CN102559188B - Nano lamellar compound rare-earth hydroxide and preparation method thereof - Google Patents
Nano lamellar compound rare-earth hydroxide and preparation method thereof Download PDFInfo
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- CN102559188B CN102559188B CN 201110452565 CN201110452565A CN102559188B CN 102559188 B CN102559188 B CN 102559188B CN 201110452565 CN201110452565 CN 201110452565 CN 201110452565 A CN201110452565 A CN 201110452565A CN 102559188 B CN102559188 B CN 102559188B
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Abstract
The invention relates to a nanoscale lamellar rare-earth hydroxide functional material and a preparation method thereof. According to the invention, the characteristic that metal ions are uniformly distributed in a lamellar rare-earth hydroxide laminate is utilized, rare-earth metal ions with similar radiuses are selected for carrying out isomorphous substitution, and a polyethyleneimine synthesis method is adopted for preparing the lamellar compound rare-earth hydroxide with the chemical formula of being RE2(OH)5Cl nH2O. Dimension of the prepared rare-earth hydroxide can be adjusted within the range from nanometer to micrometer, and isomorphous substitution by virtue of different rare-earth ions is carried out, thus a product can have a bright fluorescent light (blue light to near infrared light) with adjustable emission wavelength. According to the invention, a compound lamellar optical functional material system with uniform composition, adjustable dimension, good crystallinity, laminate rare earth ions which can be doped and exchangeable interlayer anions is constructed, and the preparation method is simple, practicable, rapid and convenient.
Description
Technical field
The invention belongs to the inorganic functional material preparation field, particularly a kind of layered composite rare earth hydroxide functional material and preparation method thereof.
Background technology
Rare earth element is the general name of IIIB family scandium, yttrium and lanthanon in the periodictable.Rare earth element has unique 4f electron structure, and the compound that causes containing rare earth has many unique physical and chemical properties, thereby is widely used in fields such as light, electricity, magnetic, catalysis, has the good reputation of industrial monosodium glutamate.In the application and development of rare earth functional materials, rare earth luminescent material has fluorescent line to be enriched, and fluorescence lifetime is long, advantages such as good stability, thereby especially noticeable.Based on the multi-functional characteristic of rare earth, the research and development of carrying out the rare earth functional materials have important theoretical research meaning and actual application value to the such rare earth big country of China.
Stratiform rare earth compound (LRHs) is the novel inorganic stratiform functional materials that a class has laminate structure, and forming general formula can be expressed as: RE
2(OH)
5ClnH
2O, wherein RE
3+For the rare earth ion in the laminate, as Y
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+Deng; N is the number of middle water molecule, and the size of n generally is subjected to the preparation method, the influence of factors such as the kind of interlayer rare earth ion and ambient moisture and changing.Trivalent rare earth positively charged ion on the laminate and hydroxyl/interlayer anion forms eight/nine coordination structures, evenly distributes on laminate.Because rare earth ion has similar radius, the trivalent rare earth ions on its laminate can be by other rare earth ion isomorphous substitution, and this replacement is conducive to integrate the characteristic of different rare earth ions, can play regulating effect to pattern and the function of rare earth compound.These are laid a good foundation for the functionalization of complex layered rare earth material.
The laminate structure of LRHs uniqueness has determined it to have the characteristic of ion-exchange, i.e. Cl between the LRHs precursor layer
–Can exchange under suitable condition with other negatively charged ion, thereby obtain needed product.
In conjunction with the characteristic of rare earth ion skeleton and this laminate structure, LRHs delivers at medicine, biomarker, and fields such as fluorescent material have good application prospects.Laurea J. Mcintyre etc. adopt ion exchange method, prepare some row intercalation RE
2(OH)
5A
0.5NH
2O, wherein A
2 –Be interlayer anion, as C
2O
4 2 –, C
2H
2O
4 2 –, C
8H
4O
4 2 –, C
10H
12SO
4 2 –Deng.People such as In Su Lee are with Eu
3+Mix and Tb
3+The LGdH that mixes is presoma, has prepared corresponding GdOCl film by annealing, by changing Eu in the presoma
3+Mix and Tb
3+The ratio of mixing regulates the emission wavelength of product, prepared the oxychloride film of gadolinium that can be multicolor luminous.
