CN109930243B - Nanofiber and preparation method thereof - Google Patents
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- CN109930243B CN109930243B CN201711383288.5A CN201711383288A CN109930243B CN 109930243 B CN109930243 B CN 109930243B CN 201711383288 A CN201711383288 A CN 201711383288A CN 109930243 B CN109930243 B CN 109930243B
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002096 quantum dot Substances 0.000 claims abstract description 134
- 239000000835 fiber Substances 0.000 claims abstract description 100
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 96
- 239000002071 nanotube Substances 0.000 claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 84
- 239000002243 precursor Substances 0.000 claims description 49
- 238000002347 injection Methods 0.000 claims description 30
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 22
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- 238000000034 method Methods 0.000 claims description 18
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Abstract
The invention discloses a nanofiber and a preparation method thereof. The nano-fiber comprises an inorganic oxide fiber nano-tube and quantum dots filled in the inorganic oxide fiber nano-tube. The inorganic oxide fiber nanotube of the invention ensures the chemical stability and the luminescence property of the quantum dot. The preparation method of the nano-fiber has easily controlled conditions, and the prepared nano-fiber with the core-shell structure has stable performance and reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a nanofiber and a preparation method thereof.
Background
The semiconductor quantum dots have the characteristics of being prepared by a wet chemical method, being capable of adjusting an emission peak through size, having high photoluminescence quantum efficiency and the like, and are widely applied to the aspects of light emitting diodes, solar cells, sensors and biomarkers. Quantum dot light-emitting diodes (QLEDs) are one of the applications of semiconductor Quantum dots, and Quantum Dots (QDs) are used as light-emitting layers of QLEDs, which have advantages that are difficult to compare with other light-emitting materials, such as controllable small-size effect, ultrahigh internal Quantum efficiency, excellent color purity and the like, and have great application prospects in the future display technology field.
While semiconductor quantum dots are widely used in light emitting diodes, solar cells, sensors, and biomarkers, quantum dots themselves have certain disadvantages, such as poor chemical/optical stability in oxygen or water, which seriously affects the practical application and commercial production of quantum dots.
In recent years, researchers have made many studies to improve the stability of quantum dots. If a liquid phase method is used for coating another semiconductor inorganic oxide shell layer (less than 10 monomolecular layers) outside a single or a plurality of quantum dots, the stability and the luminous efficiency of the quantum dots can be effectively improved, but the method has the defect that the stability is reduced along with the repeated purification and ligand exchange processes of the quantum dots. In addition, researchers have proposed that the stability of quantum dots can be improved by preparing "giant quantum dots" whose outer layer has tens of monolayers, and thus whose size is large, to effectively isolate the core from the surrounding environment. However, anions and S in the ligand on the surface of the quantum dot are easy to hydrolyze, and the ligand is easy to fall off, so that the stability of the quantum dot is affected.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a nanofiber and a preparation method thereof so as to solve the technical problem that the chemical/optical stability of the existing quantum dots is poor under the condition of oxygen or water.
In order to achieve the object, according to an aspect of the present invention, there is provided a nanofiber including inorganic oxide fiber nanotubes and quantum dots filled in the inorganic oxide fiber nanotubes.
The present invention also provides another nanofiber, which is a tubular structure, comprising:
the outer tube is an inorganic oxide fiber nanotube;
an inner tube, which is a quantum dot layer formed on the inner tube surface of the inorganic oxide fiber nanotube.
In another aspect of the present invention, a method for preparing nanofibers is provided, which comprises the following steps:
providing a quantum dot solution comprising quantum dots dispersed in a solvent and a viscosity control agent;
providing an inorganic oxide fiber precursor solution comprising an inorganic oxide fiber precursor and a viscosity control agent dispersed in the solvent;
and injecting the quantum dot solution into an inner tube of a jet needle tube, injecting an inorganic oxide fiber precursor solution into an outer tube of the jet needle tube, and preparing the nanofiber by adopting a coaxial double-tube electrospinning technology.
