CN102222548B - Method for preparing NiO@SnO2@Zn2TiO4@TiO2 coaxial four-layer nanocable - Google Patents

Method for preparing NiO@SnO2@Zn2TiO4@TiO2 coaxial four-layer nanocable Download PDF

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CN102222548B
CN102222548B CN201110057946A CN201110057946A CN102222548B CN 102222548 B CN102222548 B CN 102222548B CN 201110057946 A CN201110057946 A CN 201110057946A CN 201110057946 A CN201110057946 A CN 201110057946A CN 102222548 B CN102222548 B CN 102222548B
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CN102222548A (en
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董相廷
宋超
王进贤
于文生
刘桂霞
徐佳
浦利
于淑晶
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Changchun University of Science and Technology
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Abstract

The invention relates to a method for preparing a NiO@SnO2@Zn2TiO4@TiO2 coaxial four-layer nanocable, belonging to the technical field of preparation of nano materials. The method comprises the following three steps of: (1) preparing a spinning solution, adding tetrahydrate nickel acetate and PVP (Polyvinyl Pyrrolidone) into DMF (Dimethyl Formamide) to form a core layer spinning solution, adding pentahydrate tin tetrachloride and the PVP into the DMF to form a second layer spinning solution, adding bihydrate zinc acetate and the PVP into the DMF to form a third layer spinning solution and adding butyl titanate, the PVP and glacial acetic acid into ethanol to form a shell layer spinning solution; (2) preparing a [Ni(CH3COO)2+PVP]@[SnCl4+PVP]@[Zn(CH3COO)2+PVP]@[Ti(OC4H9)4+CH3COOH+PVP] precursor composite cable by adopting a coaxial static spinning technology under the conditions that the voltage is 19kV, the curing distance is 26 centimeters, the room temperature is 25-30 DEG C and the relative humidity is 48-55 percent; and (3) preparing the NiO@SnO2@Zn2TiO4@TiO2 coaxial four-layer nanocable: thermally treating the precursor composite cable at the temperature raising speed of 1 DEG C/minute, preserving heat at the temperature 1,000 DEG C for 8 hours, reducing the temperature to 200 DEG C at the speed of 1 DEG C/minute and naturally cooling to room temperature to obtain the NiO (core layer)@SnO2 (second layer)@Zn2TiO4 (third layer)@TiO2 (shell layer) coaxial four-layer nanocable of which the diameter is 225-415 nanometers and the length is more than 100 mum.

Description

A kind of preparation NiOSnO 2Zn 2TiO 4TiO 2The method of coaxial four layers of nano-cable
Technical field
The present invention relates to the inorganic nano material preparing technical field, relate to a kind of preparation NiOSnO specifically 2Zn 2TiO 4TiO 2The method of coaxial four layers of nano-cable.
Background technology
The preparation of one-dimensional nano structure material and property research are one of forward position focuses of present material science research field.Nano-cable (Nanocables) is because its particular performances, abundant scientific meaning, wide application prospect and the important strategic status of in following nano structure device, occupying have caused people's great attention in recent years.The research of coaxial nano cable is started in the mid-90; Development later in 2000 is swift and violent, and up to the present, people adopt different synthetic methods; Different types of material has successfully been prepared hundreds of coaxial nano cable, as: Fe/C, Zn/ZnO, C/C, SiC/C, SiGaN/SiO xN yAnd the Fe-C-BN of three-decker and α-Si 3N 4-Si-SiO 2Deng.In more than ten years in the past, people develop many methods that prepare coaxial nano cable on the basis of original preparation quasi-one-dimensional nanometer material, like: hydro thermal method, sol-gel process, based on nanometer collimation method, vapor growth method, template etc.Continue to explore new synthetic technology, constantly develop and improve the preparation science of coaxial nano cable, obtain high-quality coaxial nano cable, be still the main direction of present coaxial nano cable research.
