CN101235556A - Method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber - Google Patents
Method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber Download PDFInfo
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- CN101235556A CN101235556A CNA2008100504667A CN200810050466A CN101235556A CN 101235556 A CN101235556 A CN 101235556A CN A2008100504667 A CNA2008100504667 A CN A2008100504667A CN 200810050466 A CN200810050466 A CN 200810050466A CN 101235556 A CN101235556 A CN 101235556A
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Abstract
A method for preparing perovskite type rare-earth compound oxide super-length nanometer fiber belongs to the inorfil preparing technology field, the existing perovskite type rare-earth compound oxide is granuel-shaped as granular or thin film-like, big size and small specific surface area, the existing electrostatic spinning method is utilized to prepare the nanometer fiber of the metallic oxide. The method comprises the following steps: firstly, preparing spinning fluid, dissolving inorganic salt and the macromolecule template agent into the spinning fluid, secondly, preparing the precursor fiber of the inorganic salt or the macromolecule template agent, adopting the electrostatic spinning method, wherein the technical parameters are that: the voltage is 10-30kV, the solidification distance between the jet nozzle and the receiving screen is 8-20cm, thirdly, preparing the perovskite type rare-earth compound oxide nanometer fiber, adopting the heat treatment mode, wherein the heating rate is 0.5-3.0DEG C/min, holding the temperature between 600 DEG C and 900DEG C for 5-15h, the diameter of the prepared perovskite type rare-earth compound oxide nanometer fiber is 50-160nm, and the length of the nanometer fiber is more than 100 mu.
Description
Technical field
The present invention relates to a kind of nano-fiber material preparation method, belong to the inorfil preparing technical field.
Background technology
Nanofiber is meant the filamentary material that has bidimensional to be in nanoscale on the three dimensions yardstick of material, radial dimension is a nanometer scale usually, and length is then bigger.Because the difference of its pattern, have nano silk, nano wire, nanometer rods, nanotube, nanometer band and nano-cable etc. several.Because the radial dimension of nanofiber is little of nanometer scale, demonstrate series of characteristics, the most outstanding is that specific area is big, thereby its surface energy and active the increase, and then produce small-size effect, surface or interfacial effect, quantum size effect, macro quanta tunnel effect etc., and therefore show the specificity of a series of chemistry, physics (heat, light, sound, electricity, magnetic etc.) aspect.In the prior art, a lot of methods that prepare nanofiber are arranged, the method for for example reeling off raw silk from cocoons, template synthetic method, split-phase method and self-assembly method etc.In addition, also has arc evaporation, laser high temperature inustion, compound pyrolysismethod.These three kinds of methods in fact all are after at high temperature making compound (or simple substance) evaporation, make nanotube through pyrolysis (or directly condensation), from essence, all belong to the compound steam sedimentation.
The patent No. technical scheme of a relevant electrospinning process (electro-spinning) that has been 1975504 U.S. Patent Publication, this method is a kind of effective ways that prepare continuous, as to have macro length micro nanometer fiber, is at first proposed in 1934 by Formhals.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making charged Polymer Solution or melt in electrostatic field, to be subjected to the traction of electrostatic force and spray by nozzle, invest the receiving screen on opposite, thereby realization wire drawing, then, solvent evaporation at normal temperatures, perhaps melt is cooled to normal temperature and solidifies, and obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare the technical scheme of inorganic compound such as oxidate nano fiber at the inorfil preparing technical field, described oxide comprises TiO
2, ZrO
2, NiO, Co
3O
4, Mn
2O
3, Mn
3O
4, CuO, SiO
2, Al
2O
3, V
2O
5, ZnO, Nb
2O
5, and MoO
3Deng metal oxide.Electrospinning process can prepare big L/D ratio micro nanometer fiber or nanofiber continuously.
The general formula of perovskite-type rare-earth composite oxides is ABO
3, wherein A is thulium or alkali earth metal, and B is a transition metal, and O is an oxygen element.Perovskite-type rare-earth composite oxides is a kind of important depollution of environment catalyst, and it all has good catalytic action to carbon monoxide, methane, ethane and nitrogen oxide, is used for catalytic combustion, purifying vehicle exhaust and flue gas desulfurization etc.In addition, it also has excellent ferromagnetism, ferroelectricity, piezoelectricity, pyroelectricity, superconductivity, gas sensing property, fluorescence, catalytic activity and giant magnetoresistance effect etc.Prior art adopts solid reaction process to prepare perovskite-type rare-earth composite oxides, and the feature of this method is that the product that is obtained is particle or film 1000 ℃ of long-time roastings more than the temperature, and yardstick is big, specific area is little.Prior art also adopts coprecipitation, mechanical crushing activation method, thermal decomposition method, citric acid method and sol-gel process to prepare the perovskite-type rare-earth composite oxides nano particle.