Compared with the prior art, the inorganic oxide fiber nano tube protects the quantum dots in the inorganic oxide fiber nano tube and separates the quantum dots from the external environment, so that the quantum dots are effectively prevented from being influenced by external factors such as water vapor and oxygen, and the chemical stability, service life and luminous performance of the quantum dots in the quantum dots are effectively guaranteed.
The preparation method of the nano-fiber adopts a coaxial double-tube electrospinning technology to respectively inject the quantum dot solution and the inorganic oxide fiber precursor solution into the inner tube of the injection needle tube and the outer tube of the injection needle tube to prepare the nano-fiber, and the quantum dot is encapsulated in the inorganic oxide fiber nano-tube, so that the quantum dot is not influenced by external factors such as water vapor, oxygen and the like. The preparation method does not need a phase conversion process, so that the chemical stability and the luminescence property of the quantum dots are effectively improved; in addition, the conditions of the preparation method of the nanofiber are easy to control, the prepared nanofiber has stable performance, and the yield of the nanofiber is effectively improved, so that the photoelectric stability and the service life of the nanofiber are improved, and the production cost is reduced.
Drawings
FIG. 1 is a schematic cross-sectional structure of a nanofiber provided in example 1 or 2 of the present invention;
FIG. 2 is a schematic cross-sectional structure diagram of a tubular nanofiber structure provided in example 3 of the present invention;
FIG. 3 is a schematic process flow diagram of a nanofiber manufacturing process according to an embodiment of the present invention;
FIG. 4 is a scanning electron microscope image of the cross-sectional structure of the nanofiber provided in example 1 of the present invention;
FIG. 5 shows CdZnSe/ZnSe @ TiO in example 2 of the present invention2The luminescent wavelength change diagram of the nanofiber and the existing CdZnSe/ZnSe before and after heat treatment at 150 ℃;
FIG. 6 shows CdZnSe/ZnSe @ TiO in example 2 of the present invention2The relative luminous intensity change diagrams of the nanofiber and the prior CdZnSe/ZnSe before and after heat treatment at 150 ℃.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, embodiments of the present invention provide a nanofiber. The structure of the nanofiber is shown as two structures in the attached figures 1 and 2.
First, as shown in fig. 1, the quantum dots 2 are filled in the cavities of the inorganic oxide fiber nanotubes 1.
As shown in fig. 2, in the second type, the nanofiber has a hollow tubular structure, specifically, the nanofiber comprises an outer tube, and the outer tube is an inorganic oxide fiber nanotube 1; and the inner tube is a quantum dot layer formed on the inner tube surface of the inorganic oxide fiber nanotube, and the quantum dot layer comprises quantum dots 2.
In the nanofiber with the two structures, the quantum dots 2 are encapsulated in the inorganic oxide fiber nanotube 1, and the inorganic oxide fiber nanotube 1 plays a role in protection, so that adverse effects of external factors such as water vapor, oxygen and the like on the quantum dots are avoided.
The inorganic oxide fiber nanotube 1 is used as a protective layer of the quantum dot 2, so that the quantum dot 2 is isolated from the outside, and the adverse effect of the quantum dot 2 caused by external factors such as water vapor and oxygen is avoided. In particular embodiments, the inorganic oxide fibers comprise CeO2Fibrous material, TiO2Fiber material, NiO fiber material, SiO2Fiber material, MgO fiber material, Al2O3At least one of a fiber material and a ZnO fiber material. The inorganic oxide fiber can effectively isolate the quantum dots 2 from the environment, and prevent external factors such as water vapor, oxygen and the like of the quantum dots 2 from affecting the quantumThe dots 2 cause adverse effects, and the stability of the performance of the quantum dots 2 is ensured.
In one embodiment, when the nanofiber has the structure as shown in fig. 1, the outer diameter of the inorganic oxide fiber nanotube 1 is 100-700nm, and the inner diameter of the inorganic oxide fiber nanotube 1 is 10-200 nm.
In one embodiment, when the nanofiber has the structure shown in FIG. 2, the inner diameter of the inner tube is 5-100nm, the outer diameter of the inner tube is 20-200nm, and the outer diameter of the inorganic oxide fiber nanotube 1 is 100-700 nm.
