapsid hollow granule, double-layer hollow particle and the double-deck nucleocapsid hollow granule preparing and pattern are as shown in the A in Fig. 1, B, C and D, and A, B, C and the D in Fig. 1 illustrated that the product obtaining 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., Japan) to γ-Fe
2o
3the thing of double-deck nucleocapsid hollow granule product characterizes mutually, and showing to prepare product is γ-Fe
2o
3, as shown in the A in Fig. 7.
Embodiment 2: γ-Fe
2o
3nucleocapsid is hollow, the preparation of double-layer hollow fiber:
1): polyvinylpyrrolidone (PVP) is dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and PVP is 4: 1, heats magnetic agitation dehydration and make the concentration of solute (ironic citrate and PVP) reach 50wt.% formation electrostatic spinning precursor solution at 60 DEG C; Precursor solution is placed in the electrostatic spinning feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV to carry out electrostatic spinning under 25 DEG C of room temperatures, apart from 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 porcelain boat and it is placed in to the tube furnace of temperature programmed control together from copper mesh, rise to 500 DEG C with the temperature rise rate of 100 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed, and furnace cooling can prepare γ-Fe
2o
3nucleocapsid hollow fiber, as shown in the A in Fig. 2;
Temperature rise rate is heightened to 250 DEG C/min, repeated above-mentioned thermal treatment process and can obtain γ-Fe
2o
3double-layer hollow fiber, as shown in the B in Fig. 1.
Utilize field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan) structure to product and pattern characterize, the nucleocapsid hollow fiber preparing, the structure of double-layer hollow fiber and pattern are as shown in A and B in Fig. 2, and the A in Fig. 2 has illustrated that the product obtaining is nucleocapsid hollow fiber, and the B in Fig. 2 has illustrated that the product obtaining is double-layer hollow fiber.
Embodiment 3 α-Fe
2o
3nucleocapsid is hollow, the preparation of double-layer hollow fiber:
1) polyvinylpyrrolidone (PVP) is dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and PVP is 4: 1, heats magnetic agitation dehydration and make the concentration of solute (ironic citrate and PVP) reach 55wt.% formation electrostatic spinning precursor solution at 60 DEG C; Precursor solution is placed in the electrostatic spinning feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV to carry out electrostatic spinning under 25 DEG C of room temperatures, apart from 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 porcelain boat and it is placed in to the tube furnace of temperature programmed control together from copper mesh, rise to after 400 DEG C of pre-treatment 30min with the temperature rise rate of 100 DEG C/min, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed completely, and furnace cooling can prepare α-Fe
2o
3nucleocapsid hollow fiber.
Pre-treatment temperature rise rate is heightened to 200 DEG C/min, repeated above-mentioned thermal treatment process and can obtain α-Fe
2o
3double-layer hollow fiber.
Utilize structure and the pattern of field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan) to product to characterize, the nucleocapsid hollow fiber preparing and the structure and morphology of double-layer hollow fiber are as shown in A and B in Fig. 3.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd., Japan) to characterize mutually the thing of product, showing to prepare double-layer hollow fiber product is α-Fe
2o
3, as shown in the B in Fig. 7.
Embodiment 4:CoFe
2o
4nucleocapsid is hollow, the preparation of double-layer hollow particle:
1) polyvinylpyrrolidone (PVP) and cobaltous acetate are dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 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, at 60 DEG C, heating magnetic agitation dehydration makes the concentration of solute (ironic citrate, cobaltous acetate and PVP) reach 40wt.% formation electrostatic spray precursor solution; Precursor solution is placed in the electrostatic spray feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV to carry out electrostatic spray under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spray product---metallic compound composite particles with aluminium flake.
2) above-mentioned electrostatic spray product is placed in to the tube furnace of temperature programmed control together with aluminium flake, rises to 500 DEG C with the temperature rise rate of 50 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed, furnace cooling can prepare CoFe
2o
4nucleocapsid hollow granule;
Temperature rise rate is heightened to 100 DEG C/min, repeated above-mentioned thermal treatment process and can obtain CoFe
2o
4double-layer hollow particle.
Utilize structure and the pattern of transmission electron microscope (TEM, JEM-2100F, JEOL Co., Ltd., Japan) to product to characterize, the nucleocapsid hollow granule preparing and double-layer hollow morphology of particles and pattern are as shown in A and B in Fig. 4.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd., Japan) to characterize mutually the thing of product, showing to prepare product is CoFe
2o
4as shown in the C in Fig. 7.
Embodiment 5NiFe
2o
4nucleocapsid is hollow, the preparation of double-layer hollow particle:
1) polyvinylpyrrolidone (PVP) and nickelous acetate are dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 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, at 60 DEG C, heating magnetic agitation dehydration makes the concentration of solute (ironic citrate, nickelous acetate and PVP) reach 40wt.% formation electrostatic spray precursor solution; Precursor solution is placed in the electrostatic spray feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV to carry out electrostatic spray under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spray product with aluminium flake.