Summary of the invention
Various in background technology prepare in the method for nanofiber, the shortcoming of the method for reeling off raw silk from cocoons be solution viscosity is required too harsh; The shortcoming of template synthetic method is to prepare the continuous fibers that the root root separates; Split-phase method and self-assembly method production efficiency are all lower; And the compound steam sedimentation is owing to the demand to high temperature, so process conditions are difficult to control.And the nanofiber major diameter of above-mentioned several method preparation is than little.Though the approaching nanofiber major diameter that application obtained of electrospinning process and the present invention is bigger,, this product is limited to the metal oxide nano fiber.Various in background technology prepare in the method for perovskite-type rare-earth composite oxides, and the product that solid reaction process obtained is particle or the film that yardstick is big, specific area is little; Though the product yardstick that coprecipitation, mechanical crushing activation method, thermal decomposition method, citric acid method and sol-gel process obtain reaches nanometer scale, but, prepared perovskite-type rare-earth composite oxides is a nano particle, rather than nanofiber, and, pulverous nano particle is reunited easily, has reduced specific area.In order to obtain to have big L/D ratio perovskite-type rare-earth composite oxides nanofiber, simultaneously, the preparation method is simple, and we have proposed a kind of method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber.
The present invention is achieved in that and selects electrospinning process for use that the preparation product is the perovskite-type rare-earth composite oxides nanofiber, the steps include:
One, preparation spinning solution
Inorganic salts adopt thulium or nitrate, alkoxide or the acetate of alkali earth metal and nitrate, alkoxide or the acetate of transition metal, and the relative quantity of the two is equaled 1: 1 ratio decision by thulium or two kinds of amount of substance ratios of alkali earth metal and transition metal; High polymer templates adopts polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP); Described inorganic salts and high polymer templates be dissolved in form spinning solution in the solvent.The weight proportion of each part of this spinning solution is: inorganic salts 2.5～3.5%, and polyvinyl alcohol 8.5～9.5%, perhaps polyvinylpyrrolidone 7.0～15.5%, and all the other are solvent.
Two, preparation inorganic salts/high polymer templates precursor fibre
Adopt electrospinning process, technical parameter is: voltage is 10～30kV; Nozzle is 8～20cm to the curing distance of receiving screen.
Three, preparation perovskite-type rare-earth composite oxides nanofiber
Inorganic salts/high polymer templates the precursor fibre that is obtained is heat-treated, technical parameter is: heating rate is 0.5～3.0 ℃/min, in 600～900 ℃ of temperature ranges, be incubated 5～15h, naturally cool to room temperature with body of heater afterwards, so far obtain the perovskite-type rare-earth composite oxides nanofiber.
The diameter of prepared inorganic salts/high polymer templates precursor fibre is 100～250nm in said process, and the perovskite-type rare-earth composite oxides nanofiber diameter of final preparation is 50～160nm, length is greater than 100 μ, judge by the draw ratio that is calculated in view of the above, this is a kind of ultra-long nano fiber, has realized goal of the invention.
Description of drawings
Fig. 1 is LaCoO
3The SEM photo of nanofiber, this figure double as is a Figure of abstract.Fig. 2 is LaCoO
3The XRD spectra of nanofiber.Fig. 3 is LaFeO
3The SEM photo of nanofiber.Fig. 4 is LaFeO
3The XRD spectra of nanofiber.Fig. 5 is LaMnO
3The SEM photo of nanofiber.Fig. 6 is LaMnO
3The XRD spectra of nanofiber.Fig. 7 is LaCrO
3The SEM photo of nanofiber.Fig. 8 is LaCrO
3The XRD spectra of nanofiber.Fig. 9 is LaNiO
3The SEM photo of nanofiber.Figure 10 is LaNiO
3The XRD spectra of nanofiber.
The specific embodiment
Thulium or alkali earth metal are selected La, Y, Eu, Ce, Nd or Sr for use, and transition metal is selected Fe, Cr, Mn, Co, Ni, Zr or Ti for use.Solvent is selected deionized water or ethanol for use.High polymer templates adopts the polyvinyl alcohol of molecular weight Mr=80000 or the polyvinylpyrrolidone of molecular weight Mr=1300000 or 30000.