Because titanium dioxide TiO 2Have excellent photocatalysis, high electricity conversion, superpower chemical stability and good performance such as biocompatibility with nickel oxide NiO, thereby obtain extensive use at aspects such as photocatalysis Decomposition organic substance, photocell electrode, pearlescent material, histoorgan, disinfecting, antimicrobials.SnO 2Be a kind of semi-conducting material of extensive use, be used as opacifying agent, catalyst and the sensor material of glaze and enamel.Zn 2TiO 4Be a kind of important inorganic functional material, be widely used in microwave dielectric ceramic, solid oxide fuel cell electrode, gas sensor, high temperature desulfurizing adsorbent, alkane dehydrogenating catalyst and photochemical catalyst etc.Do not see at present through NiO, SnO 2, Zn 2TiO 4And TiO 2Make up NiOSnO 2Zn 2TiO 4TiO 2The report of coaxial four layers of nano-cable, the expression core shell structure, i.e. the construction of cable, this cable is four layers of construction of cable, the 3rd layer of shell of the sandwich layer second layer, sandwich layer is NiO, the second layer is SnO 2, the 3rd layer is Zn 2TiO 4, shell is TiO 2, this nano-cable has particular structural, uses widely in the hope of obtaining.
The patent No. is the technical scheme that 1975504 United States Patent (USP) discloses a relevant electrospinning process (electrospinning); 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 mainly is used for preparing high polymer nanometer fiber; It is characterized in that making charged Polymer Solution or melt in electrostatic field, to receive the traction of electrostatic force and spray by nozzle; Invest the receiving screen on opposite, thereby realize wire drawing, solvent evaporation at normal temperatures then; 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, Y 2O 3, Y 2O 3: RE 3+(RE 3+=Eu 3+, Tb 3+, Er 3+, Yb 3+/ Er 3+), NiO, Co 3O 4, Mn 2O 3, Mn 3O 4, CuO, SiO 2, Al 2O 3, V 2O 5, ZnO, Nb 2O 5, MoO 3, CeO 2, LaMO 3(M=Fe, Cr, Mn, Co, Ni, Al), Y 3Al 5O 12, La 2Zr 2O 7Deng metal oxide and composite oxide of metal.Electrostatic spinning technique is improved; Adopt coaxial spinning head, spinning solution is injected into respectively in interior pipe and the outer tube, when adding High Level DC Voltage; Solution in the inner and outer pipes is pulled out by electric field force simultaneously; Solidify the back and form coaxial nano cable, also promptly obtain the coaxial double-layer nano-cable, this technology promptly is a coaxial electrostatic spinning technology.This technology of usefulness such as Wang Ce has prepared silica polymer co-axial nano fiber (SCI, 2005,26 (5): 985-987); The expression core shell structure, the material of front is a sandwich layer, the material of back is a shell; Be the sandwich layer shell structurre, also be the double-deck construction of cable; Utilizations such as Dong Xiangting should technology prepare TiO 2SiO 2Sub-micron coaxial cable (chemical journal, 2007,65 (23): 2675-2679), ZnOSiO 2Coaxial nano cable (Chinese Journal of Inorganic Chemistry, 2010,26 (1), 29-34) and Al 2O 3/ SiO 2Coaxial ultra micro cable (silicate journal, 2009,37 (10): 1712-1717); Han, et al adopt should technology have prepared PU (core)/PC (Shell) composite nano fiber (Polymer Composites, 2006,10:381-386).At present, do not see and utilize coaxial electrostatic spinning technology to prepare NiOSnO 2Zn 2TiO 4TiO 2The relevant report of coaxial four layers of nano-cable.
When utilizing electrostatic spinning technique to prepare nano material, the structure of the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter, Technology for Heating Processing and spinning head all has material impact to the pattern and the size of final products.The present invention adopts coaxial electrostatic spinning technology, and coaxial four layers of spinning head that spinning head is nested together and is formed by four syringe needles that cut flat different-diameters are with four water acetic acid nickel (CH 3COO) 24H 2O, polyvinylpyrrolidone PVP and N, the mixed liquor of dinethylformamide DMF are the sandwich layer spinning solution, with stannic chloride pentahydrate SnCl 45H 2The mixed liquor of O, PVP and DMF is a second layer spinning solution, with zinc acetate dihydrate Zn (CH 3COO) 22H 2The mixed liquor of O, PVP and DMF is the 3rd a layer of spinning solution, with PVP, absolute ethyl alcohol CH 3CH 2OH, glacial acetic acid CH 3COOH and butyl titanate Ti (OC 4H 9) 4Mixed liquor be shell layer spinning solution, the viscosity of control spinning solution is most important, under the process conditions of the best, obtains [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable, i.e. the 3rd layer of shell structurre composite cable of the sandwich layer second layer, pass through high-temperature heat treatment again after, obtain the NiOSnO of novel structure 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable.