The functionalization of present LRHs material has two big developing direction.The one, give the ability of LRHs material fluorescent emission.LRHs itself has the ability of medicine delivery, can realize its biomedical applications better after the combined with fluorescent performance again.The LRHs material realizes that fluorescent characteristic mainly contains rear-earth-doped and loading fluorescence molecule dual mode at present.Rear-earth-doped mainly is the doping of Eu and two kinds of elements of Tb.But this kind mode faces problems such as the low and luminescence spectrum dullness of fluorescence efficiency.The medicine carrying capacity that loading fluorescence molecule such as green fluorescent protein have then taken LRHs can't realize the medicine carrying of LRHs and the integrated application of imaging.Therefore realize that the fluorescent emission of LRHs and the ability of its medicine delivery of reservation are one of striving directions of present material supply section scholar.Second developing direction is that the LRHs material is carried out surface organic modification.There is a large amount of activity hydroxies on the surface of LRHs, and is soft-agglomerated easily, and bad with the consistency of organic materials, reduces stability and the mechanical property of substrate material when using as organic additive easily.Therefore, the LRHs material is carried out surface organic modification, improve its stability and with the consistency of organic substrate, realize that its application in fields such as organic additive and biomaterials also is one of everybody research direction.
LRHs needs its size to reach nano level in the application in fields such as biology, medical science, and in solution good stability, monodispersity is strong.The preparation method of LRHs is mainly derived from the preparation method of traditional layered double hydroxide (LDHs) at present, comprises coprecipitation method and hydrothermal method.Co-precipitation takes place with the mixing salt solution of the rare-earth cation of formation LRHs laminate in coprecipitation method under the effect of alkali (being generally NaOH), wherein contain the interlayer anion group that will synthesize in the rare-earth cation mixed solution or in the alkaline solution, throw out crystallization under certain condition can obtain target product.The mixing salt solution that hydrothermal method is about to constitute the rare-earth cation of LRHs laminate places the pressurized vessel of sealing, is solvent with water, carries out chemical reaction and obtain product under the condition of High Temperature High Pressure.
But the LRHs of above two kinds of traditional methods preparation needs the pH of solution is carried out meticulous regulation and control, has increased the reaction difficulty; Reaction times is generally 6 – 48h, long reaction time; And prepared product particle diameter generally big (greater than 1 μ M), and assemble easily, be unfavorable for that LRHs is in the application of aspects such as biology.Therefore, the preparation technology of a kind of LRHs of nano level easily and fast is the target that people pursue always.
Summary of the invention
The object of the present invention is to provide a kind of stratiform rare earth hydroxide functional material and preparation method thereof.
The laminate metal ion of this stratiform rare-earth hydroxide provided by the present invention is rare earth cation RE
3+, interlayer anion is Cl
–, chemical formula is RE
2(OH)
5ClnH
2O, wherein RE
3+Be Y
3+, Ce
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+Or Lu
3+In a kind of or several, 0.3≤n≤3, and layer of polyethylene imines film has been wrapped up on its surface.
Our prepared stratiform rare earth hydroxide functional material has two distinguishing features in the present invention.The one, one deck PEI film has been wrapped up on its surface.Contain a large amount of free amino groups in the PEI molecule, it can make prepared LRHs material in multiple organic-inorganic solvent good solubility be arranged as tensio-active agent, and a large amount of amino existence in surface can be used as functional group and multiple macromole coupling, have strengthened the biologic applications prospect of LRHs significantly.The surface active function that second distinguishing feature is PEI can also significantly improve the LRHs substrate and accept rear-earth-doped ability, thereby the doping that can realize multiple rare earth element is luminous.For example we prepared LRHs has observed Ce first by mixing
3+Bright blue emission and the Nd of ion
3+The infrared emission of ion.We have also realized Eu simultaneously
3+, Tb
3+And Ce
3+, Tb
3+The fluorescent emission of mixing altogether, luminescent spectrum has expanded to infrared band from blue wave band, has also enriched its luminescence spectrum when having kept LRHs matrix medicine carrying capacity.Generally speaking, we have the following advantages by prepared stratiform rare-earth hydroxide function material: the particle good crystallinity, and dispersed strong, water soluble and multiple organic solvent; Chemical constitution and structure are adjustable on microcosmic; Particle size can be at nano level to conveniently regulating and controlling between micron order; Utilize the equally distributed characteristic of metal ion in the stratiform rare-earth hydroxide laminate, can select the rare earth ion of similar radius to carry out isomorphous substitution, obtain lanthanide doped layered composite rare earth hydroxide; And by the different rare earth ion of isomorphous substitution, make product have the bright fluorescence (blue light-near infrared light) of emission wavelength tunable
The invention provides a kind of polymine synthesis method for preparing the stratiform rare-earth hydroxide, stratiform rare-earth hydroxide nanoparticle is prepared according to following steps:
A. prepare RECl
3With the aqueous solution of tensio-active agent polymine, the used solvent of above-mentioned solution is deionized water, wherein RE
3+Be Y
3+, Ce
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+Or Lu
3+In a kind of or several.