The diameter of the inorganic oxide fiber nanotube 1 is adjusted and controlled, the size of the nanofiber can be adjusted and controlled, and the nanofiber material suitable for device preparation can be obtained on the premise of ensuring the stability and the luminous performance of the quantum dot 2.
The quantum dots contained in the quantum dots 2 can be the conventional single-core quantum dots, core-shell quantum dots or alloy quantum dots. By way of example, the quantum dots may be selected from CdSe, CdS, ZnSe, ZnS, PbSe, PbS, CdTe, ZnO, MgO, CeO2、NiO、TiO2、InP、CaF2、NaYF4、NaCdF4Any one or more of CdZnS, CdZnSe, CdZnS, CdSeS, PbSeS, ZnCdTe, CdSeSn, CdZnSeS, CdS/ZnS, CdZnS/ZnS, CdZnSe/ZnSe, CdSeS/CdSeS/CdS, CdSe/CdZnSe/CdZnSe/ZnSe, CdSe/CdZnSe/ZnS, CdSe/ZnS, CdZnSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/ZnS, CdSe/CdZnSe/ZnS, and InP/ZnS.
On the basis of the nanofiber, the embodiment of the invention also provides a preparation method of the nanofiber. The technological process of the nanofiber preparation method is shown in fig. 3, and comprises the following steps:
s01, providing a quantum dot solution: the quantum dot solution comprises quantum dots and a viscosity control agent dispersed in a solvent;
s02, providing an inorganic oxide fiber precursor solution, wherein the inorganic oxide nanotube precursor solution comprises an inorganic oxide fiber precursor and a viscosity control agent which are dispersed in the solvent;
s03, injecting the quantum dot solution into an inner tube of a jet needle tube, injecting an inorganic oxide fiber precursor solution into an outer tube of the jet needle tube, and preparing the nanofiber by adopting a coaxial double-tube electrospinning technology.
In the step S01, the quantum dots are commonly used single-core quantum dots, core-shell quantum dots, or alloy quantum dots. By way of example, the quantum dots may be selected from CdSe, CdS, ZnSe, ZnS, PbSe, PbS, CdTe, ZnO, MgO, CeO2, NiO, TiO2、InP、CaF2、NaYF4、NaCdF4Any one or more of CdZnS, CdZnSe, CdZnS, CdSeS, PbSeS, ZnCdTe, CdSeSn, CdZnSeS, CdS/ZnS, CdZnS/ZnS, CdZnSe/ZnSe, CdSeS/CdSeS/CdS, CdSe/CdZnSe/CdZnSe/ZnSe, CdSe/CdZnSe/ZnS, CdSe/ZnS, CdZnSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/ZnS, CdSe/CdZnSe/ZnS, and InP/ZnS.
The solvent in the step S01 is selected from one or more of chloroform, toluene, octane, N-hexane, cyclohexane, chlorobenzene, dimethyl sulfoxide, water, ethanol, butanol, octanol, heptanol, N 'N-dimethylformamide, N' N-dimethylacetamide and tetrahydrofuran.
In one embodiment, the quantum dot solution is prepared according to the concentration of the quantum dots being 3-60 mg/mL. The concentration not only can enable the quantum dots to be uniformly dispersed in the solvent, but also can ensure that the concentration is not too high to cause quantum dot fluorescence quenching, and in addition, the quantum dot precursor liquid in the concentration range can be effectively prepared into nano fibers through electrospinning, and the quantum dots are encapsulated in oxide fibers.
In the step S01, a viscosity control agent is added to the quantum dot solution, wherein the viscosity control agent is at least one selected from polyvinylpyrrolidone, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, polymethyl methacrylate, polyacrylamide and polyethylene oxide. The viscosity control agents can be uniformly dispersed in the precursor solution, and the dispersibility of the quantum dots in the precursor solution can be improved; meanwhile, the quantum dot precursor solution has certain viscosity, so that the precursor can form stable and uniformly sprayed fibers when entering a high-voltage electric field through the spraying needle head; in the spinning process, the viscosity control agent can effectively prevent external environments such as water and gas from entering the inorganic oxide fiber nanotube, so that the quantum dots 2 are isolated from the external environments to ensure the stability of the quantum dots 2.