Summary of the invention
The method for preparing coaxial nano cable in background technology has hydro thermal method, sol-gel process, based on nanometer collimation method, vapor growth method, template etc.; What the use coaxial electrostatic spinning technology in the background technology prepared is coaxial double-layer nanometer cables such as inorganic matter inorganic matter, inorganic matter macromolecule and macromolecule high molecular nanometer cable, and the structure of employed raw material, template, solvent, spinning head is different with method of the present invention with the final objective product.The present invention uses coaxial electrostatic spinning technology, adopts coaxial four layers of spinning head to prepare the NiOSnO of novel structure 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable are sandwich layer with NiO, and diameter is 35-55nm; The second layer is SnO 2, thickness is 30-50nm; The 3rd layer is Zn 2TiO 4, thickness is 25-40nm, shell is TiO 2, thickness is 40-90nm, the diameter of coaxial four layers of nano-cable is 225-415nm, cable length＞100 μ m.
The present invention is achieved in that and at first prepares the sandwich layer with certain viscosity, the second layer, the 3rd layer and the shell layer spinning solution that is used for coaxial electrostatic spinning technology that the viscosity of control spinning solution is most important.Adopt coaxial four layers of spinning head, application coaxial electrostatic spinning technology to carry out electrostatic spinning, under the process conditions of the best, obtain [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable, promptly the 3rd layer of shell structurre composite cable of the sandwich layer second layer passes through high-temperature heat treatment, PVP and CH 3Volatilize the Ni (CH in the sandwich layer after the COOH oxidation Decomposition 3COO) 2Decomposing oxidation generates NiO, constitutes the sandwich layer of the nano-cable that is generated, the SnCl in the second layer 4Decomposing oxidation generates SnO 2, constitute the second layer of the nano-cable generated, the Zn (CH in the 3rd layer 3COO) 2With in the shell with the 3rd layer of approaching part Ti (OC 4H 9) 4Oxidation reaction at high temperature takes place generated Zn 2TiO 4, constituted the 3rd layer of the nano-cable that generated, remaining Ti (OC in the shell 4H 9) 4Decomposing oxidation has generated TiO 2, having constituted the shell of nano-cable, to prepare the coaxial double-layer nano-cable different with employing coaxial electrostatic spinning technology of report in the past for these, finally obtain the NiOSnO of novel structure 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable.The steps include:
(1) preparing spinning solution
High polymer templates adopts polyvinylpyrrolidone PVP in the spinning solution, and molecular weight is 90000, and four water acetic acid nickel (CH are used in the nickel source 3COO) 24H 2O, Xi Yuan uses stannic chloride pentahydrate SnCl 45H 2O, zinc acetate dihydrate Zn (CH is used in the zinc source 3COO) 22H 2O, butyl titanate Ti (OC is used in the titanium source 4H 9) 4, solvent adopts absolute ethyl alcohol CH 3CH 2OH and N, dinethylformamide DMF, glacial acetic acid CH 3COOH is an additive.With Ni (CH 3COO) 24H 2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the sandwich layer spinning solution, and the mass percent of each material is in the sandwich layer spinning solution: Ni (CH 3COO) 24H 2O is 7%, and PVP is 11%, and DMF is 82%; With SnCl 45H 2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms second layer spinning solution, and the mass percent of each material is in the second layer spinning solution: SnCl 45H 2O is 8%, and PVP is 11%, and DMF is 81%; With Zn (CH 3COO) 22H 2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the 3rd layer of spinning solution, and the mass percent of each material is in the 3rd layer of spinning solution: Zn (CH 3COO) 22H 2O is 9%, and PVP is 12%, and DMF is 79%; With Ti (OC 4H 9) 4, PVP and CH 3COOH joins CH 3CH 2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms shell layer spinning solution, and the mass percent of each material is in the shell layer spinning solution: Ti (OC 4H 9) 4Be 20%, PVP is 8%, CH 3COOH is 18%, CH 3CH 2OH is 54%.