Embodiment 1: at first polyvinyl alcohol is placed conical flask, add deionized water, make its abundant swelling more than the static 5h.Then conical flask is placed water bath with thermostatic control, 80 ℃ of constant temperature 1h stir 10h in the room temperature lower magnetic force again, can obtain homogeneous, transparent polyvinyl alcohol water solution.With La (NO
3)
36H
2O and Co (CH
3COO)
24H
2O evenly mixes and is dissolved in and obtains inorganic salt solution in the deionized water.While stirring this inorganic salt solution is dropwise joined in the polyvinyl alcohol water solution, under room temperature, continue to stir 5h, can obtain colloidal sol shape [La (NO
3)
3+ Co (CH
3COO)
2]/polyvinyl alcohol spinning solution, its weight proportion is: polyvinyl alcohol 9%, [La (NO
3)
3+ Co (CH
3COO)
2] 3%, all the other are deionized water.With electrostatic spinning behind the spinning solution room temperature ageing 24h, voltage 18kV solidifies apart from 15cm, and nozzle and horizontal angle are 15 °, and room temperature is 20 ℃, and relative humidity 45% obtains [La (NO
3)
3+ Co (CH
3COO)
2]/polyvinyl alcohol precursor fibre.With 2 ℃/min heating rate heat treatment temperature is risen to 600 ℃,, obtain LaCoO precursor fibre sintering 10h
3Nanofiber.LaCoO
3Diameter 60～the 150nm of nanofiber, length is greater than 100 μ, as shown in Figure 1.Product is the LaCoO of pure phase
3, belong to typical perovskite structure, see shown in Figure 2.
Embodiment 2: at first polyvinyl alcohol is placed conical flask, add deionized water, make its abundant swelling more than the static 5h.Then conical flask is placed water bath with thermostatic control, 80 ℃ of constant temperature 1h stir 10h in the room temperature lower magnetic force again, can obtain homogeneous, transparent polyvinyl alcohol water solution.With La (NO
3)
36H
2O and Fe (NO
3)
39H
2O evenly mixes and is dissolved in and obtains inorganic salt solution in the deionized water.While stirring this inorganic salt solution is dropwise joined in the polyvinyl alcohol water solution, under room temperature, continue to stir 5h, can obtain colloidal sol shape [La (NO
3)
3+ Fe (NO
3)
3]/polyvinyl alcohol spinning solution, its weight proportion is: polyvinyl alcohol 9.5%, [La (NO
3)
3+ Fe (NO
3)
3] 3.5%, all the other are deionized water.With electrostatic spinning behind the spinning solution room temperature ageing 24h, voltage 10kV solidifies apart from 8cm, and nozzle and horizontal angle are 15 °, and room temperature is 20 ℃, and relative humidity 50% obtains [La (NO
3)
3+ Fe (NO
3)
3]/polyvinyl alcohol precursor fibre.With 0.5 ℃/min heating rate heat treatment temperature is risen to 750 ℃,, obtain LaFeO precursor fibre sintering 12h
3Nanofiber.LaFeO
3Diameter 50～the 150nm of nanofiber, length is greater than 100 μ, as shown in Figure 3.Product is the LaFeO of pure phase
3, belong to typical perovskite structure, see shown in Figure 4.
Embodiment 3: at first polyvinyl alcohol is placed conical flask, add deionized water, make its abundant swelling more than the static 5h.Then conical flask is placed water bath with thermostatic control, 80 ℃ of constant temperature 1h stir 10h in the room temperature lower magnetic force again, can obtain homogeneous, transparent polyvinyl alcohol water solution.With La (NO
3)
36H
2O and Mn (CH
3COO)
24H
2O evenly mixes and is dissolved in and obtains inorganic salt solution in the deionized water.While stirring this inorganic salt solution is dropwise joined in the polyvinyl alcohol water solution, under room temperature, continue to stir 5h, can obtain colloidal sol shape [La (NO
3)
3+ Mn (CH
3COO)
2]/polyvinyl alcohol spinning solution, its weight proportion is: polyvinyl alcohol 8.5%, [La (NO
3)
3+ Mn (CH
3COO)
2] 3.5%, all the other are deionized water.With electrostatic spinning behind the spinning solution room temperature ageing 24h, voltage 25kV solidifies apart from 20cm, and nozzle and horizontal angle are 15 °, and room temperature is 20 ℃, and relative humidity 50% obtains [La (NO
3)
3+ Mn (CH
3COO)
2]/polyvinyl alcohol precursor fibre.With 3 ℃/min heating rate heat treatment temperature is risen to 900 ℃,, obtain LaMnO precursor fibre sintering 5h
3Nanofiber.LaMnO
3Diameter 90～the 160nm of nanofiber, length is greater than 100 μ, as shown in Figure 5.Product is the LaMnO of pure phase
3, belong to typical perovskite structure, see shown in Figure 6.