2) above-mentioned electrostatic spray product is placed in to the tube furnace of temperature programmed control together with aluminium flake substrate, rise to 500 DEG C with the temperature rise rate of 50 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed, furnace cooling can prepare CoFe
2o
4nucleocapsid hollow granule.
Temperature rise rate is heightened to 100 DEG C/min, repeated above-mentioned thermal treatment process and can obtain CoFe
2o
4double-layer hollow particle.
Utilize structure and the pattern of transmission electron microscope (TEM, JEM-2100F, JEOL Co., Ltd., Japan) to product to characterize, the nucleocapsid hollow granule preparing and double-layer hollow morphology of particles and pattern are as shown in A and B in Fig. 5.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd., Japan) to characterize mutually the thing of product, the thing that shows to prepare product is NiFe mutually
2o
4, as shown in the D in Fig. 7.
Embodiment 6BaFe
12o
19the preparation of double-layer hollow fiber
1) polyvinylpyrrolidone (PVP) and barium acetate are dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 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, at 60 DEG C, heating magnetic agitation dehydration makes the concentration of solute (ironic citrate, barium acetate and PVP) reach 50wt.% formation electrostatic spinning precursor solution; Precursor solution is placed in the electrostatic spinning feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV to carry out electrostatic spinning under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spinning conjugated fibre with copper mesh.
2) above-mentioned electrostatic spinning conjugated fibre is transferred to porcelain boat and it is placed in to the tube furnace of temperature programmed control together from copper mesh, rise to after 400 DEG C of pre-treatment 30min with the temperature rise rate of 200 DEG C/min, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed completely, and furnace cooling can prepare BaFe
12o
19double-layer hollow fiber.
Utilize structure and the pattern of field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan) to product to characterize, prepare the structure and morphology of double-layer hollow fiber as shown in Figure 6.Utilize X-ray diffraction (XRD, D/max-III A, Rigaku Co., Ltd., Japan) to characterize mutually the thing of product, the thing that shows to prepare product is BaFe mutually
12o
19, as shown in the E in Fig. 7.
Each raw material that the present invention is cited, and the bound of the each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention's (can reach the effect of embodiment 1-6), do not enumerate embodiment at this.
Claims (6)
1. the preparation method of a metal oxide hollow particle, it is characterized in that it comprises the steps: 1) polyvinylpyrrolidone is dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and polyvinylpyrrolidone is 5:4, heats magnetic agitation dehydration and make the concentration of ironic citrate and polyvinylpyrrolidone reach 40wt.% formation electrostatic spray precursor solution at 60 DEG C; Electrostatic spray precursor solution is placed in the electrostatic spray feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV to carry out electrostatic spray under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spray product with aluminium flake, obtain PVP/ ironic citrate composite particles;
2) above-mentioned PVP/ ironic citrate composite particles is placed in to the tube furnace of temperature programmed control together with aluminium flake, rise to 500 DEG C with the temperature rise rate of 10 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed, furnace cooling, prepares γ-Fe
2o
3individual layer hollow granule;
Temperature rise rate is heightened to 20 DEG C/min, repeated above-mentioned thermal treatment process, obtain γ-Fe
2o
3nucleocapsid hollow granule;
Temperature rise rate is heightened to 50 DEG C/min, repeated above-mentioned thermal treatment process, obtain γ-Fe
2o
3double-layer hollow particle;
Temperature rise rate is heightened to 250 DEG C/min, repeated above-mentioned thermal treatment process, obtain γ-Fe
2o
3double-deck nucleocapsid hollow granule.
2. a preparation method for metal oxide hollow fiber, is characterized in that it comprises the steps:
1): polyvinylpyrrolidone is dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and polyvinylpyrrolidone is 4:1, heats magnetic agitation dehydration and make the concentration of ironic citrate and polyvinylpyrrolidone reach 50 wt.% formation electrostatic spinning precursor solutions at 60 DEG C; Precursor solution is placed in the electrostatic spinning feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV to carry out electrostatic spinning under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spray product with copper mesh, obtain PVP/ ironic citrate conjugated fibre;
2) above-mentioned PVP/ ironic citrate conjugated fibre is transferred to porcelain boat and it is placed in to the tube furnace of temperature programmed control together from copper mesh, rise to 500 DEG C with the temperature rise rate of 100 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed, and furnace cooling can prepare γ-Fe
2o
3nucleocapsid hollow fiber;
Temperature rise rate is heightened to 250 DEG C/min, repeated above-mentioned thermal treatment process, obtain γ-Fe
2o
3double-layer hollow fiber.