(2) preparation [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable
Coaxial four layers of spinning head that spinning head is nested together and is formed by four syringe needles that cut flat different-diameters, the sandwich layer shower nozzle is for cutting the 5# stainless steel syringe needle after putting down, and external diameter is 0.5mm, and internal diameter is 0.232mm; Second layer shower nozzle is the 12# stainless steel syringe needle that cuts after putting down, and external diameter is 1.2mm, and internal diameter is 0.790mm, and the 3rd layer of shower nozzle is for cutting the 20# stainless steel syringe needle after putting down; External diameter is 2.0mm, and internal diameter is 1.7mm, and the shell shower nozzle is for cutting the veterinary syringe syringe needle after putting down, and external diameter is 3.6mm; Internal diameter is 2.0mm, and in the pipe, second layer spinning solution joined in the second layer pipe in the sandwich layer spinning solution for preparing was joined; The 3rd layer of spinning solution joins in the 3rd layer of pipe, and shell layer spinning solution joins in the outer tube, and successfully flow out to guarantee each layer spinning solution in the gap of regulating sandwich layer shower nozzle, second layer shower nozzle, the 3rd layer of shower nozzle and shell shower nozzle; Adopt coaxial electrostatic spinning technology, adopt perpendicular spray mode, shower nozzle is vertical with horizontal plane; Applying voltage is 19kV, and shower nozzle is 26cm to the curing distance of receiving screen wire netting, 25 ℃-30 ℃ of indoor temperatures; Relative humidity is 48%-55%, along with the volatilization of solvent, on as the wire netting of negative pole, just can collect [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable.
(3) preparation NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable
To [Ni (the CH that is obtained 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable heat-treats, and heating rate is 1 ℃/min, at 1000 ℃ of insulation 8h, naturally cools to room temperature after reducing to 200 ℃ with the speed of 1 ℃/min then, so far obtains NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable.
The NiOSnO of prepared novel structure in the said process 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable are sandwich layer with NiO, and diameter is 35-55nm, and the second layer is SnO 2, thickness is 30-50nm, the 3rd layer is Zn 2TiO 4, thickness is 25-40nm, shell is TiO 2, thickness is 40-90nm, the diameter of coaxial four layers of nano-cable is 225-415nm, cable length＞100 μ m.Realized goal of the invention.
Description of drawings
Fig. 1 is [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the SEM photo of presoma composite cable.
Fig. 2 is NiOSnO 2Zn 2TiO 4TiO 2The XRD spectra of coaxial four layers of nano-cable.
Fig. 3 is NiOSnO 2Zn 2TiO 4TiO 2The SEM photo of coaxial four layers of nano-cable.
Fig. 4 is NiOSnO 2Zn 2TiO 4TiO 2The EDS spectrogram of coaxial four layers of nano-cable.
Fig. 5 is NiOSnO 2Zn 2TiO 4TiO 2The TEM photo of coaxial four layers of nano-cable, the double accompanying drawing that makes an abstract of this figure.
Embodiment
Embodiment: with four water acetic acid nickel (CH 3COO) 24H 2O and polyvinylpyrrolidone PVP (molecular weight is 90000) join N, and among the dinethylformamide DMF, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the sandwich layer spinning solution, and the mass percent of each material is in the sandwich layer spinning solution: Ni (CH 3COO) 24H 2O is 7%, and PVP is 11%, and DMF is 82%; With stannic chloride pentahydrate SnCl 45H 2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms second layer spinning solution, and the mass percent of each material is in the second layer spinning solution: SnCl 45H 2O is 8%, and PVP is 11%, and DMF is 81%; With zinc acetate dihydrate Zn (CH 3COO) 22H 2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the 3rd layer of spinning solution, and the mass percent of each material is in the 3rd layer of spinning solution: Zn (CH 3COO) 22H 2O is 9%, and PVP is 12%, and DMF is 79%; With butyl titanate Ti (OC 4H 9) 4, PVP and glacial acetic acid CH 3COOH joins absolute ethyl alcohol CH 3CH 2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms shell layer spinning solution, and the mass percent of each material is in the shell layer spinning solution: Ti (OC 4H 9) 4Be 20%, PVP is 8%, CH 3COOH is 18%, CH 3CH 2OH is 54%.Adopt coaxial electrostatic spinning technology to spray silk.Coaxial four layers of spinning head that spinning head is nested together and is formed by four syringe needles that cut flat different-diameters, the sandwich layer shower nozzle is for cutting the 5# stainless steel syringe needle after putting down, and external diameter is 0.5mm, and internal diameter is 0.232mm; Second layer shower nozzle is the 12# stainless steel syringe needle that cuts after putting down, and external