Preferably, the mass concentration of the viscosity control agent in the quantum dot solution is 5-35%. The concentration range can enable the viscosity control agent to be effectively dispersed in the precursor solution, enable the precursor of the quantum dot to be effectively dispersed in the precursor solution, enable the precursor solution to have proper viscosity and form uniform and stable sprayed fibers in a high-voltage electric field.
In the step S02, the solvent is one or more selected from water, ethanol, butanol, octanol, heptanol, N 'N-dimethylformamide, N' N-dimethylacetamide, tetrahydrofuran, propionic acid, acetic acid, chloroform, toluene, octane, N-hexane, cyclohexane, chlorobenzene, and dimethyl sulfoxide.
In one embodiment, the inorganic oxide is dispersed in the solvent at a molar concentration of 0.01 to 1mmol/mL to prepare an inorganic oxide fiber precursor solution. The concentration not only can effectively and uniformly disperse the inorganic oxide in the solvent, but also can ensure that the precursor solution forms stably-sprayed fibers in a high-voltage electric field, so that the inorganic oxide is uniformly dispersed in the fibers, and the dispersion uniformity of the inorganic oxide in the formed inorganic oxide fiber nanotubes is improved.
The inorganic oxide fiber precursor may be nitrate, chloride or acetate of zinc, magnesium, nickel, aluminum and cerium, including: zinc complex, magnesium acetate, nickel acetate, aluminum acetate, cerium acetate, zinc nitrate, magnesium nitrate, aluminum nitrate, cerium nitrate, zinc chloride and magnesium chloride. The inorganic oxide fiber precursor may also be a short chain organic containing titanium, silicon, etc., including: tetrabutyl titanate, titanium isopropoxide, ethyl orthosilicate, methyl orthosilicate, and the like are not limited thereto.
In the step S02, a viscosity controller is added to the inorganic oxide fiber precursor solution. The viscosity control agents can be uniformly dispersed in the precursor solution, so that the dispersibility of the oxide in the precursor solution is improved; meanwhile, the inorganic oxide fiber precursor solution has certain viscosity, so that a stable and uniformly sprayed fiber nanotube can be formed when entering a high-voltage electric field through a spraying needle; in the spinning process, the viscosity control agent can enable the oxide to form uniform liquid drops on the surface of the quantum dot solution, and shell layer fibers are formed in a high-voltage electric field to cover the surface of a fiber structure formed by the quantum dots, so that the blocking uniformity of the inorganic oxide fiber nanotube is improved, and the blocking performance and stability of the quantum dots and the environment are improved. In one embodiment, the mass concentration of the viscosity control agent in the inorganic oxide fiber precursor solution is 5 to 25%. The concentration range can effectively disperse the viscosity control agent in the precursor solution, effectively disperse the oxide in the precursor solution, enable the precursor solution to have proper viscosity, uniformly spread on the surface of the quantum dot liquid drop and form uniform and stable sprayed fibers in a high-voltage electric field.
In the quantum dot solution and the inorganic oxide fiber precursor solution, the viscosity control agent is the same or different and is selected from at least one of polyvinylpyrrolidone, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, polymethyl methacrylate, polyacrylamide and polyethylene oxide.
The step S01 and the step S02 are not in sequence.
In the step S03, the nanofiber of the present invention is formed by injecting the inorganic oxide fiber precursor solution into the outer tube of the injector needle tube and the quantum dot solution into the inner tube of the injector needle tube by a coaxial double-tube electrospinning method. The inorganic oxide fiber nanotube is formed by the inorganic oxide fiber precursor solution, and quantum dots in the injection needle tube quantum dot solution are encapsulated into the inorganic oxide fiber nanotube by the method. The inorganic oxide fiber nanotube is used as a protective layer of the quantum dot, so that the quantum dot is isolated from the outside, and the quantum dot is prevented from being adversely affected by external factors such as water vapor and oxygen. The preparation method does not need a phase conversion process, so that the chemical stability and the luminescence property of the quantum dot are effectively improved. In addition, the conditions of the nanofiber preparation method are easy to control, the performance of the nanofiber of the prepared structural fiber is stable, and the yield of the nanofiber is effectively improved, so that the photoelectric stability and the service life of the nanofiber are improved, and the production cost is reduced.
