CN102618283A - Method for preparing bowknot-shaped terbium-mixed Teflon gadolinium sodium green luminous nanometer materials - Google Patents
Method for preparing bowknot-shaped terbium-mixed Teflon gadolinium sodium green luminous nanometer materials Download PDFInfo
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- CN102618283A CN102618283A CN2012100429592A CN201210042959A CN102618283A CN 102618283 A CN102618283 A CN 102618283A CN 2012100429592 A CN2012100429592 A CN 2012100429592A CN 201210042959 A CN201210042959 A CN 201210042959A CN 102618283 A CN102618283 A CN 102618283A
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Abstract
The invention relates to a method for preparing bowknot-shaped terbium-mixed Teflon gadolinium sodium green luminous nanometer materials, which belongs to the technical field of nanometer material preparation and comprises three steps of (1) preparing mixed solution, using nitric acid to dissolve Tb4O7, evaporating to obtain Tb(NO3)3, adding deionized water, then adding Gd(NO3)3-6H2O, achieving mixed solution of [Gd(NO3)3+Tb(NO3)3], forming mixed solution of [Gd(NO3)3+Tb(NO3)3 + herring sperm deoxyribonucleic acid (DNA)]; (2) preparing NaGdF4: 5%Tb3 + sediment, and dropwise adding NaF water solution into the mixed solution to obtain the NaGdF4: 5%Tb3 + sediment; (3) preparing a bowknot-shaped NaGdF4: 5%Tb3 + green luminous nanometer material, transferring the NaGdF4: 5%Tb3 + sediment into a hydrothermal reaction kettle to react for 16 hours at the temperature of 160 DEG C, taking out the reaction kettle to be cooled to the room temperature, and continuing to age for 12 hours to obtain the bowknot-shaped NaGdF4: 5%Tb3 + green luminous nanometer material with good crystallinity. The length of the bowknot-shaped NaGdF4: 5%Tb3 + green luminous nanometer material is 831+/-72nm, the diameter of the bowknot position of the bowknot-shaped NaGdF4: 5%Tb3 + green luminous nanometer material is 166+/-14nm, and the diameter of each nanometer bar in the bowknot-shaped nanometer material is 110+/-9nm. The method is simple and practicable, economic and environmental0friendly, and wide in application prospect.
Description
Technical field
The present invention relates to the nano material preparation research field, relate to a kind of method that bow tie is mixed terbium tetrafluoro gadolinium sodium green emitting nano material for preparing specifically.
Background technology
The rare earth tetrafluoride is one of present efficient rare-earth ion doping luminous host owing to have abundant 4f energy level and lower phonon ability.Mix terbium tetrafluoro gadolinium sodium NaGdF
4: Tb
3+Be a kind of important green luminescent material, have important application.Adopt methods such as the precipitator method, sol-gel method, microemulsion method, presoma pyrogenic silica, hydro-thermal and solvent-thermal method, polyvalent alcohol method, high boiling point ligand solvent method, method of electrostatic spinning, prepared NaGdF
4: Tb
3+Nano materials such as nanocrystalline, nanometer rod, sheet, hollow tubular structures, nano wire, fusiform.Bow tie is mixed terbium tetrafluoro gadolinium sodium NaGdF
4: Tb
3+Nano material is a kind of novel green luminescent material, will obtain important application in fields such as luminous and demonstration, biomarker, false proof, medical science detection, solar cell, chemistry and biosensor, nano-devices, has broad application prospects.At present, do not see that bow tie mixes terbium tetrafluoro gadolinium sodium NaGdF
4: Tb
3+The report of nano material.
With DNA is the existing report of template synthesizing inorganic nano material.For example, employing DNA such as Liu Xianhua are that template has been assembled zinc oxide nano-chain (Chinese invention patent, application number: 200910229007.X); Employing DNA such as Xu Hui are that template has prepared metal nano conductor (Chinese invention patent, application number: 200810031316.1); Employing DNA such as Li Na are that template has prepared chain shaped barium fluoride nanospheres (Chinese invention patent, application number: 200810079482.9); Employing DNA such as Dong Xiangting are that template has prepared and mixes europium lanthanum fluoride porous nanoparticles (Chinese invention patent, application number: 201010550250.4).At present, do not see that adopting DNA is that template prepares bow tie NaGdF
4: Tb
3+The report of nano material.
It is template that the present invention adopts herring sperm dna, with six nitric hydrate gadolinium Gd (NO
3)
36H
2O, terbium sesquioxide Tb
4O
7With Sodium Fluoride NaF be raw material, be solvent with the deionized water, use hydrothermal method, under the experiment condition of the best, prepared bow tie NaGdF
4: Tb
3+Nano material, in the present invention, the molecular fraction of adulterated terbium ion is 5%, is labeled as NaGdF
4: 5%Tb
3+, i.e. that the present invention is prepared is bow tie NaGdF
4: 5%Tb
3+Nano material.
