CN114015444A - Preparation method of rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance - Google Patents

Preparation method of rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance Download PDF

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CN114015444A
CN114015444A CN202111252293.9A CN202111252293A CN114015444A CN 114015444 A CN114015444 A CN 114015444A CN 202111252293 A CN202111252293 A CN 202111252293A CN 114015444 A CN114015444 A CN 114015444A
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nitrate
rare earth
titanate
polyvinylpyrrolidone
nanotube material
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CN114015444B (en
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于洪全
田壮
陈宝玖
孙佳石
程丽红
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Dalian Maritime University
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Dalian Maritime University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Abstract

The invention discloses a preparation method of a rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance, which comprises the following steps: s1: dissolving polyvinylpyrrolidone in a solvent containing butyl titanate and rare earth nitrate, stirring and carrying out electrostatic spinning to obtain titanate/polyvinylpyrrolidone precursor composite fiber; s2: and (4) drying, calcining, cooling and cooling the titanate/polyvinylpyrrolidone precursor composite fiber in the step S1 to obtain the rare earth titanate nanotube material. The invention discloses a preparation method of a rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance, wherein the titanate nanotube is prepared by combining the traditional electrostatic spinning technology and the accurate high-temperature annealing process to obtain a rare earth doped nanometer up-conversion luminescence material with controllable inner and outer diameters. The wall thickness of the rare earth titanate nanotube can be adjusted between 20 nm and 60nm, the outer diameter can be adjusted between 150nm and 300nm, and the length of the nanotube is 500nm to 1000 nm.