3. a preparation method for metal oxide hollow fiber, is characterized in that it comprises the steps:
1) polyvinylpyrrolidone is dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and polyvinylpyrrolidone is 4:1, heats magnetic agitation dehydration and make the concentration of ironic citrate and polyvinylpyrrolidone reach 55 wt.% formation electrostatic spinning precursor solutions at 60 DEG C; Precursor solution is placed in the electrostatic spinning feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV to carry out electrostatic spinning under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spray product with copper mesh, obtain PVP/ ironic citrate conjugated fibre;
2) above-mentioned PVP/ ironic citrate conjugated fibre is transferred to porcelain boat and it is placed in to the tube furnace of temperature programmed control together from copper mesh, rise to after 400 DEG C of pre-treatment 30 min with the temperature rise rate of 100 DEG C/min, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed completely, and furnace cooling can prepare α-Fe
2o
3nucleocapsid hollow fiber;
Pre-treatment temperature rise rate is heightened to 200 DEG C/min, repeated above-mentioned thermal treatment process and can obtain α-Fe
2o
3double-layer hollow fiber.
4. a preparation method for metal oxide hollow particle, is characterized in that it comprises the steps:
1) polyvinylpyrrolidone and cobaltous acetate are dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and polyvinylpyrrolidone is 5:4, the mol ratio of ironic citrate and cobaltous acetate is 2:1, heats magnetic agitation dehydration and make the concentration of ironic citrate, cobaltous acetate and polyvinylpyrrolidone reach 40 wt.% formation electrostatic spray precursor solutions at 60 DEG C; Precursor solution is placed in the electrostatic spray feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV to carry out electrostatic spray under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spray product with aluminium flake;
2) above-mentioned electrostatic spray product is placed in to the tube furnace of temperature programmed control together with aluminium flake, rises to 500 DEG C with the temperature rise rate of 50 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed, furnace cooling, prepares CoFe
2o
4nucleocapsid hollow granule;
Temperature rise rate is heightened to 100 DEG C/min, repeated above-mentioned thermal treatment process, obtain CoFe
2o
4double-layer hollow particle.
5. a preparation method for metal oxide hollow particle, is characterized in that it comprises the steps:
1) polyvinylpyrrolidone and nickelous acetate are dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and polyvinylpyrrolidone is 5:4, the mol ratio of ironic citrate and nickelous acetate is 2:1, heats magnetic agitation dehydration and make the concentration of ironic citrate, nickelous acetate and polyvinylpyrrolidone reach 40 wt.% formation electrostatic spray precursor solutions at 60 DEG C; Precursor solution is placed in the electrostatic spray feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.1mL/h, adopt the operating voltage of 25kV to carry out electrostatic spray under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spray product with aluminium flake;
2) above-mentioned electrostatic spray product is placed in to the tube furnace of temperature programmed control together with aluminium flake substrate, rises to 500 DEG C with the temperature rise rate of 50 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed, furnace cooling, prepares CoFe
2o
4nucleocapsid hollow granule;
Temperature rise rate is heightened to 100 DEG C/min, repeated above-mentioned thermal treatment process, obtain CoFe
2o
4double-layer hollow particle.
6. a preparation method for metal oxide hollow fiber, is characterized in that it comprises the steps:
1) polyvinylpyrrolidone and barium acetate are dissolved in the ironic citrate solution that concentration that 30mL prepares is in advance 0.1g/mL, the mass ratio of ironic citrate and polyvinylpyrrolidone is 4:1, the mol ratio of ironic citrate and nickelous acetate is 12:1, heats magnetic agitation dehydration and make the concentration of ironic citrate, barium acetate and polyvinylpyrrolidone reach 50 wt.% formation electrostatic spinning precursor solutions at 60 DEG C; Precursor solution is placed in the electrostatic spinning feeding device that diameter is 0.6mm syringe needle is housed, the feed speed of solution is 0.3mL/h, adopt the operating voltage of 25kV to carry out electrostatic spinning under 25 DEG C of room temperatures, apart from syringe needle 15cm place, collect electrostatic spinning conjugated fibre with copper mesh;
2) above-mentioned electrostatic spinning conjugated fibre is transferred to porcelain boat and it is placed in to the tube furnace of temperature programmed control together from copper mesh, rise to after 400 DEG C of pre-treatment 30 min with the temperature rise rate of 200 DEG C/min, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min, then at this temperature, continue calcining 2h, PVP and ironic citrate are decomposed completely, and furnace cooling can prepare BaFe
12o
19double-layer hollow fiber.
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| JP6512883B2 (en) * | 2015-03-20 | 2019-05-15 | 花王株式会社 | Method of producing hollow particles |
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| CN106395913B (en) * | 2016-08-26 | 2018-01-09 | 天津大学 | A kind of ferromagnetic nano α Fe with iron defect2O3And preparation method thereof |
| CN107098405B (en) * | 2017-04-01 | 2019-07-16 | 中南大学 | A kind of method that a step prepares multi-layer core-shell structure transition metal oxide |
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| CN114433084B (en) * | 2021-12-29 | 2023-09-08 | 杭州臻尚环境科技有限公司 | Preparation method and application of hollow carbon/silicon composite microsphere catalyst with core-shell structure |
| CN114735763B (en) * | 2022-04-01 | 2023-11-21 | 青岛爱尔家佳新材料股份有限公司 | Hollow multi-shell metal oxide, preparation method thereof and explosion-proof polyurea for shelter |
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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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