Embodiment 4: at first polyvinyl alcohol is placed conical flask, add deionized water, make its abundant swelling more than the static 5h.Then conical flask is placed water bath with thermostatic control, 80 ℃ of constant temperature 1h stir 10h in the room temperature lower magnetic force again, can obtain homogeneous, transparent polyvinyl alcohol water solution.With La (NO
3)
36H
2O and Cr (NO
3)
39H
2O evenly mixes and is dissolved in and obtains inorganic salt solution in the deionized water.While stirring this inorganic salt solution is dropwise joined in the polyvinyl alcohol water solution, under room temperature, continue to stir 5h, can obtain colloidal sol shape [La (NO
3)
3+ Cr (NO
3)
3]/polyvinyl alcohol spinning solution, its weight proportion is: polyvinyl alcohol 9%, [La (NO
3)
3+ Fe (NO
3)
3] 2.5%, all the other are deionized water.With electrostatic spinning behind the spinning solution room temperature ageing 24h, voltage 30kV solidifies apart from 8cm, and nozzle and horizontal angle are 15 °, and room temperature is 17 ℃, and relative humidity 55% obtains [La (NO
3)
3+ Cr (NO
3)
3]/polyvinyl alcohol precursor fibre.With 2 ℃/min heating rate heat treatment temperature is risen to 600 ℃,, obtain LaCrO precursor fibre sintering 10h
3Nanofiber.LaCrO
3Diameter 50～the 140nm of nanofiber, length is greater than 100 μ, as shown in Figure 7.Product is the LaCrO of pure phase
3, belong to typical perovskite structure, see shown in Figure 8.
Embodiment 5: at first polyvinyl alcohol is placed conical flask, add deionized water, make its abundant swelling more than the static 5h.Then conical flask is placed water bath with thermostatic control, 80 ℃ of constant temperature 1h stir 10h in the room temperature lower magnetic force again, can obtain homogeneous, transparent polyvinyl alcohol water solution.With La (NO
3)
36H
2O and Ni (CH
3COO)
24H
2O evenly mixes and is dissolved in and obtains inorganic salt solution in the deionized water.While stirring this inorganic salt solution is dropwise joined in the polyvinyl alcohol water solution, under room temperature, continue to stir 5h, can obtain colloidal sol shape [La (NO
3)
3+ Ni (CH
3COO)
2]/polyvinyl alcohol spinning solution, its weight proportion is: polyvinyl alcohol 9%, [La (NO
3)
3+ Mn (CH
3COO)
2] 3%, all the other are deionized water.With electrostatic spinning behind the spinning solution room temperature ageing 24h, voltage 18kV solidifies apart from 15cm, and nozzle and horizontal angle are 15 °, and room temperature is 19 ℃, and relative humidity 50% obtains [La (NO
3)
3+ Ni (CH
3COO)
2]/polyvinyl alcohol precursor fibre.With 2 ℃/min heating rate heat treatment temperature is risen to 600 ℃,, obtain LaMnO precursor fibre sintering 10h
3Nanofiber.LaNiO
3Diameter 50～the 100nm of nanofiber, length is greater than 100 μ, as shown in Figure 9.Product is the LaNiO of pure phase
3, belong to typical perovskite structure, see shown in Figure 10.
Embodiment 6: polyvinylpyrrolidone (Mr=1300000) is added absolute ethyl alcohol, stir 1h, obtain even, transparent polyvinylpyrrolidone ethanolic solution.With Sr (CH
3COO)
2H
2O and [CH
3(CH
2)
3O] Ti evenly mixes and is dissolved in and obtains the inorganic salts ethanolic solution in the absolute ethyl alcohol.Described two kinds of ethanolic solutions are mixed, magnetic agitation 2h at room temperature, ageing 0.5h then finally obtains evenly, oyster white and the colloidal sol shape [Sr (CH of certain viscosity is arranged
3COO)
2+ [CH
3(CH
2)
3O] Ti]/the polyvinylpyrrolidone spinning solution, its weight proportion is: polyvinylpyrrolidone 7%, [Sr (CH
3COO)
2+ [CH
3(CH
2)
3O] Ti] 2.5%, all the other are absolute ethyl alcohol.With the spinning solution electrostatic spinning, voltage 15kV solidifies apart from 20cm, and nozzle and horizontal angle are 30 °, obtain [Sr (CH
3COO)
2+ [CH
3(CH
2)
3O] Ti]/the polyvinylpyrrolidone precursor fibre.With 1 ℃/min heating rate heat treatment temperature is risen to 600 ℃,, obtain SrTiO precursor fibre sintering 10h
3Nanofiber.SrTiO
3Diameter 60～the 100nm of nanofiber, length is greater than 100 μ.Product is the SrTiO of pure phase
3, belong to typical perovskite structure.