Description

Preparation method of rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance
Technical Field
The invention relates to the field of up-conversion luminescent materials, in particular to a preparation method of a rare earth titanate nanotube material with up-conversion luminescent/photothermal performance.
Background
The rare earth titanate has many special properties and has wide application in the fields of light, electricity, magnetism and the like. By rare earth doping, up-conversion luminescence can be achieved. After the rare earth titanate luminescent material is subjected to nanocrystallization, the property of the rare earth titanate luminescent material can be greatly changed, and the application range of the rare earth titanate luminescent material can be expanded to the fields of photosensitive detection, solar cells, biological medical treatment and the like. At present, the nano-scale rare earth titanate luminescent material with the shapes of nano wires, nano particles and the like can be obtained by adopting a solid phase method, a coprecipitation method, a sol-gel method, an electrostatic spinning method and the like for synthesis, and the size of the material is dozens of nanometers to hundreds of nanometers.
Disclosure of Invention
The invention provides a preparation method of a rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance, which meets the requirements of the rare earth titanate material on drug loading, photo-thermal treatment and the like in the biomedical field.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance is characterized by comprising the following steps:
s1: dissolving polyvinylpyrrolidone in a solution containing butyl titanate and rare earth nitrate, stirring and carrying out electrostatic spinning to obtain titanate/polyvinylpyrrolidone precursor composite fiber;
s2: and (4) drying, calcining, cooling and cooling the titanate/polyvinylpyrrolidone precursor composite fiber in the step S1 to obtain the rare earth titanate nanotube material.
Further, in the step S1, the molar ratio of the butyl titanate to the rare earth nitrate is 1.02-1.05: 1.0.
further, preferably, in step S1, the polyvinylpyrrolidone: rare earth nitrate: the mass ratio of the solvent is 0.08-0.12: 0.03-0.06: 0.82-0.89.
Further, preferably, in step S1, the polyvinylpyrrolidone: rare earth nitrate: the mass ratio of the solvent is 0.09-0.11: 0.04-0.06: 0.83-0.87.
Further, in step S1, the rare earth nitrate includes a substrate nitrate and a doping nitrate, and the molar ratio of the substrate nitrate to the doping nitrate is 0.80-0.95: 0.05-0.20; the nitrate used for the matrix is one or more of gadolinium nitrate, lutetium nitrate and yttrium nitrate; the nitrate for doping is one or more of erbium nitrate, holmium nitrate, thulium nitrate and ytterbium nitrate.
Further, in step S1, the solvent is one or more of ethanol, N-N dimethylformamide, and acetic acid.
Further, in the step S1, the volume ratio of ethanol, N-N dimethylformamide and acetic acid is 0.46 to 0.49: 0.46-0.49: 0.08-0.02.
Further, in the step S1, the nozzle caliber of the electrostatic spinning is 0.9-1.4mm, the direct current voltage is 10-17kV, and the receiving distance is 10-15 cm.
Further, in the step S2, the temperature is raised to 500-900 ℃ at a temperature raising rate of 0.5-2 ℃/min during the calcination, and the temperature is maintained at the temperature for 4-10 h.
The invention discloses a preparation method of a rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance, wherein the titanate nanotube is prepared by combining the traditional electrostatic spinning technology and the accurate high-temperature annealing process to obtain a rare earth doped nanometer up-conversion luminescence material with controllable inner and outer diameters. The wall thickness of the rare earth titanate nanotube can be adjusted between 20 nm and 60nm, the outer diameter can be adjusted between 150nm and 300nm, and the length of the nanotube is 500nm to 1000 nm. The nano tube has a large specific surface area, can well load various anti-cancer drugs, has a photo-thermal treatment function, is suitable for the biomedical fields of drug delivery, cancer diagnosis and treatment and the like, and can modify functional groups on the inner surface and the outer surface of the nano tube to obtain a multifunctional biomedical functional material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows the present invention Y2Ti2O7：1％Ho3+/5％Yb3+SEM image of nanotube;
FIG. 2 shows a schematic view of the present invention Y2Ti2O7：1％Ho3+/5％Yb3+TEM image of nanotubes;
FIG. 3 shows Y of different doping ratios of rare earth ions2Ti2O7XRD patterns of the nanotube emissive materials;
FIG. 4 is Y2Ti2O7：1％Ho3+/5％Yb3+A first upconversion luminescence spectrum of the nanotube luminescent material;