Summary of the invention
Preparation NaGdF in background technology
4: Tb
3+Nano materials such as nanocrystalline, nanometer rod, sheet, hollow tubular structures, nano wire, fusiform have adopted methods such as the precipitator method, sol-gel method, microemulsion method, presoma pyrogenic silica, hydro-thermal and solvent-thermal method, polyvalent alcohol method, high boiling point ligand solvent method, method of electrostatic spinning; With DNA is the inorganic nano material that template has been synthesized patterns such as nano chain, nm-class conducting wire, nanometer ball and porous nanoparticles.The pattern of employed template, preparation product is all different with method of the present invention in the background technology.It is template that the present invention adopts herring sperm dna, uses hydrothermal method, has prepared bow tie NaGdF
4: 5%Tb
3+The green emitting nano material.
The present invention is achieved in that herring sperm dna is dissolved in the deionized water, prepares the certain density herring sperm dna aqueous solution.Use nitric acid HNO
3Dissolving Tb
4O
7The back evaporation obtains Tb (NO
3)
3Crystal adds deionized water, obtains Tb (NO
3)
3Solution adds Gd (NO again
3)
36H
2O obtains Gd (NO
3)
3And Tb (NO
3)
3Mixing solutions, the herring sperm dna aqueous solution is joined Gd (NO
3)
3And Tb (NO
3)
3Mixing solutions in, add NaF solution again and precipitate, the mixture that obtains is transferred to is carried out hydrothermal treatment consists in the hydrothermal reaction kettle, afterwards deposition is carried out spinning, absolute ethanol washing and vacuum drying treatment after, obtain bow tie NaGdF
4: 5%Tb
3+The green emitting nano material.The steps include:
(1) preparation mixing solutions
Take by weighing the 0.06g herring sperm dna and be dissolved in the 25ml deionized water, obtain the aqueous dna that concentration is 3mg/ml; Take by weighing 0.0374g terbium sesquioxide Tb
4O
7, use nitric acid HNO
3The evaporation of dissolving back obtains Tb (NO
3)
3Crystal adds the 40ml deionized water, adds 1.7152g Gd (NO again
3)
36H
2O obtains [Gd (NO after the dissolving fully
3)
3+ Tb (NO
3)
3] mixing clear aqueous solution, wherein Gd
3+With Tb
3+Mol ratio be 95: 5; The herring sperm dna aqueous solution is joined [Gd (NO
3)
3+ Tb (NO
3)
3] in the mixing solutions, form [Gd (NO
3)
3+ Tb (NO
3)
3+ herring sperm dna] mixing solutions;
(2) preparation NaGdF
4: 5%Tb
3+Deposition
To described [Gd (NO
3)
3+ Tb (NO
3)
3+ herring sperm dna] mixed solution and dripping 20ml contains the aqueous solution of 2.016g NaF, obtains NaGdF
4: 5%Tb
3+Deposition;
(3) preparation bow tie NaGdF
4: 5%Tb
3+The green emitting nano material
With described NaGdF
4: 5%Tb
3+Deposition is transferred in 2 50ml hydrothermal reaction kettles, hydrothermal reaction kettle is put in the loft drier, in 160 ℃ of reaction 16h; Naturally cool to room temperature after taking out reaction kettle, and continue ageing 12h, open reaction kettle afterwards; Deposition after the hydro-thermal is carried out spinning; After absolute ethyl alcohol is given a baby a bath on the third day after its birth time,, obtain bow tie NaGdF in 70 ℃ of vacuum-drying 6h
4: 5%Tb
3+Green emitting nano material, the length of bow tie nano material are 831 ± 72nm, and the diameter at bow-knot-double place is 166 ± 14nm in the bow tie nano material, and the diameter of every nanometer rod is 110 ± 9nm in the bow tie nano material.
At the bow tie NaGdF described in the said process
4: 5%Tb
3+The green emitting nano material has good crystallinity; The length of bow tie nano material is 831 ± 72nm; The diameter at bow-knot-double place is 166 ± 14nm in the bow tie nano material, and the diameter of every nanometer rod is 110 ± 9nm in the bow tie nano material, has realized goal of the invention.