B. in reactor, add above-mentioned solution; and add the generation that an amount of dehydrated alcohol is avoided rare earth oxide; the total mol concentration of trivalent rare earth ions is 5 –, 100 mM in the mixed solution, and the concentration of polymine is 2 –, 20 g/L, stirs under the nitrogen atmosphere protection under the room temperature.
C. reactor is moved in the pre-heated stove crystallization 2 – 48h under 80 – 200oC.
D. allow reactor at room temperature cool off, with the solution centrifugal of gained, washing is dissolved in the deionized water again, obtains the aqueous solution of stratiform rare-earth hydroxide.
In the polymine synthesis method of the stratiform rare-earth hydroxide that this patent provides, water plays the effect that makes solute ionsization, and ethanol can provide the environment of reductibility to avoid the generation of rare earth oxide.The adding of polyethenieimine surfactants has the following advantages.The first, need not additionally to regulate and control the pH value of reaction system.Polymine contains a large amount of amino, and the protonated environment that makes is alkalescence in the aqueous solution, provides the stratiform rare-earth hydroxide to form needed alkaline environment, makes easy to prepare quick.Secondly, prepared stratiform rare-earth hydroxide surface has a large amount of amino, in water and multiple organic solvent good solubility is arranged.The 3rd, polyethenieimine surfactants adds the doping that is conducive to rare earth element at the initial period of reaction and the rare earth element chelating in the solution, thereby the polychrome of realizing the stratiform rare-earth hydroxide mixes luminous.
The inventive method has following unusual effect:
1. this reaction is a Rong Xie – recrystallization process, be that raw material dissolves in water solvent earlier, form with ion, molecular grouping enters solution, utilize the strong convection current that produces owing to heating in the still that these ions, molecule or ionic group are transported to vitellarium (being cold zone) and form supersaturated solution, then crystallization, so the particle purity height of preparation, good dispersity, good crystalline and controlled;
2. the used hydrolysis of tensio-active agent polymine in solution can provide the stratiform rare-earth hydroxide to form required alkaline environment, omit the needed monitoring of traditional method and regulated the pH process, save time and instrument cost, be conducive to industrial production;
3. owing to do not need raw material is carried out mix grinding technology, production technique is simple, and is with short production cycle, is conducive to reduce production costs;
But 4. the stratiform rare-earth hydroxide granular size conveniently regulating and controlling of Sheng Chaning, in nanometer in micrometer range.
Description of drawings
Fig. 1 is the XRD figure spectrum of the stratiform rare-earth hydroxide of the yttrium that obtains of the embodiment of the invention 3,6,7,8, and data are gathered by German Brooker D8 type X-ray diffractometer.As can be seen from the figure, the stratiform rare-earth hydroxide of the present invention's preparation is good crystallinity, and the simplification compound of chemical constitution and even structure has and Y
2(OH)
5ClnH
2The crystalline structure that O is similar.
Fig. 2 be the yttrium that obtains of the invention process example 3 the stratiform rare-earth hydroxide respectively with the XRD figure spectrum of three kinds of organic anion ion-exchange after products.Prepared as seen from Figure 2 rare earth layered hydroxide has the characteristic of ion-exchange.
Fig. 3 is the transmission electron microscope photo of the stratiform rare-earth hydroxide of the yttrium that obtains of the embodiment of the invention 2; Electromicroscopic photograph is finished in the 2010 HT transmission electron microscope photographs that NEC company produces.The stratiform rare-earth hydroxide size homogeneous of the prepared yttrium of hydro-thermal 2.5 h under 100 ° of C temperature as seen from the figure, good dispersity, size is about 100 nm, and adopting Ma Erwen Zetasizer-3000 type laser particle analyzer to record its mean sizes is 96 nm.