FIG. 5 is Y2Ti2O7：1％Ho3+/5％Yb3+A second upconversion luminescence spectrum of the nanotube luminescent material;
FIG. 6 is Y2Ti2O7：1％Ho3+/5％Yb3+Temperature-variable spectroscopy of nanotube light-emitting materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
4.0g of polyvinylpyrrolidone (Mw 40, 0000-130,0000) was dissolved in 40ml of a mixed solution of anhydrous ethanol and N-N dimethylformamide (mass ratio of anhydrous ethanol to N-N dimethylformamide is 1:1) until it was clarified. And then 2ml of glacial acetic acid and a certain amount of yttrium nitrate, butyl titanate, holmium nitrate and ytterbium nitrate are added into the solution. Wherein the stoichiometric ratio of yttrium nitrate to butyl titanate is 1.0: 1.02; the stoichiometric ratio of yttrium nitrate to holmium nitrate is 100.0: 5.0; the stoichiometric ratio of yttrium nitrate to ytterbium nitrate is 100.0: 5.0. stirring is continuously carried out by using a magnetic stirrer to obtain uniform and stable spinning solution. Carrying out electrostatic spinning on the obtained spinning solution by taking a copper drum as a fiber collector, controlling the spinning voltage to be 13.8kV, controlling the spinning receiving distance to be 15cm, keeping the air humidity to be (40% +/-10%), carrying out electrostatic spinning on the spinning solution to obtain titanate/polyvinylpyrrolidone (PVP) precursor composite fiber, putting the titanate/polyvinylpyrrolidone (PVP) precursor composite fiber into a vacuum oven to carry out normal-temperature drying for 12h, calcining the dried precursor composite fiber, heating to 500 ℃ at the heating rate of 1 ℃/min during calcination, calcining at 500 ℃ for 4h, continuously heating to 800 ℃ at the heating rate of 1 ℃/min, calcining at 800 ℃ for 6h, and then naturally cooling to obtain Y2Ti2O7：Ho3+/Yb3+A nanotube sample.
Example 2:
4.0g of polyvinylpyrrolidone (Mw 40, 0000-130,0000) was dissolved in 40ml of a mixed solution of anhydrous ethanol and N-N dimethylformamide (mass ratio of anhydrous ethanol to N-N dimethylformamide is 1:1) until it was clarified. And then 2ml of glacial acetic acid and a certain amount of yttrium nitrate, butyl titanate, holmium nitrate and ytterbium nitrate are added into the solution. Wherein the stoichiometric ratio of yttrium nitrate to butyl titanate is 1.0: 1.02; the stoichiometric ratio of yttrium nitrate to holmium nitrate is 100.0: 5.0; the stoichiometric ratio of yttrium nitrate to ytterbium nitrate was 100.0: 10.0. Stirring is continuously carried out by using a magnetic stirrer to obtain uniform and stable spinning solution. Performing electrostatic spinning on the obtained spinning solution by taking a copper drum as a fiber collector, and controllingSpinning at a spinning voltage of 13.8kV and a spinning receiving distance of 15cm, performing electrostatic spinning on a spinning solution by keeping the air humidity at 40% +/-10% to obtain titanate/polyvinylpyrrolidone (PVP) precursor composite fiber, putting the composite fiber into a vacuum oven to dry at normal temperature for 12h, calcining the dried precursor composite fiber, raising the temperature to 500 ℃ at a temperature raising rate of 1 ℃/min, calcining at 500 ℃ for 4h, raising the temperature to 800 ℃ at a speed of 1 ℃/min, calcining at 800 ℃ for 6h, and naturally cooling to obtain Y2Ti2O7：Ho3+/Yb3+A nanotube sample.
Example 3:
4.0g of polyvinylpyrrolidone (Mw 40, 0000-130,0000) was dissolved in 40ml of a mixed solution of anhydrous ethanol and N-N dimethylformamide (mass ratio of anhydrous ethanol to N-N dimethylformamide is 1:1) until it was clarified. And then 2ml of glacial acetic acid and a certain amount of yttrium nitrate, butyl titanate, holmium nitrate and ytterbium nitrate are added into the solution. Wherein the stoichiometric ratio of yttrium nitrate to butyl titanate is 1.0: 1.02; the stoichiometric ratio of yttrium nitrate to holmium nitrate is 100.0: 5.0; the stoichiometric ratio of yttrium nitrate to ytterbium nitrate was 100.0: 20.0. Stirring is continuously carried out by using a magnetic stirrer to obtain uniform and stable spinning solution. Carrying out electrostatic spinning on the obtained spinning solution by taking a copper drum as a fiber collector, controlling the spinning voltage to be 13.8kV, controlling the spinning receiving distance to be 15cm, keeping the air humidity to be (40% +/-10%), carrying out electrostatic spinning on the spinning solution to obtain titanate/polyvinylpyrrolidone (PVP) precursor composite fiber, putting the titanate/polyvinylpyrrolidone (PVP) precursor composite fiber into a vacuum oven to carry out normal-temperature drying for 12h, calcining the dried precursor composite fiber, heating to 500 ℃ at the heating rate of 1 ℃/min during calcination, calcining at 500 ℃ for 4h, continuously heating to 800 ℃ at the heating rate of 1 ℃/min, calcining at 800 ℃ for 6h, and then naturally cooling to obtain Y2Ti2O7:Ho3+/Yb3+A nanotube sample.