diameter is 1.2mm, and internal diameter is 0.790mm, and the 3rd layer of shower nozzle is for cutting the 20# stainless steel syringe needle after putting down; External diameter is 2.0mm, and internal diameter is 1.7mm, and the shell shower nozzle is for cutting the veterinary syringe syringe needle after putting down, and external diameter is 3.6mm; Internal diameter is 2.0mm, and in the pipe, second layer spinning solution joined in the second layer pipe in the sandwich layer spinning solution for preparing was joined; The 3rd layer of spinning solution joins in the 3rd layer of pipe, and shell layer spinning solution joins in the outer tube, and successfully flow out to guarantee each layer spinning solution in the gap of regulating sandwich layer shower nozzle, second layer shower nozzle, the 3rd layer of shower nozzle and shell shower nozzle; Adopt coaxial electrostatic spinning technology, adopt perpendicular spray mode, shower nozzle is vertical with horizontal plane; Applying voltage is 19kV, and shower nozzle is 26cm to the curing distance of receiving screen wire netting, 25 ℃-30 ℃ of indoor temperatures; Relative humidity is 48%-55%, along with the volatilization of solvent, on as the wire netting of negative pole, just can collect [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable.With spun [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable puts into the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, at 1000 ℃ of insulation 8h, naturally cools to room temperature after reducing to 200 ℃ with the speed of 1 ℃/min then, so far obtains NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable.Prepared [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable, see shown in Figure 1.Prepared NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable have good crystal formation, are sandwich layer with NiO, SnO 2Be the second layer, the d value of its diffraction maximum and relative intensity and SnO 2The listed d value of PDF standard card (29-1484) and relative intensity coincide, belong to orthorhombic system, space group is P2 12 12 1, the 3rd layer is Zn 2TiO 4, the d value of its diffraction maximum and relative intensity and Zn 2TiO 4The listed d value of PDF standard card (25-1164) and relative intensity coincide, belong to cubic system, space group is Fd-3m, TiO 2Be shell, the d value of its diffraction maximum and relative intensity and TiO 2The listed d value of standard card PDF (21-1276) consistent with relative intensity, belong to rutile TiO 2, being tetragonal crystal system, space group is P4 2/ mnm sees shown in Figure 2.Prepared NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable diameter are 225-415nm, and cable length＞100 μ m is seen shown in Figure 3.NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable are formed (the Au conductive layer of surface plating when Au comes from the SEM sample preparation) by Ni, Sn, Zn, Ti and O element, see shown in Figure 4.Prepared NiOSnO 2Zn 2TiO 4TiO 2The diameter of the sandwich layer NiO of coaxial four layers of nano-cable is 35-55nm, second layer SnO 2Thickness be 30-50nm, the 3rd layer of Zn 2TiO 4Thickness be 25-40nm, shell is TiO 2Thickness be 40-90nm, see shown in Figure 5.
The polyvinylpyrrolidone that the present invention selected for use, absolute ethyl alcohol, N, N-2 NMF, butyl titanate, four water acetic acid nickel, stannic chloride pentahydrate, zinc acetate dihydrate and glacial acetic acid are commercially available analysis net product.Used glass apparatus and equipment are commonly used in the laboratory.
Certainly; The present invention also can have other various embodiments; Under the situation that does not deviate from spirit of the present invention and essence thereof; Those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.

Claims (2)

1. one kind prepares NiOSnO 2Zn 2TiO 4TiO 2The method of coaxial four layers of nano-cable is characterized in that, uses coaxial electrostatic spinning technology, coaxial four layers of spinning head that spinning head is nested together and is formed by four syringe needles that cut flat different-diameters, and the preparation product is NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable, i.e. the 3rd layer of shell structurre of the sandwich layer second layer, sandwich layer is NiO, the second layer is SnO 2, the 3rd layer is Zn 2TiO 4, shell is TiO 2, the steps include:
(1) preparing spinning solution