The sizes of the nano fibers can be adjusted and controlled by selecting the pipe diameters of the inner pipe of the injection needle tube and the outer pipe of the injection needle tube. In one embodiment, the diameter of the cavity of the inner tube of the injection needle tube of the coaxial double-tube electrospinning device is 0.2-0.6mm, and the diameter of the cavity of the outer tube of the injection needle tube is 0.6-1.2 mm.
In one embodiment, the processing conditions for forming the nanofibers by using the coaxial double-tube electrospinning method are as follows: the range of the high-voltage power supply is 12-50kV, the range of the solution spraying rate is 0.3-2mL/h, and the solution spraying distance is 8-25 cm. Under the conditions, the prepared nano-fiber can obtain nano-fibers with different morphologies according to the change of the spraying rate, when the spraying rate is 0.3-1.2mL/h, the formed nano-fiber is the fiber shown in figure 1, and the quantum dots 2 are filled in the inorganic oxide fiber nano-tubes 1. The outer diameter of the inorganic oxide fiber nanotube 1 is 100-700nm, and the inner diameter of the inorganic oxide fiber nanotube 1 is 10-200 nm. When the injection rate is 1.2-2mL/h, the injection rate of the quantum dot solution is high, liquid drops are rapidly formed at the injection pipe orifice, the diameter of the fiber formed by the high-voltage electric field is increased, the inner diameter of the inner pipe is 5-100nm, the outer diameter of the inner pipe is 20-200nm, and the outer diameter of the inorganic oxide fiber nanotube 1 is 100-700 nm. The size range of the formed nano-fiber ensures the dispersibility and the filling property of the quantum dot in the inorganic oxide fiber nanotube, and the luminescent property of the quantum dot is not influenced by the dense packing; meanwhile, the quantum dots can be effectively protected, so that the quantum dots are isolated from water and gas in the external environment, and the stability of the quantum dots is improved.
In addition, after the nano fiber is formed by adopting a coaxial double-tube electrospinning method, the method also comprises the step of drying the nano fiber, wherein the drying temperature is 60-400 ℃, so that a small amount of residual solvent or viscosity regulator in the prepared nano fiber is removed. The reason is that after the precursor nanofibers are formed by adopting a coaxial double-tube electrospinning method, a small amount of solvent or viscosity regulator (including in one embodiment, a small amount of solvent or viscosity regulator is remained in the inorganic oxide fiber nanotubes besides the quantum dots, and in another embodiment, a small amount of solvent or viscosity regulator is remained in the quantum dot layers) remains in the structure of the formed inorganic oxide fiber nanotubes and in the quantum dot materials, and the viscosity controllers and the solvent have low boiling points and are volatilized after being stored in the air for a long time or react with water and gas, so that the stability of the morphology, the structure and the performance of the nanofibers is influenced. It is therefore necessary to remove it as thoroughly as possible in order to ensure the stability of the fibres.
The nanofiber disclosed by the invention can be widely applied to the fields of light-emitting diodes, solar cells, sensors, biomarkers and the like. Wherein, when applied to a light emitting diode, the nanofiber is used as a light emitting layer material of the light emitting diode. When applied to solar cells, biomarkers, the nanofibers described above replace quantum dots in quantum dot solar cells and biomarkers. Due to the good chemical and luminous stability of the quantum dots in the nano-fibers, the working performance and the service life of related devices such as light emitting diodes, solar cells, sensors, biomarkers and drug tracking can be improved, and meanwhile, the production cost can be effectively reduced.
The present invention will now be described in further detail with reference to specific examples. In the following examples, "/" indicates the meaning of a mixture.