Description of drawings
Fig. 1 is bow tie NaGdF
4: 5%Tb
3+The XRD figure of green emitting nano material;
Fig. 2 is bow tie NaGdF
4: 5%Tb
3+The SEM photo of green emitting nano material, this figure double as Figure of abstract;
Fig. 3 is bow tie NaGdF
4: 5%Tb
3+The length distribution histogram of green emitting nano material;
Fig. 4 is bow tie NaGdF
4: 5%Tb
3+The diameter Distribution histogram at bow-knot-double place in the green emitting nano material;
Fig. 5 is bow tie NaGdF
4: 5%Tb
3+The diameter Distribution histogram of every nanometer rod in the green emitting nano material;
Fig. 6 is bow tie NaGdF
4: 5%Tb
3+The EDS spectrogram of green emitting nano material;
Fig. 7 is bow tie NaGdF
4: 5%Tb
3+The exciting light spectrogram of green emitting nano material;
Fig. 8 is bow tie NaGdF
4: 5%Tb
3+The emmission spectrum figure of green emitting nano material.
Embodiment
The six nitric hydrate gadolinium Gd (NO that the present invention selected for use
3)
36H
2O, nitric acid HNO
3, Sodium Fluoride NaF, herring sperm dna and absolute ethyl alcohol be commercially available analytical pure product, terbium sesquioxide Tb
4O
7Purity be 99.99%, deionized water is made by oneself by the laboratory; Used glassware and equipment are instrument and equipments commonly used in the laboratory.
Embodiment: take by weighing the 0.06g herring sperm dna and be dissolved in the 25ml deionized water, obtain the aqueous dna that concentration is 3mg/ml; Take by weighing 0.0374g terbium sesquioxide Tb
4O
7, use nitric acid HNO
3The evaporation of dissolving back obtains Tb (NO
3)
3Crystal adds the 40ml deionized water, adds 1.7152g Gd (NO again
3)
36H
2O obtains [Gd (NO after the dissolving fully
3)
3+ Tb (NO
3)
3] mixing clear aqueous solution, wherein Gd
3+With Tb
3+Mol ratio be 95: 5; The herring sperm dna aqueous solution is joined [Gd (NO
3)
3+ Tb (NO
3)
3] in the mixing solutions, form [Gd (NO
3)
3+ Tb (NO
3)
3+ herring sperm dna] mixing solutions; To described [Gd (NO
3)
3+ Tb (NO
3)
3+ herring sperm dna] mixed solution and dripping 20ml contains the aqueous solution of 2.016g NaF, obtains NaGdF
4: 5%Tb
3+Deposition; With described NaGdF
4: 5%Tb
3+Deposition is transferred in 2 50ml hydrothermal reaction kettles, hydrothermal reaction kettle is put in the loft drier, in 160 ℃ of reaction 16h; Naturally cool to room temperature after taking out reaction kettle, and continue ageing 12h, open reaction kettle afterwards; Deposition after the hydro-thermal is carried out spinning; After absolute ethyl alcohol is given a baby a bath on the third day after its birth time,, obtain bow tie NaGdF in 70 ℃ of vacuum-drying 6h
4: 5%Tb
3+The green emitting nano material.Described bow tie NaGdF
4: 5%Tb
3+The green emitting nano material has good crystallinity, the spacing d value of its diffraction peak and relative intensity and NaGdF
4The listed d value of PDF standard card (27-0699) consistent with relative intensity, belong to hexagonal system, see shown in Figure 1.Described bow tie NaGdF
4: 5%Tb
3+The green emitting nano material is bow tie, sees shown in Figure 2.With the Shapiro-Wilk method length of bow tie nano material is carried out normal distribution-test, under 95% degree of confidence, the length distribution of bow tie nano material belongs to normal distribution, and length is 831 ± 72nm, sees shown in Figure 3.With the Shapiro-Wilk method diameter at bow-knot-double place in the bow tie nano material is carried out normal distribution-test; Under 95% degree of confidence; The diameter Distribution at bow-knot-double place belongs to normal distribution in the bow tie nano material, and diameter is 166 ± 14nm, sees shown in Figure 4.With the Shapiro-Wilk method diameter of every nanometer rod in the bow tie nano material is carried out normal distribution-test; Under 95% degree of confidence; The diameter Distribution of every nanometer rod belongs to normal distribution in the bow tie nano material, and diameter is 110 ± 9nm, sees shown in Figure 5.Bow tie NaGdF
4: 5%Tb
3+The green emitting nano material is seen shown in Figure 6 by Na, Gd, F and Tb elementary composition (the Au conductive layer of sample surfaces plating when Au derives from the SEM sample preparation, the silicon chip of carrying sample when Si derives from the SEM sample preparation).When the monitoring wavelength is 545nm, described bow tie NaGdF
4: 5%Tb
3+The excitation spectrum main peak of green emitting nano material is positioned at the strong bands of a spectrum at 274nm place, belongs to Gd
3+Ionic
8S
7/2→
6I
JTransition is seen shown in Figure 7.Under the ultraviolet excitation of 274nm, bow tie NaGdF
4: 5%Tb
3+The green emitting nano material is launched the bright green glow that main peak is positioned at 545nm and 491nm, and it is corresponding to Tb
3+Ionic
5D
4→
7F
5With
5D
4→
7F
6Transition is seen shown in Figure 8.