Fig. 4 is the transmission electron microscope photo of the stratiform rare-earth hydroxide of the yttrium that obtains of the embodiment of the invention 4.The particle diameter that as seen from the figure temperature of reaction is risen to 200 ° of C after products obviously increases during than 100 ° of C, and electromicroscopic photograph shows that its median size is about 1.5 μ M.
Fig. 5 is the infrared spectrogram of the stratiform rare-earth hydroxide of the yttrium that obtains of the embodiment of the invention 3; Data are finished collection at the AVATAR360 type Fourier infrared spectrograph of U.S. Buddhist nun's high-tensile strength company.3540 cm
– 1The strong absorption peak at place can belong to the feature stretching vibration peak of O – H key, 2850 and, 2920 cm
– 1The peak at place has shown CH
2The existence of root, 1430 and, 1565 cm
1The strong absorption peak at place can belong to a large amount of free amino group on surface, and what show particle is coated with layer of polyethylene imines film.
Fig. 6 is the white light photo of the dissolving of stratiform rare-earth hydroxide in four kinds of solvents such as water, ethanol, ethylene glycol, dimethyl sulfoxide (DMSO) of the yttrium that obtains of the embodiment of the invention 3.The polymine that can see the surface parcel makes prepared stratiform rare-earth hydroxide in multiple organic solvent good solubility arranged, and is conducive to it as the Application of Additives prospect.
Fig. 7 is the Y that the embodiment of the invention 10 obtains
3+– Ce
3+The luminescent spectrum of stratiform complex hydroxide.Prepared nano level Y as seen from the figure
3+– Ce
3+The absorbing wavelength of stratiform complex hydroxide is 280nm, and the crest of emmission spectrum is positioned at 415nm, and the peak width at half height of emmission spectrum is about 50nm.
Fig. 8 is the Y that the embodiment of the invention 11 obtains
3+– Nd
3+The luminescent spectrum of stratiform complex hydroxide.Prepared Y as seen from the figure
3+– Nd
3+The crest of the emmission spectrum of stratiform complex hydroxide is positioned at 875nm, belongs to near-infrared band, has the prospect of biologic applications.
Fig. 9 is the Y that the embodiment of the invention 12 obtains
3+– Ce
3+– Tb
3+The luminescent spectrum of stratiform complex hydroxide.Ce as seen from the figure
3+Feature glow peak and Tb
3+Glow peak all embodied.The relative luminous intensity of the two can be regulated by the doping content of regulating the two.
Embodiment
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
(1) Yttrium trichloride, tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Yttrium trichloride is 0.1 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 1 mL yttrium chloride solution, 15 mL ethanol, 1 mL polyethyleneimine: amine aqueous solution are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 80 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain the aqueous solution of the nano lamellar oxyhydroxide of yttrium.
(1) Yttrium trichloride, tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Yttrium trichloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 1 mL yttrium chloride solution, 15 mL ethanol, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 100 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain the aqueous solution of the nano lamellar oxyhydroxide of yttrium.
Embodiment 3
(1) Yttrium trichloride, tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Yttrium trichloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 1 mL yttrium chloride solution, 15 mL ethanol, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 160 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain the aqueous solution of the nano lamellar oxyhydroxide of yttrium.
The ion-exchange of the nano lamellar oxyhydroxide of yttrium: the typical case, prepared a LYH is dissolved in the 10 mL ultrapure waters, add the sodium salt of the negatively charged ion of three times of required exchanges, as Soduxin, sodium phthalate and sodium oleate etc.Feed one minute nitrogen in the test tube and play atmosphere protection.Then mixed solution was at room temperature stirred 12 hours, centrifugal, washing can obtain the product after the ion-exchange.
The nano lamellar oxyhydroxide 1mg of yttrium is dissolved in 3 mL water respectively, ethanol, ethylene glycol, in the dimethyl sulfoxide (DMSO), concussion is dissolved, and can detect the solvability of nano lamellar oxyhydroxide in organic solvent and inorganic solvent of prepared yttrium.
(1) Yttrium trichloride, tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Yttrium trichloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 1 mL yttrium chloride solution, 15 mL ethanol, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 200 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain the aqueous solution of the layered hydroxide of micron order yttrium.
Embodiment 5
(1) Yttrium trichloride, tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Yttrium trichloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:10 mL;
(2) successively 5 mL yttrium chloride solutions, 15 mL ethanol, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 200 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain the aqueous solution of the layered hydroxide of micron order yttrium.