Example 1
The embodiment provides a nanofiber and a preparation method thereof. The nano-fiber comprises an inorganic oxide fiber nano-tube and quantum dots filled in the cavity of the inorganic oxide fiber nano-tube; wherein the material of the quantum dot comprises CdS/Cd1-xZnxS/CdyZn1-yS/ZnS quantum dots, wherein the inorganic oxide fiber nano-tube is made of oily ZnO.
The preparation method of the nanofiber comprises the following steps:
s11, preparation of a quantum dot solution:
the prepared CdS/Cd1-xZnxS/CdyZn1-yDrying the S/ZnS quantum dots to prepare a 10mg/mL n-hexane solution, adding 15% by mass of polyvinylpyrrolidone into the n-hexane solution, magnetically stirring for 2 hours, and standing for 30min for later use after the solution is uniformly dissolved;
s12, preparing an inorganic oxide fiber precursor solution:
firstly preparing oily ZnO, preparing the dried ZnO into a chloroform solution with the concentration of 20mg/mL, adding polymethyl methacrylate with the mass ratio of 20% into the chloroform solution, and magnetically stirring for 6 hours. Standing for 30min for later use after the solution is dissolved uniformly;
s13, preparation of nano fibers:
respectively filling a quantum dot solution and an inorganic oxide fiber precursor solution into an inner tube and an outer tube of a coaxial electrospinning device by adopting a coaxial electrospinning technology, wherein the inner diameter of an inner tube injection tube is 0.4mm, the injection rate is 0.5mL/h, the inner diameter of an outer tube injection tube is 0.8mm, the injection rate is 0.8mL/h, the high-voltage power supply voltage is set to be 18kV, the inner tube is aligned with the outer edge of an outer tube injection head, the distance from the injection tube to a receiving device is 18cm, spinning for 3h to obtain the nanofiber with the structure shown in the figure 1, and drying the nanofiber at 200 ℃ for 12h to obtain CdS/Cd1-xZnxS/CdyZn1-yS/ZnS @ ZnO nanofiber. The scanning electron microscope photograph of the nano-fiber is shown in figure 4, the outer diameter of the ZnO inorganic oxide fiber nano-tube is 400nm, and the CdS/Cd filled in the ZnO inorganic oxide fiber nano-tube1-xZnxS/CdyZn1-yThe diameter of a core layer formed by the S/ZnS quantum dots is 150 nm.
Example 2
The embodiment provides a nanofiber and a preparation method thereof. The nano-fiber comprises an inorganic oxide fiber nano-tube and quantum dots filled in the cavity of the inorganic oxide fiber nano-tube; wherein the quantum dot material comprises Cd1- xZnxSe/ZnSe quantum dot, the inorganic oxide fiberThe material of the vitamin nano tube is TiO2。
The preparation method of the nanofiber comprises the following steps:
s21, preparation of a quantum dot solution:
the prepared Cd1-xZnxDrying the Se/ZnSe quantum dots to prepare a n-hexane solution of 5mg/mL, adding polyvinylpyrrolidone with the mass ratio of 25% into the n-hexane solution, magnetically stirring for 2 hours, and standing for 30min for later use after the solution is uniformly dissolved;
s22, preparing an inorganic oxide fiber precursor solution:
weighing 0.5g of polyvinylpyrrolidone, dissolving the polyvinylpyrrolidone in 6.25g of ethanol, adding 0.5g of titanium isopropoxide into PVP-ethanol solution, and magnetically stirring for 2 hours; then adding 2.25g of acetic acid into the mixed solution, stirring for 30min at 50 ℃, and then aging in air at room temperature for 6h to obtain a titanium oxide solution;
s23, preparation of nano fibers:
respectively filling a quantum dot solution and an inorganic oxide fiber precursor solution into an inner tube and an outer tube of a coaxial electrospinning device by adopting a coaxial electrospinning technology, wherein the inner diameter of an inner tube injection tube is 0.2mm, the injection rate is 0.3mL/h, the inner diameter of an outer tube injection tube is 0.6mm, the injection rate is 0.5mL/h, the voltage of a high-voltage power supply is set to be 30kV, the inner tube is aligned with the outer edge of an outer tube injection head, the distance from the injection tube to a receiving device is 12cm, spinning for 3h to obtain the nano-fiber with the structure shown in the figure 1, and drying the nano-fiber at 200 ℃ for 12h to obtain Cd1-xZnxSe/ZnSe@TiO2And (3) nano fibers. The TiO is2The inorganic oxide fiber nanotube has an outer diameter of 500nm and is filled in TiO2Cd in inorganic oxide fiber nanotubes1-xZnxThe core layer formed by the Se/ZnSe quantum dots has the diameter of 200 nm.