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 domain of the appended claim of the present invention.
Claims (1)
1. one kind prepares the method that bow tie is mixed terbium tetrafluoro gadolinium sodium green emitting nano material, it is characterized in that, adopts hydrothermal method, uses herring sperm dna to be template, and the employing deionized water is a solvent, and the preparation product is bow tie NaGdF
4: 5%Tb
3+The green emitting nano material the steps include:
(1) preparation mixing solutions
Take by weighing the 0.06g herring sperm dna and be dissolved in the 25ml deionized water, obtain the aqueous dna that concentration is 3mg/ml; Take by weighing 0.0374g terbium sesquioxide Tb
4O
7, use nitric acid HNO
3The evaporation of dissolving back obtains Tb (NO
3)
3Crystal adds the 40ml deionized water, adds 1.7152g Gd (NO again
3)
36H
2O obtains [Gd (NO after the dissolving fully
3)
3+ Tb (NO
3)
3] mixing clear aqueous solution, wherein Gd
3+With Tb
3+Mol ratio be 95: 5; The herring sperm dna aqueous solution is joined [Gd (NO
3)
3+ Tb (NO
3)
3] in the mixing solutions, form [Gd (NO
3)
3+ Tb (NO
3)
3+ herring sperm dna] mixing solutions;
(2) preparation NaGdF
4: 5%Tb
3+Deposition
To described [Gd (NO
3)
3+ Tb (NO
3)
3+ herring sperm dna] mixed solution and dripping 20ml contains the aqueous solution of 2.016g NaF, obtains NaGdF
4: 5%Tb
3+Deposition;
(3) preparation bow tie NaGdF
4: 5%Tb
3+The green emitting nano material
With described NaGdF
4: 5%Tb
3+Deposition is transferred in 2 50ml hydrothermal reaction kettles, hydrothermal reaction kettle is put in the loft drier, in 160 ℃ of reaction 16h; Naturally cool to room temperature after taking out reaction kettle, and continue ageing 12h, open reaction kettle afterwards; Deposition after the hydro-thermal is carried out spinning; After absolute ethyl alcohol is given a baby a bath on the third day after its birth time,, obtain bow tie NaGdF in 70 ℃ of vacuum-drying 6h
4: 5%Tb
3+Green emitting nano material, the length of bow tie nano material are 831 ± 72nm, and the diameter at bow-knot-double place is 166 ± 14nm in the bow tie nano material, and the diameter of every nanometer rod is 110 ± 9nm in the bow tie nano material.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464776A (en) * | 2013-08-26 | 2013-12-25 | 成都理工大学 | Metal nano ring based on natural polymer DNA template and preparation method thereof |
| CN104357056A (en) * | 2014-11-13 | 2015-02-18 | 南京信息工程大学 | Preparation method of europium-doped sodium gadolinium fluoride red light-emitting porous nanocrystal material |
| CN116285988A (en) * | 2023-03-28 | 2023-06-23 | 中国科学院长春应用化学研究所 | Rare earth-framework nucleic acid nanocomposite and preparation method and application thereof |
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|---|---|---|---|---|
| CN101260561A (en) * | 2007-12-17 | 2008-09-10 | 天津理工大学 | Hydrothermal growth method for near-infrared up-conversion fluoride crystal |
| CN102078786A (en) * | 2010-11-19 | 2011-06-01 | 长春理工大学 | Method for preparing terbium-doped cerium fluoride porous nanospheres based on herring sperm DNA template |
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2012
- 2012-02-24 CN CN201210042959.2A patent/CN102618283B/en not_active Expired - Fee Related
Patent Citations (2)
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| CN101260561A (en) * | 2007-12-17 | 2008-09-10 | 天津理工大学 | Hydrothermal growth method for near-infrared up-conversion fluoride crystal |
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|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464776A (en) * | 2013-08-26 | 2013-12-25 | 成都理工大学 | Metal nano ring based on natural polymer DNA template and preparation method thereof |
| CN103464776B (en) * | 2013-08-26 | 2016-01-06 | 成都理工大学 | Based on metal nano ring and the preparation method of natural polymer DNA profiling |
| CN104357056A (en) * | 2014-11-13 | 2015-02-18 | 南京信息工程大学 | Preparation method of europium-doped sodium gadolinium fluoride red light-emitting porous nanocrystal material |
| CN104357056B (en) * | 2014-11-13 | 2017-02-22 | 南京信息工程大学 | Preparation method of europium-doped sodium gadolinium fluoride red light-emitting porous nanocrystal material |
| CN116285988A (en) * | 2023-03-28 | 2023-06-23 | 中国科学院长春应用化学研究所 | Rare earth-framework nucleic acid nanocomposite and preparation method and application thereof |
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