CN102586950B - Method for preparing zinc selenide (ZnSe) nanofiber - Google Patents
Method for preparing zinc selenide (ZnSe) nanofiber Download PDFInfo
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- CN102586950B CN102586950B CN 201210042967 CN201210042967A CN102586950B CN 102586950 B CN102586950 B CN 102586950B CN 201210042967 CN201210042967 CN 201210042967 CN 201210042967 A CN201210042967 A CN 201210042967A CN 102586950 B CN102586950 B CN 102586950B
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Abstract
The invention relates to a method for preparing a zinc selenide (ZnSe) nanofiber, belonging to the technical field of nano material preparation. The method is characterized by adopting a double-crucible method and combining the electrospinning technology and the selenization technology to prepare the ZnSe nanofiber. The method comprises the following three steps of: (1) preparing a spinning liquid: adding Zn(NO3)2.6H2O and PVP to a DMF (dimethylformamide) solution to form the spinning liquid; (2) preparing a ZnO nanofiber: preparing a PVP/Zn(NO3)2 composite nanofiber by adopting the electrospinning technology and then carrying out heat treatment on the composite nanofiber to obtain the ZnO nanofiber; and (3) preparing the ZnSe nanofiber: carrying out selenization on the ZnO nanofiber withselenium powder by adopting the double-crucible method to obtain the ZnSe nanofiber. The ZnSe nanofiber has good crystal form, diameter of 70-140nm and length more than 100mu m. The ZnSe nanofiber isa novel important functional material and can be applied in such fields as lasers, biomedicine, solar cells, panel display, information storage and transmission, flashers and catalysis. The preparation method is simple and practical, can realize batch production and has a broad application prospect.
Description
Technical field
The present invention relates to the nano material preparing technical field, relate to specifically a kind of method for preparing the zinc selenide nanofiber.
Background technology
Nanofiber refers to have bidimensional to be in the filamentary material of nanoscale at the three dimensions yardstick of material, and radial dimension is nanometer scale usually, and length is then larger.Because the radial dimension of nanofiber is little of nanometer scale, demonstrate series of characteristics, the most outstanding is that specific area is large, 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, such as the method for 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 nanofiber or nanotube through pyrolysis (or directly condensation), from essence, all belong to the compound steam sedimentation.
Zinc selenide ZnSe crystal belongs to direct band gap II-VI family semiconductor, is a kind of good luminescent material, has direct transition type band structure, and energy gap is 2.67eV when room temperature.The storage and transmission, solar cell, chemistry and the fields such as biology sensor, biomedical mark, ray detector, semiconductor scintillator and catalysis that are widely used in light emitting diode, laser instrument, FPD, information.Because its unique performance, the ZnSe of different morphologies is produced out such as nanometer rods, nano wire, nanobelt, nanocrystalline, nanosphere, polycrystalline Nano film, quadruped structure, flower shape structure and hollow nanostructures may etc.The method that adopts comprises: hydro-thermal method, solvent-thermal method, solution thermal reduction, surperficial soft mode method, chemical vapour deposition (CVD), molecular beam epitaxial growth, electron beam irradiation synthetic method, chemical vapor transportation method, sol-gel process etc.At present, prepare the relevant report of ZnSe nanofiber there are no adopting electrostatic spinning technique to combine with the selenizing technology.
The patent No. is the technical scheme that 1975504 United States Patent (USP) discloses a relevant electrospinning process (electrospinning), the 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 sprayed by nozzle, invest the receiving screen on opposite, thereby realization wire drawing, then, at normal temperatures solvent evaporation, perhaps melt cooling solidifies to normal temperature, 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.The employing electrostatic spinning techniques such as Wang Jinxian have prepared rare earth fluoride/rare earth oxyfluoride composite nano fibre (Chinese invention patent, application number: 200810050959.0).Electrospinning process can continuous production big L/D ratio micrometer fibers or nanofiber.At present, prepare the relevant report of ZnSe nanofiber there are no adopting electrostatic spinning technique to combine with the selenizing technology.
When utilizing electrostatic spinning technique to prepare nano material, the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter and Technology for Heating Processing have material impact to pattern and the size of final products.The present invention adopts first electrostatic spinning technique, with zinc nitrate hexahydrate Zn (NO
3)
26H
2O is raw material, adds solvent DMF DMF and high polymer templates polyvinylpyrrolidone PVP, obtains carrying out electrostatic spinning behind the spinning solution, under the experiment condition of the best, prepares PVP/Zn (NO
3)
2Original nanofiber is heat-treated it in air, obtain the ZnO nano fiber, adopts double crucible method, carries out selenizing take selenium powder as selenizing agent, has prepared the ZnSe nanofiber of novel structure pure phase.