Example 3
The embodiment provides a nanofiber and a preparation method thereof. The nano fiber hollow tubular structure comprises an inorganic oxide fiber nano tube and a quantum dot layer formed on the inner wall surface of the inorganic oxide fiber nano tube cavity, wherein the quantum dot layer enclosesForming a hollow portion of the nanofiber; wherein the quantum dot material of the quantum dot layer comprises Cd1-xZnxSe/ZnSe quantum dots, and the material of the inorganic oxide fiber nano-tube is SiO2。
The preparation method of the nanofiber comprises the following steps:
s31, preparing a quantum dot solution for forming a quantum dot layer:
the prepared Cd1-xZnxSe/CdyZn1-yDrying the S/ZnS quantum dots to prepare a 50mg/mL octane solution, adding 30% polyvinyl chloride by mass into the n-hexane solution, magnetically stirring for 2h, and standing for 30min for later use after the solution is uniformly dissolved;
s32, preparing an inorganic oxide fiber precursor solution:
weighing 600mg of tetraethoxysilane, adding the tetraethoxysilane into a mixed solution of 6mL of ethanol and 1.5mL of water, then adding 0.5g of polyvinyl chloride into the solution, magnetically stirring for 2 hours, and then aging in the air at room temperature for 30min to obtain SiO2A solution;
s33, preparation of nano fibers:
respectively filling a quantum dot solution and an inorganic oxide fiber precursor solution into an inner tube and an outer tube of a coaxial electrospinning device by adopting a coaxial electrospinning technology, wherein the inner diameter of an inner tube injection tube is 0.6mm, the injection rate is 1.5mL/h, the inner diameter of an outer tube injection tube is 1.2mm, the injection rate is 1.8mL/h, the high-voltage power supply voltage is set to be 50kV, the inner tube is aligned with the outer edge of an outer tube injection head, the distance from the injection tube to a receiving device is 25cm, spinning for 3h to obtain the nanofiber with the tubular structure shown in figure 2, and drying the nanofiber at 400 ℃ for 12h to obtain Cd1-xZnxSe/CdyZn1-yS/ZnS@SiO2And (3) nano fibers. The SiO2The inorganic oxide fiber nanotube has an outer diameter of 500nm and is filled in SiO2Cd in inorganic oxide fiber nanotubes1-xZnxThe outer diameter of a quantum dot layer formed by Se/ZnSe quantum dots is 200nm, and the diameter of a hollow part formed by enclosing the quantum dot layer is 80 nm.
And (3) testing the luminescence stability of the nanofiber:
the nanofibers of example 2 and the existing Cd that was not coated with inorganic oxide fiber nanotubes 11-xZnxThe Se/ZnSe quantum dots are respectively subjected to heat treatment in the air at 150 ℃ for 60min, and the trend of the change of the luminescence wavelength and the relative luminescence intensity of each nanofiber before and after the heat treatment along with time is tested. Wherein Cd in example 21-xZnxSe/ZnSe@TiO2Nanofibers and existing Cd1-xZnxThe change in luminescence wavelength before and after heat treatment of Se/ZnSe at 150 ℃ is shown in FIG. 5, and the change in relative luminescence intensity is shown in FIG. 6. As can be seen from FIGS. 5 and 6, Cd in example 21-xZnxSe/ZnSe@TiO2The luminescent wavelength of the nano-fiber is almost unchanged before and after the heat treatment process, and the reduction degree of the luminescent intensity is relatively higher than that of the existing Cd1-xZnxThe Se/ZnSe quantum dots are obviously small, which shows that the luminous stability of the quantum dots coated by the inorganic oxide fiber nanotubes is effectively improved. Further analysis of the results of the luminescence stability of the nanofibers provided in examples 1 and 3 shows that the nanofibers provided in examples 1 and 3 all have excellent luminescence stability as the nanofibers in example 2. Therefore, the nanofiber provided by the embodiment of the invention effectively improves the chemical and luminescent stability of the quantum dots in the quantum dots.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A nanofiber, characterized in that the nanofiber is a tubular structure, the nanofiber comprising:
the outer tube is an inorganic oxide fiber nanotube;
an inner tube which is a quantum dot layer formed on the inner tube surface of the inorganic oxide fiber nanotube;
the inorganic oxide fiber material in the inorganic oxide fiber nano-tube is selected from CeO2Fiber material, NiO fiber material, MgO fiber material, Al2O3At least one of fiber material and ZnO fiber material, wherein the outer diameter of the inorganic oxide fiber nanotube is 100-700nm, the inner diameter of the inner tube is 5-100nm, and the outer diameter of the inner tube is 20-200 nm.