High polymer templates adopts polyvinylpyrrolidone PVP, and four water acetic acid nickel (CH are used in the nickel source 3COO) 24H 2O, Xi Yuan uses stannic chloride pentahydrate SnCl 45H 2O, zinc acetate dihydrate Zn (CH is used in the zinc source 3COO) 22H 2O, butyl titanate Ti (OC is used in the titanium source 4H 9) 4, solvent adopts absolute ethyl alcohol CH 3CH 2OH and N, dinethylformamide DMF, glacial acetic acid CH 3COOH is an additive, with Ni (CH 3COO) 24H 2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the sandwich layer spinning solution, and the mass percent of each material is in the sandwich layer spinning solution: Ni (CH 3COO) 24H 2O is 7%, and PVP is 11%, and DMF is 82%, with SnCl 45H 2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms second layer spinning solution, and the mass percent of each material is in the second layer spinning solution: SnCl 45H 2O is 8%, and PVP is 11%, and DMF is 81%, with Zn (CH 3COO) 22H 2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the 3rd layer of spinning solution, and the mass percent of each material is in the 3rd layer of spinning solution: Zn (CH 3COO) 22H 2O is 9%, and PVP is 12%, and DMF is 79%, with Ti (OC 4H 9) 4, PVP and CH 3COOH joins CH 3CH 2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms shell layer spinning solution, and the mass percent of each material is in the shell layer spinning solution: Ti (OC 4H 9) 4Be 20%, PVP is 8%, CH 3COOH is 18%, CH 3CH 2OH is 54%;
(2) preparation [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable
Coaxial four layers of spinning head that spinning head is nested together and is formed by four syringe needles that cut flat different-diameters, the sandwich layer shower nozzle is for cutting the 5# stainless steel syringe needle after putting down, and external diameter is 0.5mm, and internal diameter is 0.232mm; Second layer shower nozzle is the 12# stainless steel syringe needle that cuts after putting down, and external diameter is 1.2mm, and internal diameter is 0.790mm, and the 3rd layer of shower nozzle is for cutting the 20# stainless steel syringe needle after putting down; External diameter is 2.0mm, and internal diameter is 1.7mm, and the shell shower nozzle is for cutting the veterinary syringe syringe needle after putting down; External diameter is 3.6mm, and in the pipe, second layer spinning solution joined in the second layer pipe in the sandwich layer spinning solution for preparing was joined; The 3rd layer of spinning solution joins in the 3rd layer of pipe, and shell layer spinning solution joins in the outer tube, and successfully flow out to guarantee each layer spinning solution in the gap of regulating sandwich layer shower nozzle, second layer shower nozzle, the 3rd layer of shower nozzle and shell shower nozzle; Adopt coaxial electrostatic spinning technology, adopt perpendicular spray mode, shower nozzle is vertical with horizontal plane; Applying voltage is 19kV, and shower nozzle is 26cm to the curing distance of receiving screen wire netting, 25 ℃-30 ℃ of indoor temperatures; Relative humidity is 48%-55%, along with the volatilization of solvent, on as the wire netting of negative pole, just can collect [Ni (CH 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable;
(3) preparation NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable
To [Ni (the CH that is obtained 3COO) 2+ PVP] [SnCl 4+ PVP] [Zn (CH 3COO) 2+ PVP] [Ti (OC 4H 9) 4+ CH 3COOH+PVP] the presoma composite cable heat-treats, and heating rate is 1 ℃/min, at 1000 ℃ of insulation 8h, naturally cools to room temperature after reducing to 200 ℃ with the speed of 1 ℃/min then, so far obtains NiOSnO 2Zn 2TiO 4TiO 2Coaxial four layers of nano-cable.
2. a kind of preparation NiOSnO according to claim 1 2Zn 2TiO 4TiO 2The method of coaxial four layers of nano-cable is characterized in that, high polymer templates is the polyvinylpyrrolidone of molecular weight Mr=90000.
CN201110057946A 2011-03-11 2011-03-11 Method for preparing NiO@SnO2@Zn2TiO4@TiO2 coaxial four-layer nanocable Expired - Fee Related CN102222548B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1975504A (en) * 1929-12-07 1934-10-02 Richard Schreiber Gastell Process and apparatus for preparing artificial threads
CN1858308A (en) * 2006-04-21 2006-11-08 东南大学 Preparing low density porous tin dioxide nano fiber laser target material by electro-static spinning method
CN101694018A (en) * 2009-10-14 2010-04-14 长春理工大学 Process for preparing uropium-doped yttrium oxide @ silicon dioxide bean-shaped nano-cables
CN101763917A (en) * 2010-03-04 2010-06-30 长春理工大学 Method for preparing tin dioxide and titanium dioxide nano cable
CN101786600A (en) * 2010-03-04 2010-07-28 长春理工大学 SnO2/ZnO composite polycrystal nanobelt preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1975504A (en) * 1929-12-07 1934-10-02 Richard Schreiber Gastell Process and apparatus for preparing artificial threads
CN1858308A (en) * 2006-04-21 2006-11-08 东南大学 Preparing low density porous tin dioxide nano fiber laser target material by electro-static spinning method
CN101694018A (en) * 2009-10-14 2010-04-14 长春理工大学 Process for preparing uropium-doped yttrium oxide @ silicon dioxide bean-shaped nano-cables
CN101763917A (en) * 2010-03-04 2010-06-30 长春理工大学 Method for preparing tin dioxide and titanium dioxide nano cable
CN101786600A (en) * 2010-03-04 2010-07-28 长春理工大学 SnO2/ZnO composite polycrystal nanobelt preparation method

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