And (3) characterization:
y obtained in examples 1 to 3 was used2Ti2O7:Ho3+/Yb3+Nano meterTube samples were analyzed using a Scanning Electron Microscope (SEM), as shown in FIG. 1, where Y is2Ti2O7：1％Ho3+/20％Yb3+The nanotube has an outer diameter of about 150nm to 300nm, a wall thickness of 20 to 60nm, a rough surface and a length of several hundred nanometers to several micrometers.
As shown in FIG. 2, is Y2Ti2O7:1％Ho3+/20％Yb3+TEM images of nanotubes confirming that the nanotubes have diameters of about 150nm to 300nm and wall thicknesses of 20 to 60 nm.
As shown in FIG. 3, is Y2Ti2O7:1％Ho3+/20％Yb3+XRD pattern of nanotubes, illustrating Y produced2Ti2O7Are all phase pure samples.
As shown in FIG. 4, Y is excited by 980nm laser2Ti2O7:1％Ho3+/20％Yb3+The up-conversion luminescence spectrum of the nanotube shows that the luminescence intensity of the nanotube gradually increases along with the increase of the working current of the laser.
As shown in FIG. 5, is Y2Ti2O7:1％Ho3+/20％Yb3+The up-conversion emission intensity of the nanotube is in a relation graph with the change of the laser working current, and it can be seen that the red light emission intensity of the nanotube is almost unchanged with the increase of the laser working current, and the green light emission intensity is gradually increased with the increase of the laser working current.
As shown in FIG. 6, is Y2Ti2O7:1％Ho3+/20％Yb3+The variable temperature spectrogram of the nanotube can see Y2Ti2O7：1％Ho3+/20％Yb3+The up-conversion luminescence intensity of the red light and the green light of the nanotube gradually decreases with the increase of the temperature of the sample.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. A preparation method of a rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance is characterized by comprising the following steps:
s1: dissolving polyvinylpyrrolidone in a solvent containing butyl titanate and rare earth nitrate, stirring and carrying out electrostatic spinning to obtain an inorganic salt/polyvinylpyrrolidone precursor composite fiber;
s2: and (4) drying, calcining, cooling and cooling the inorganic salt/polyvinylpyrrolidone precursor composite fiber in the step S1 to obtain the rare earth titanate nanotube material.
2. The method of claim 1, wherein in step S1, the molar ratio of butyl titanate to rare earth nitrate is 1.02-1.05: 1.0.
3. the method of claim 1, wherein in step S1, the ratio of polyvinylpyrrolidone: rare earth nitrate: the mass ratio of the solvent is 0.08-0.12: 0.03-0.06: 0.82-0.89.
4. The method of claim 3, wherein in step S1, the ratio of polyvinylpyrrolidone: rare earth nitrate: the mass ratio of the solvent is 0.09-0.11: 0.04-0.06: 0.83-0.87.
5. The method for preparing a rare earth titanate nanotube material with upconversion luminescence/photothermal performance according to any one of claims 1-4, wherein in step S1, the rare earth nitrate comprises a host nitrate and a dopant nitrate, and the molar ratio of the host nitrate to the dopant nitrate is 0.80-0.95: 0.05-0.20; the nitrate used for the matrix is one or more of gadolinium nitrate, lutetium nitrate and yttrium nitrate; the nitrate for doping is one or more of erbium nitrate, holmium nitrate, thulium nitrate and ytterbium nitrate.
6. The method of claim 1, wherein in step S1, the solvent is one or more of ethanol, N-N dimethylformamide, and acetic acid.
7. The method for preparing a rare earth titanate nanotube material with upconversion luminescence/photothermal performance according to claim 6, wherein in step S1, the volume ratio of ethanol, N-N dimethylformamide and acetic acid is 0.46-0.49: 0.46-0.49: 0.08-0.02.
8. The method of claim 1, wherein in step S1, the nozzle diameter of the electrostatic spinning is 0.9-1.4mm, the dc voltage is 10-17kV, and the receiving distance is 10-15 cm.
9. The method as claimed in claim 1, wherein in step S2, the temperature is raised to 500-900 ℃ at a rate of 0.5-2 ℃/min and kept at this temperature for 4-10 h.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114843494A (en) * 2022-03-04 2022-08-02 大连海事大学 Rare earth titanate electrode material with tube centerline structure and preparation method thereof

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* Cited by examiner, † Cited by third party
Title
ERKANG HU ET AL.: "Fluorescent Thermal Feedback in Ho3+/Yb3+ Doped Y2Ti2O7 Electrospun Nanofibers" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114843494A (en) * 2022-03-04 2022-08-02 大连海事大学 Rare earth titanate electrode material with tube centerline structure and preparation method thereof
CN114843494B (en) * 2022-03-04 2024-02-20 大连海事大学 Rare earth titanate electrode material with tube centerline structure and preparation method thereof

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