CN105565358A - Preparation method of polyol solvent of rare earth oxide nanoparticles - Google Patents

Preparation method of polyol solvent of rare earth oxide nanoparticles Download PDF

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Publication number
CN105565358A
CN105565358A CN201510949158.8A CN201510949158A CN105565358A CN 105565358 A CN105565358 A CN 105565358A CN 201510949158 A CN201510949158 A CN 201510949158A CN 105565358 A CN105565358 A CN 105565358A
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earth oxide
rare
nano particles
gadolinium
oxide nano
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欧梅桂
杨春林
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Guizhou University
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Guizhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Geology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a method for polyol solvent preparation and size control of rare earth oxide nanoparticles. The method comprises the following steps: with polyethylene glycol as a solvent, mixing gadolinium trichloride with terbium trichloride, and completely dissolving the gadolinium trichloride and terbium trichloride; adding a sodium hydroxide solution for a synthesis reaction to obtain Tb<3+>-doped gadolinium oxide nanoparticles with magnetism and luminescence property; and wrapping the surfaces of the gadolinium oxide nanoparticles with a polysiloxane layer to obtain core-shell structure rare earth nanoparticles. By adopting the method disclosed by the invention, the prepared nanoparticles have stable properties and good dispersity, the particle size can be controlled through the change of relevant parameters, and the properties play an important role in applying the core-shell structure rare earth nanoparticles as a novel bioprobe to a biosensor for the sensing and detection of biomolecules.