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.Use electrostatic spinning technique in the background technology has prepared metal oxide, composite oxide of metal nanofiber and rare earth fluoride/rare earth oxyfluoride composite nano fibre.Prior art adopts hydro-thermal method, solvent-thermal method, the solution thermal reduction, surface soft mode method, chemical vapour deposition (CVD), molecular beam epitaxial growth, the electron beam irradiation synthetic method, the chemical vapor transportation method, sol-gel process etc. have prepared ZnSe nanometer rods, nano wire, nanobelt, nanocrystalline, nanosphere, polycrystalline Nano film, quadruped structure, flower shape structure and hollow nanostructures may etc.In order to provide the ZnSe nanofiber a kind of new preparation method, we combine electrostatic spinning technique with the selenizing technology, invented a kind of preparation method of ZnSe nanofiber.
The present invention is achieved in that the spinning solution with certain viscosity of at first preparing for electrostatic spinning, uses electrostatic spinning technique and carries out electrostatic spinning, under the experiment condition of the best, prepares PVP/Zn (NO
3)
2Original nanofiber is heat-treated it in air, obtain the ZnO nano fiber, adopts double crucible method, carries out selenizing take selenium powder as selenizing agent, has prepared the ZnSe nanofiber of novel structure pure phase.The steps include:
(1) preparation spinning solution
That use in the zinc source is zinc nitrate hexahydrate Zn (NO
3)
26H
2O, high polymer templates adopts polyvinylpyrrolidone PVP, and molecular weight is 1300000, and adopting DMF DMF is solvent, takes by weighing a certain amount of Zn (NO
3)
26H
2O and PVP join in an amount of DMF solvent, stir 4h in the room temperature lower magnetic force, and leave standstill 2h, namely form spinning solution, and the mass percent of this each part of spinning solution is: zinc nitrate content 8%, PVP content 14%, solvent DMF content 78%;
(2) making ZnO nanofiber
The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 1mm, the angle of adjusting shower nozzle and horizontal plane is 30 °, applies the DC voltage of 18kV, solidifies apart from 20cm, 18～25 ℃ of room temperatures, relative humidity is 50%～60%, obtains PVP/Zn (NO
3)
2Composite nano fiber is with described PVP/Zn (NO
3)
2Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, and at 600 ℃ of constant temperature 4h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the ZnO nano fiber;
(3) preparation ZnSe nanofiber
Selenizing reagent uses selenium powder, adopt double crucible method, selenium powder is put into monkey, the above covers carbon-point, described ZnO nano fiber is placed on above the carbon-point, monkey is put into larger crucible, between interior outer crucible, add excessive selenium powder, add that at outer crucible the crucible lid puts into tube furnace, when room temperature, pass into Ar argon gas 30min, discharge the air in the boiler tube, with the heating rate to 700 of 5 ℃/min ℃, insulation 3h, be down to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cool to afterwards room temperature, obtain the ZnSe nanofiber, diameter is 70～140nm, and length is greater than 100 μ m.
Have good crystal formation at the ZnSe nanofiber described in the said process, diameter is 70～140nm, and length has realized goal of the invention greater than 100 μ m.
Description of drawings
Fig. 1 is the XRD spectra of ZnSe nanofiber;
Fig. 2 is the SEM photo of ZnSe nanofiber, and this figure doubles as Figure of abstract;
Fig. 3 is the EDS spectrogram of ZnSe nanofiber;
Fig. 4 is the dielectric constant figure of ZnSe nanofiber;
Fig. 5 is the dielectric loss figure of ZnSe nanofiber;
Fig. 6 is the conductivity map of ZnSe nanofiber.
The specific embodiment
Zinc nitrate hexahydrate Zn (the NO that the present invention is selected
3)
26H
2O, polyvinylpyrrolidone PVP, molecular weight 1300000, DMF DMF, selenium powder, carbon-point are commercially available analysis net product; Used glass apparatus, crucible and equipment are instrument and equipments commonly used in the laboratory.