2. The nanofiber according to claim 1, wherein the inorganic oxide fiber nanotube is composed of an inorganic nanofiber, and the material of the quantum dot layer is a quantum dot.
3. The nanofiber according to claim 1, wherein the quantum dots are selected from the group consisting of ZnSe, CdTe, CeO2、TiO2、CaF2、NaYF4、NaCdF4Any one or more of CdZnSe, CdZnS, CdSeS, PbSeS, ZnCdTe, CdSeSn, CdZnSeS, CdS/ZnS, CdZnS/ZnSe, CdSeS/CdS, CdSe/CdZnSe/CdZnSe/ZnSe, CdS/CdZnS/CdZnS, CdSe/ZnS, CdZnSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/ZnS, CdZnSe/CdZnS/ZnS and InP/ZnS.
4. A method for preparing nanofibres according to any of claims 1-3, characterised in that it comprises the following steps:
providing a quantum dot solution comprising quantum dots dispersed in a solvent and a viscosity control agent;
providing an inorganic oxide fiber precursor solution, wherein the inorganic oxide fiber precursor solution comprises an inorganic oxide fiber precursor and a viscosity control agent which are dispersed in a solvent;
injecting the quantum dot solution into an inner tube of a jet needle tube, injecting an inorganic oxide fiber precursor solution into an outer tube of the jet needle tube, and preparing the nanofiber by adopting a coaxial double-tube electrospinning technology;
wherein the mass concentration of the viscosity control agent in the quantum dot solution is 5-35%; the technological conditions for forming the nano-fiber by adopting the coaxial double-tube electrospinning method are as follows:
the range of a high-voltage power supply is 12-50kV, the range of the solution spraying rate is 1.2-2mL/h, and the solution spraying distance is 8-25 cm.
5. The preparation method according to claim 4, wherein the preparation method comprises the steps of injecting the quantum dot solution into an inner tube of a spray needle tube, injecting the inorganic oxide fiber precursor solution into an outer tube of the spray needle tube, and preparing the nanofiber by adopting a coaxial double-tube electrospinning technology, and then drying the nanofiber, wherein the drying temperature is 60-400 ℃.
6. The preparation method according to claim 4 or 5, characterized in that the inorganic oxide fiber precursor is dispersed in the solvent to prepare the inorganic oxide fiber precursor solution, with the molar volume ratio of the inorganic oxide fiber precursor to the solvent being 0.01 to 1 mmol/mL; and/or
In the inorganic oxide fiber precursor solution, the mass fraction of the viscosity control agent is 5-25%.
7. The preparation method according to claim 4, wherein the viscosity control agent in the quantum dot solution and the viscosity control agent in the inorganic oxide fiber precursor solution are the same or different, and the viscosity control agent is selected from at least one of polyvinylpyrrolidone, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, polymethyl methacrylate, polyacrylamide and polyethylene oxide.
8. The production method according to claim 4 or 5, wherein the inner tube diameter of the injection needle tube is 0.2 to 0.6 mm; and/or
The diameter of the outer tube of the injection needle tube is 0.6-1.2 mm.
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