Description

A kind of polyol solvent preparation method of rare-earth oxide nano particles
Technical field
The present invention relates to technical field of nano material, especially a kind of polyol solvent preparation method of rare-earth oxide nano particles.
Background technology
The rear-earth-doped Gd of magneto-optic double-function 2o 3nano material has very large application prospect in biological tracing, fluorescence imaging and medicament slow release field, and obtains a lot of research: people's hydrothermal methods such as Xu Dekang, the Gd of different-shape (OH) that utilized different additive to synthesize 3presoma, obtains rear-earth-doped Gd after 700 DEG C of annealing 2o 3nano material; People's reverse microemulsion process such as Wu Yanli, have first synthesized spherical Gd 2(CO) 3: Eu 3+presoma, then 600 DEG C of annealing obtain Gd 2o 3: Eu 3+nanocrystalline.
PEG has great effect in the stably dispersing of nano particle and the control of appearance and size: the superfine discovery of Lee, to Nano-meter SiO_2 2the method that aqeous suspension adopts macromolecule to combine with small-molecular-weight PEG can obtain desirable dispersion effect; The people such as Luo Wei take PEG200 as solvent, have obtained the flower-like structure Ni nanoparticle be made up of nanometer sheet, and research finds that PEG200 serves the effect of structure directing; The people such as Miao Yu take PEG6000 as dispersion agent, and direct precipitation method has synthesized nanometer Mg (OH) 2, result shows that appropriate PEG can make reactant mix, and can effectively suppress the growth of crystal grain and prevent particle agglomeration, and excessive PEG6000 on the contrary can the carrying out of inhibited reaction, makes Mg (OH) 2particle diameter increase; The ZnO nano powder that has been soft template Hydrothermal Synthesis with PEG such as Sun Jian, along with the increase of PEG molecular weight, the particle diameter of nano-ZnO is less, and PEG further suppress the polar growth of ZnO, makes it to become subglobose particle from bar-shaped.But the PEG of the employing different molecular weight (200,400,600) of system is solvent, synthesizes Gd under room temperature 2o 3: Tb 3+nano particle there is not been reported to the research of its coated polysiloxane shell.
Summary of the invention
The object of the invention is: the polyol solvent preparation method that a kind of rare-earth oxide nano particles is provided, its method is easy, easy to operate, the Core-shell Structure Nanoparticles Stability Analysis of Structures prepared, good dispersity, size are controlled, and have fluorescence and magnetic property, to overcome the deficiencies in the prior art.
The present invention is achieved in that the preparation method of rare-earth oxide nano particles, take molecular weight as the polyoxyethylene glycol of 200 be solvent, six water gadolinium trichlorides and six water terbium trichlorides are added in polyoxyethylene glycol by the mol ratio of 90-95:5-10 and mixes, and make six water gadolinium trichlorides and six water terbium trichlorides be dissolved completely in polyoxyethylene glycol, obtain precursor liquid; In precursor liquid, add sodium hydroxide solution carry out building-up reactions, what obtain having luminous and magnetic is doped with Tb 3+gadolinium oxide nanoparticles; Coated reagent is adopted by this Gadolinium oxide nanoparticles to carry out silicone layer more coated, the composition of coated reagent comprises covering liquid and hydrolyzed solution, wherein, covering liquid is made up of tetraethyl orthosilicate and 3-aminopropyl-triethoxy silicon, hydrolyzed solution is mixed by triethylamine and distilled water and forms, and obtains the rare-earth oxide nano particles of nucleocapsid structure after being covered to complete.
Six described water gadolinium trichlorides and the mol ratio of six water terbium trichlorides are 90-95:5-10.
The solvent of described sodium hydroxide solution is polyoxyethylene glycol.
The mol ratio of described covering liquid mesosilicic acid tetra-ethyl ester and 3-aminopropyl-triethoxy silicon is 55-65:35-45; In described hydrolyzed solution, the mol ratio of triethylamine and distilled water is 1:30-40.
The molecular weight of described polyoxyethylene glycol is 200-600.
In precursor liquid, the concentration of Gd is 24mol/L, and all the other amount of substances all can calculate according to stoichiometric number proportionlity and try to achieve.
Owing to have employed technique scheme, compared with prior art, the present invention is based on dispersiveness, the stability of improving Core-shell Structure Nanoparticles, effectively control the size of nano particle and improve the thinking of its detection signal.Adopt PEG200 as solvent, instead of water, be because PEG has good dispersiveness, and avoid water as the generation of sodium hydroxide pellets during solvent, to guarantee the productive rate of nano particle, and adjust the parameters of reaction within the specific limits, the nano particle of acquisition different size that can be controlled.The nano particle nucleocapsid structure that the present invention prepares is clear, can stable dispersion among solvent, size uniform, and particle is larger, can long-term storage and do not produce reunion, and luminescent properties is superior.
Accompanying drawing explanation
Fig. 1 is the particle size distribution figure of product;
Fig. 2 is the SEM figure of product;
Fig. 3, Fig. 4 are Gd 2o 3: Tb 3+the nanocrystalline energy spectrum analysis carrying out observing under a scanning electron microscope;
Fig. 5 is that different molecular weight PEG makes solvent to nano particle excitation spectrum;
Fig. 6 is that different molecular weight PEG makes solvent to nano particle emmission spectrum;
Fig. 7,8 is the relaxation time of product.
Embodiment
Embodiments of the invention 1: the preparation method of rare-earth oxide nano particles, get 4.56mmolGdCl 36H 2o and 0.24mmolTbCl 36H 2o mixing is placed in round-bottomed flask, and the PEG adding 200mL dissolves, and room temperature lower magnetic force stirs 12h and makes precursor liquid, then adds the 1.44mLNaOH solution dissolved with 200mLPEG, continues to stir 6h, synthesizes and be suspended with Gd 2o 3: Tb 3+the gluey clear solution of nano particle; Then the Gd prepared 2o 3: Tb 3+nano grain surface carries out the coated of silicone layer, and coated reagent, by wrapping up liquid and hydrolyzed solution forms, wherein wraps up liquid and provides Si element (mol ratio of Si and Gd is 1:1) for shell, formed by APTES and TEOS with the mixed in molar ratio of 60:40; Hydrolyzed solution is mixed by TEA and distilled water, and the mol ratio of TEA and distilled water is 1:35; Under the lucifuge condition of 40 DEG C, to synthesizing Gd 2o 3: Tb 3+gluey clear solution in add 30% parcel liquid, 30% hydrolyzed solution, 70% parcel liquid and 70% hydrolyzed solution respectively every 1h, magnetic agitation 48h obtains being suspended with Gd 2o 3: Tb 3+/ SiO xthe gluey clear solution of nano particle; Respectively with PEG200, PEG400, PEG600 for solvent, prepared three groups of samples and compared research.
The Gd prepared 2o 3: Tb 3+/ SiO xthe pattern of nano particle is as shown in Fig. 2 (SEM), product is spherical, there is not the growth of polarity in nano particle, in PEG200, granular core shell structure is clear, dispersed very well, and in PEG400 and PEG600 the nucleocapsid structure of nano particle is not too obviously and have slight reunion.
By the Gd in embodiment 2o 3: Tb 3+/ SiO xnano particle laser particle size analyzer particle tested size, result is as shown in Fig. 1 and table 1.
Table 1
PEG molecular weight 200 400 600
Particle size (Gd 2O 3:Tb 3+, nm） 78 21 28
Particle size (Gd 2O 3:Tb 3+/SiO x, nm） 140 32 38
By the Gd in embodiment 2o 3: Tb 3+nanocrystalline carrying out under a scanning electron microscope is observed and energy spectrum analysis, and result as shown in Figure 3,4.
Observe different molecular weight PEG by fluorescence pattern and do the impact of solvent on nano particle excitation spectrum and emmission spectrum, as shown in Figure 5,6.
The relaxation time of the product of embodiment as shown in Figures 7 and 8.
According to above detection, the mean sizes of the nucleocapsid structure rare earth nanometer particle of acquisition is 100nm; This Core-shell Structure Nanoparticles has magnetic and luminous, can be used for the field such as bio-sensing and molecular detection.
Show that the solvent PEG of different molecular weight and other experiment parameters (add-on etc. as NaOH, covering liquid) have impact to the size of nano particle and the characteristics of luminescence through photoluminescence spectra detected result.
It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.