Embodiment: take by weighing a certain amount of Zn (NO
3)
26H
2O and PVP join in an amount of DMF solvent, stir 4h in the room temperature lower magnetic force, and leave standstill 2h, namely form spinning solution, and the mass percent of this each part of spinning solution is: zinc nitrate content 8%, PVP content 14%, solvent DMF content 78%; The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 1mm, the angle of adjusting shower nozzle and horizontal plane is 30 °, applies the DC voltage of 18kV, solidifies apart from 20cm, 18～25 ℃ of room temperatures, relative humidity is 50%～60%, obtains PVP/Zn (NO
3)
2Composite nano fiber is with described PVP/Zn (NO
3)
2Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, and at 600 ℃ of constant temperature 4h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the ZnO nano fiber; Selenizing reagent uses selenium powder, adopt double crucible method, selenium powder is put into monkey, the above covers carbon-point, described ZnO nano fiber is placed on above the carbon-point, monkey is put into larger crucible, between interior outer crucible, add excessive selenium powder, add that at outer crucible the crucible lid puts into tube furnace, when room temperature, pass into Ar argon gas 30min, discharge the air in the boiler tube, with the heating rate to 700 of 5 ℃/min ℃, insulation 3h is down to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cool to afterwards room temperature, obtain the ZnSe nanofiber.Described ZnSe nanofiber has good crystallinity, and listed d value and the relative intensity of the d value of its diffraction maximum and relative intensity and the PDF standard card (65-9602) of ZnSe is consistent, belongs to cubic system, and space group is F-43m, as shown in Figure 1.The diameter of described ZnSe nanofiber is 70～140nm, and length is greater than 100 μ m, as shown in Figure 2.The ZnSe nanofiber forms (the Au conductive layer of plated surface when Au derives from the SEM sample preparation) by Zn and Se element, as shown in Figure 3.The dielectric constant of ZnSe nanofiber reduces with the increase of ac frequency, as shown in Figure 4.The dielectric loss of ZnSe nanofiber reduces with the increase of ac frequency, as shown in Figure 5.The electrical conductivity of ZnSe nanofiber increases along with the increase of ac frequency, as shown in Figure 6.
Certainly; the present invention also can have other various embodiments; in 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 according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (1)
1. method for preparing the zinc selenide nanofiber, it is characterized in that, adopt double crucible method, electrostatic spinning technique is combined with the selenizing technology, use the polyvinylpyrrolidone PVP of molecular weight Mr=1300000 to be high polymer templates, adopt N, dinethylformamide DMF is solvent, selenizing reagent uses selenium powder, and the preparation product is the ZnSe nanofiber, the steps include:
(1) preparation spinning solution
Take by weighing a certain amount of zinc nitrate hexahydrate Zn (NO
3)
26H
2O and polyvinylpyrrolidone PVP join in an amount of DMF DMF solvent, stir 4h in the room temperature lower magnetic force, and leave standstill 2h, namely form spinning solution, the mass percent of this each part of spinning solution is: zinc nitrate content 8%, PVP content 14%, solvent DMF content 78%;
(2) making ZnO nanofiber
The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 1mm, the angle of adjusting shower nozzle and horizontal plane is 30 °, applies the DC voltage of 18kV, solidifies apart from 20cm, 18～25 ℃ of room temperatures, relative humidity is 50%～60%, obtains PVP/Zn (NO
3)
2Composite nano fiber is with described PVP/Zn (NO
3)
2Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, and at 600 ℃ of constant temperature 4h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the ZnO nano fiber;
(3) preparation ZnSe nanofiber
Selenizing reagent uses selenium powder, adopt double crucible method, selenium powder is put into monkey, the above covers carbon-point, described ZnO nano fiber is placed on above the carbon-point, monkey is put into larger crucible, between interior outer crucible, add excessive selenium powder, add that at outer crucible the crucible lid puts into tube furnace, when room temperature, pass into Ar argon gas 30min, discharge the air in the boiler tube, with the heating rate to 700 of 5 ℃/min ℃, insulation 3h, be down to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cool to afterwards room temperature, obtain the ZnSe nanofiber, diameter is 70～140nm, and length is greater than 100 μ m.
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| CN103840076B (en) * | 2014-03-18 | 2016-09-07 | 哈尔滨师范大学 | A kind of carbon fiber/zinc oxide-zinc selenide bivalve micro-line nano generator nano material and its preparation method and application |
| CN104862817A (en) * | 2015-06-02 | 2015-08-26 | 天津工业大学 | Preparation method of health-care fiber containing nanometer selenium |
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| CN109755527B (en) * | 2019-01-04 | 2021-06-04 | 中南大学 | Preparation method and application of zinc selenide/carbon fiber energy storage material |
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| CN112670507B (en) * | 2020-12-22 | 2022-05-20 | 江苏大学 | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery |
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