Embodiment 7: polyvinylpyrrolidone (Mr=300000) is added absolute ethyl alcohol, stir 1h, obtain even, transparent polyvinylpyrrolidone ethanolic solution.With La (NO
3)
36H
2O and Ti (OC
3H
7)
4Evenly mix and be dissolved in and obtain the inorganic salts ethanolic solution in the absolute ethyl alcohol.Described two kinds of ethanolic solutions are mixed, magnetic agitation 2h at room temperature, ageing 0.5h then finally obtains evenly, oyster white and the colloidal sol shape [La (NO of certain viscosity is arranged
3)
3+ Ti (OC
3H
7)
4]/polyvinylpyrrolidone spinning solution, its weight proportion is: polyvinylpyrrolidone 15.5%, [La (NO
3)
3+ Ti (OC
3H
7)
4] 3%, all the other are absolute ethyl alcohol.With the spinning solution electrostatic spinning, voltage 15kV solidifies apart from 18cm, and nozzle and horizontal angle are 30 °, obtain [La (NO
3)
3+ Ti (OC
3H
7)
4]/polyvinylpyrrolidone precursor fibre.With 1 ℃/min heating rate heat treatment temperature is risen to 600 ℃,, obtain LaTiO precursor fibre sintering 10h
3Nanofiber.LaTiO
3 Diameter 70～the 120nm of nanofiber, length is greater than 100 μ.Product is the LaTiO of pure phase
3, belong to typical perovskite structure.
Polyvinyl alcohol, polyvinylpyrrolidone, Co (CH that such scheme is selected
3COO)
24H
2O, Fe (NO
3)
39H
2O, Mn (CH
3COO)
24H
2O, Cr (NO
3)
39H
2O, Ti (OC
3H
7)
4, [CH
3(CH
2)
3O] Ti, Sr (CH
3COO)
2H
2O and Ni (CH
3COO)
24H
2O is commercially available analysis net product, La (NO
3)
36H
2O purity is 99.99%.
Claims (5)
1, a kind of method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber is characterized in that, selects electrospinning process for use, and the preparation product is the perovskite-type rare-earth composite oxides nanofiber, the steps include:
One, preparation spinning solution
Inorganic salts adopt thulium or nitrate, alkoxide or the acetate of alkali earth metal and nitrate, alkoxide or the acetate of transition metal, and the relative quantity of the two is equaled 1: 1 ratio decision by thulium or two kinds of amount of substance ratios of alkali earth metal and transition metal; High polymer templates adopts polyvinyl alcohol or polyvinylpyrrolidone; Described inorganic salts and high polymer templates be dissolved in form spinning solution in the solvent; The weight proportion of each part of this spinning solution is: inorganic salts 2.5～3.5%, and polyvinyl alcohol 8.5～9.5%, perhaps polyvinylpyrrolidone 7.0～15.5%, and all the other are solvent;
Two, preparation inorganic salts/high polymer templates precursor fibre
Adopt electrospinning process, technical parameter is: voltage is 10～30kV; Nozzle is 8～20cm to the curing distance of receiving screen;
Three, preparation perovskite-type rare-earth composite oxides nanofiber
Inorganic salts/high polymer templates the precursor fibre that is obtained is heat-treated, technical parameter is: heating rate is 0.5～3.0 ℃/min, in 600～900 ℃ of temperature ranges, be incubated 5～15h, naturally cool to room temperature with body of heater afterwards, so far obtain the perovskite-type rare-earth composite oxides nanofiber.
2, the method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber according to claim 1 is characterized in that, thulium or alkali earth metal are selected La, Y, Eu, Ce, Nd or Sr for use.
3, the method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber according to claim 1 is characterized in that, transition metal is selected Fe, Cr, Mn, Co, Ni, Zr or Ti for use.
4, the method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber according to claim 1 is characterized in that, solvent is selected deionized water or ethanol for use.
5, the method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber according to claim 1, it is characterized in that it is that 80000 polyvinyl alcohol or molecular weight are 1300000 or 30000 polyvinylpyrrolidone that high polymer templates adopts molecular weight.
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