Claims (6)

1. a polyol solvent preparation method for rare-earth oxide nano particles, is characterized in that: take polyoxyethylene glycol as solvent, is added in polyoxyethylene glycol by six water gadolinium trichlorides and mixes, and make it to dissolve completely with six water terbium trichlorides, obtains precursor liquid; In precursor liquid, add sodium hydroxide solution carry out building-up reactions, obtain being doped with Tb 3+gadolinium oxide nanoparticles; Coated reagent is adopted by this Gadolinium oxide nanoparticles to carry out silicone layer more coated, the composition of coated reagent comprises covering liquid and hydrolyzed solution, wherein, covering liquid is made up of tetraethyl orthosilicate and 3-aminopropyl-triethoxy silicon, hydrolyzed solution is mixed by triethylamine and distilled water and forms, and obtains the rare-earth oxide nano particles of nucleocapsid structure after being covered to complete.
2. the polyol solvent preparation method of rare-earth oxide nano particles according to claim 1, is characterized in that: six described water gadolinium trichlorides and the mol ratio of six water terbium trichlorides are 90-95:5-10.
3. the polyol solvent preparation method of rare-earth oxide nano particles according to claim 1, is characterized in that: the solvent of described sodium hydroxide solution is polyoxyethylene glycol.
4. the polyol solvent preparation method of rare-earth oxide nano particles according to claim 1, is characterized in that: the mol ratio of described covering liquid mesosilicic acid tetra-ethyl ester and 3-aminopropyl-triethoxy silicon is 55-65:35-45; In described hydrolyzed solution, the mol ratio of triethylamine and distilled water is 1:30-40.
5. the polyol solvent preparation method of the rare-earth oxide nano particles according to claim 1-4 any one, is characterized in that: the molecular weight of described polyoxyethylene glycol is 200-600.
6. the polyol solvent preparation method of the rare-earth oxide nano particles according to claim 1-4 any one, is characterized in that: in precursor liquid, the concentration of Gd is 24mol/L.
CN201510949158.8A 2015-12-18 2015-12-18 Preparation method of polyol solvent of rare earth oxide nanoparticles Pending CN105565358A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109321245A (en) * 2018-10-22 2019-02-12 贵阳学院 A kind of rare earth codope functional nanocomposite and preparation method thereof
CN109568602A (en) * 2018-12-12 2019-04-05 贵州大学 A kind of rare-earth oxide nano particles and its application
CN110184058A (en) * 2019-05-20 2019-08-30 贵州大学 A kind of preparation method of Gadolinium oxide nanoparticles

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381093A (en) * 2008-10-15 2009-03-11 东华大学 Preparation of rare-earth-doped fluoride LnF3:Re<3+> nano luminescent particles by fractional step method
CN101941676A (en) * 2010-08-26 2011-01-12 吉林大学 Method for preparing Ln2O3:RE<3+> and Ln2O3:RE<3+>@SiO2 monodisperse rare earth nano particles
CN104164233A (en) * 2014-05-23 2014-11-26 贵州大学 Preparation method of core-shell-structured rare earth nanoparticles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381093A (en) * 2008-10-15 2009-03-11 东华大学 Preparation of rare-earth-doped fluoride LnF3:Re<3+> nano luminescent particles by fractional step method
CN101941676A (en) * 2010-08-26 2011-01-12 吉林大学 Method for preparing Ln2O3:RE<3+> and Ln2O3:RE<3+>@SiO2 monodisperse rare earth nano particles
CN104164233A (en) * 2014-05-23 2014-11-26 贵州大学 Preparation method of core-shell-structured rare earth nanoparticles

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109321245A (en) * 2018-10-22 2019-02-12 贵阳学院 A kind of rare earth codope functional nanocomposite and preparation method thereof
CN109568602A (en) * 2018-12-12 2019-04-05 贵州大学 A kind of rare-earth oxide nano particles and its application
CN110184058A (en) * 2019-05-20 2019-08-30 贵州大学 A kind of preparation method of Gadolinium oxide nanoparticles
CN110184058B (en) * 2019-05-20 2022-05-17 贵州大学 Preparation method of gadolinium oxide nanoparticles

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Application publication date: 20160511