Embodiment 6
(1) Dysprosium trichloride, tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Dysprosium trichloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 1 mL Dysprosium trichloride solution, 15 mL dehydrated alcohols, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 160 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain the aqueous solution of the stratiform complex hydroxide of nano level dysprosium.
Embodiment 7
(1) Erbium trichloride, tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Erbium trichloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 1 mL Erbium trichloride solution, 15 mL dehydrated alcohols, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 160 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain the aqueous solution of the stratiform complex hydroxide of nano level erbium.
Embodiment 8
(1) terbium chloride, tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of terbium chloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 1 mL terbium chloride solution, 15 mL dehydrated alcohols, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 160 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain the aqueous solution of the stratiform complex hydroxide of nano level terbium.
Embodiment 9
(1) Yttrium trichloride, Gadolinium trichloride tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Yttrium trichloride and Cerium II Chloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 0.9 mL yttrium chloride solution, 0.1 mL Gadolinium trichloride solution, 15 mL ethanol, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 160 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, with deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain Gd content and be 10% nano level Y
3+– Gd
3+The aqueous solution of stratiform complex hydroxide.
(1) Yttrium trichloride, Cerium II Chloride tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Yttrium trichloride and Cerium II Chloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 0.9 mL yttrium chloride solution, 0.1 mL solution of cerium chloride by oxidation, 15 mL ethanol, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 200 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, with deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain Ce content and be 10% nano level Y
3+– Ce
3+The aqueous solution of stratiform complex hydroxide, and adopt Hatachi F-4500 fluorophotometer to detect its absorption and luminescent spectrum.
Embodiment 11
(1) Yttrium trichloride, Neodymium trichloride tensio-active agent polymine are dissolved in respectively in the deionized water, the neodymium concentration of Yttrium trichloride and chlorination is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 0.9 mL yttrium chloride solution, 0.1 mL neodymium chloride solution, 15 mL ethanol, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 200 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, with deionized water and absolute ethanol washing 3 times, be dissolved in again in the 5 mL deionized waters, obtain Nd content and be 10% nano level Y
3+– Nd
3+The aqueous solution of stratiform complex hydroxide, and measured its emmission spectrum with the solid statelaser of 800 nm as excitation light source.
Embodiment 12
(1) Yttrium trichloride, Cerium II Chloride, terbium chloride and tensio-active agent polymine are dissolved in respectively in the deionized water, the concentration of Yttrium trichloride, Cerium II Chloride, terbium chloride is 0.5 mol/L, and the quality of polymine and the volume ratio of solvent are 1 g:50 mL;
(2) successively 0.82 mL yttrium chloride solution, 0.1 mL solution of cerium chloride by oxidation and 0.08mL terbium chloride solution, 15 mL ethanol, 5 mL polyethyleneimine: amine aqueous solutions are added reactor, under the nitrogen atmosphere protection, stir energetically under the room temperature and solution was mixed in 5 ~ 10 minutes.
(3) reactor is moved in the pre-heated stove crystallization 2.5 h under 200 oC.
(4) allow reactor at room temperature cool off, with the solution centrifugal of gained, use deionized water and absolute ethanol washing 3 times, be dissolved in the 5 mL deionized waters again, obtaining Ce content is that 10%, Tb content is 8% Y
3+– Ce
3+– Tb
3+The aqueous solution of stratiform complex hydroxide, and adopt Hatachi F-4500 fluorophotometer to detect its absorption and luminescent spectrum.
Claims (8)
1. a nano level stratiform rare earth hydroxide functional material is characterized in that, its laminate metal ion is rare earth cation RE
3+, interlayer anion is Cl
–, chemical formula is RE
2(OH)
5ClnH
2O, wherein RE
3+Be Y
3+, Ce
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+Or Lu
3+In a kind of or several, 0.3≤n≤3, and layer of polyethylene imines film has been wrapped up on its surface.
2. stratiform rare earth hydroxide functional material according to claim 1 is characterized in that, its granular size is at Nano grade, and can not be adjusted to micron level as required.
3. stratiform rare earth hydroxide functional material according to claim 1 is characterized in that, its la m rare earth ion is Nd
3+, chemical formula is Nd
2(OH)
5ClnH
2O, it has Nd
3+The near-infrared fluorescent emission characteristic.
4. stratiform rare earth hydroxide functional material according to claim 1 is characterized in that, its la m rare earth ion is Y
3+And Ce
3+, consist of (Y
xCe
1-x)
2(OH)
5ClnH
2O, 0.8≤x＜1, it has Ce
3+The blue emission characteristic.
5. stratiform rare earth hydroxide functional material according to claim 1 is characterized in that, its la m rare earth ion is Y
3+And Eu
3+, consist of (Y
xEu
1-x)
2(OH)
5ClnH
2O, 0.8≤x＜1, it has Eu
3+The red emission characteristic.
6. stratiform rare earth hydroxide functional material according to claim 1 is characterized in that,, its la m rare earth ion is Y
3+And Tb
3+, consist of (Y
xTb
1-x)
2(OH)
5ClnH
2O, 0.8≤x＜1, it has Tb
3+The green emission characteristic.
7. stratiform rare earth hydroxide functional material according to claim 1 is characterized in that, its la m rare earth ion is Y
3+, Ce
3+And Tb
3+, consist of (Y
xCe
yTb
1-x-y)
2(OH)
5ClnH
2O, 0.8≤x＜1,0＜y＜0.2 has Ce simultaneously
3+Blue emission characteristic and Tb
3+The green emission characteristic.
8. the preparation method of the layered rare earth hydroxide functional material of claim 1 is characterized in that, its concrete steps are as follows:
A. prepare RECl
3With the aqueous solution of tensio-active agent polymine, the used solvent of above-mentioned solution is deionized water;
B. in reactor, add above-mentioned solution, and add the generation that an amount of dehydrated alcohol is avoided rare earth oxide, the total mol concentration of trivalent rare earth ions is 5 –, 100 mM in the mixed solution, and the concentration of PEI is 2 –, 20 g/L, stirs under the nitrogen atmosphere protection under the room temperature;
C. reactor was moved in the pre-heated stove under 80 – 200oC crystallization 2 – 48 hours;
D. allow reactor at room temperature cool off, with the solution centrifugal of gained, washing is dissolved in the deionized water again, obtains the aqueous solution of stratiform rare-earth hydroxide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525540A (en) * | 2009-04-08 | 2009-09-09 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing fluorescent nano material converted on NaYF4 |
| CN101812295A (en) * | 2010-02-09 | 2010-08-25 | 北京化工大学 | Layered composite rare earth hydroxide functional material and preparation method thereof |
| JP2010241899A (en) * | 2009-04-02 | 2010-10-28 | National Institute For Materials Science | Rare earth oxide fluorescent material, thin film using the same, and methods for producing them |
| CN102071027A (en) * | 2011-03-01 | 2011-05-25 | 吉林大学 | Water-soluble rare-earth terbium ion-doped cerium fluoride nanocrystallines and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010241899A (en) * | 2009-04-02 | 2010-10-28 | National Institute For Materials Science | Rare earth oxide fluorescent material, thin film using the same, and methods for producing them |
| CN101525540A (en) * | 2009-04-08 | 2009-09-09 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing fluorescent nano material converted on NaYF4 |
| CN101812295A (en) * | 2010-02-09 | 2010-08-25 | 北京化工大学 | Layered composite rare earth hydroxide functional material and preparation method thereof |
| CN102071027A (en) * | 2011-03-01 | 2011-05-25 | 吉林大学 | Water-soluble rare-earth terbium ion-doped cerium fluoride nanocrystallines and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Byung-II Lee, et al..Synthesis of colloidal aqueous suspensions of a layered gadolinium hydroxide:a potential MRI contrast agent.《Dalton Transactions》.2009,第2490页. |
| Layered Rare-Earth Hydroxides (LRHs) of (Y1-xEux)2(OH)5NO3 3 nH2O(x=0-1):Structural Variations by Eu 3+ Doping, Phase Conversion to Oxides, and the Correlation of Photoluminescence Behaviors;Qi Zhu, et al.;《Chemistry of Materials》;20100702;第22卷(第14期);第4204页 * |
| QiZhu et al..Layered Rare-Earth Hydroxides (LRHs) of (Y1-xEux)2(OH)5NO3 3 nH2O(x=0-1):Structural Variations by Eu 3+ Doping |
| Synthesis of colloidal aqueous suspensions of a layered gadolinium hydroxide:a potential MRI contrast agent;Byung-II Lee, et al.;《Dalton Transactions》;20090213;第2490页 * |
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