CN109158062A - Silicon dioxide colloid compound rare-earth core-shell type microballoon and preparation method thereof - Google Patents
Silicon dioxide colloid compound rare-earth core-shell type microballoon and preparation method thereof Download PDFInfo
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- CN109158062A CN109158062A CN201811094377.2A CN201811094377A CN109158062A CN 109158062 A CN109158062 A CN 109158062A CN 201811094377 A CN201811094377 A CN 201811094377A CN 109158062 A CN109158062 A CN 109158062A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 61
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 41
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000084 colloidal system Substances 0.000 title claims abstract description 18
- -1 compound rare-earth Chemical group 0.000 title claims description 32
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000002910 rare earth metals Chemical group 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 239000010703 silicon Substances 0.000 claims abstract 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 18
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000000575 pesticide Substances 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 7
- 239000004005 microsphere Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 125000005907 alkyl ester group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 7
- 238000003980 solgel method Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000005136 cathodoluminescence Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910002617 Gd(NO3)3·6H2O Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012921 fluorescence analysis Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000005916 Methomyl Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QGLZXHRNAYXIBU-WEVVVXLNSA-N aldicarb Chemical compound CNC(=O)O\N=C\C(C)(C)SC QGLZXHRNAYXIBU-WEVVVXLNSA-N 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
- 229960005286 carbaryl Drugs 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 description 1
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- YFGYUFNIOHWBOB-UHFFFAOYSA-N pirimicarb Chemical compound CN(C)C(=O)OC1=NC(N(C)C)=NC(C)=C1C YFGYUFNIOHWBOB-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Silicon Compounds (AREA)
Abstract
本发明公开了一种二氧化硅胶体复合稀土核‑壳型微球的制备方法，其特征在于所述方法包括以下步骤：(1)纳米二氧化硅核的合成：将无水乙醇、正硅酸烷基酯、氨水和水按照体积比100:5‑15:5‑10:20‑30混合，得到纳米二氧化硅颗粒，洗涤至中性后，分散至无水乙醇中，得到纳米二氧化硅分散液，其浓度为0.2g/mL‑0.8g/mL；(2)采用浸渍‑水热法的稀土核‑壳型微球的合成：将至少两种稀土金属的水溶性盐混合，之后与步骤(1)的纳米二氧化硅分散液研磨直至产生颗粒状混合物，高温干燥，得到产物。本发明还涉及二氧化硅胶体复合稀土核‑壳型微球及其用途。
The invention discloses a preparation method of silica colloid composite rare earth core-shell microspheres, which is characterized in that the method comprises the following steps: (1) Synthesis of nano-silica cores: The acid alkyl ester, ammonia water and water are mixed according to the volume ratio of 100:5-15:5-10:20-30 to obtain nano-silicon dioxide particles, washed to neutrality, and dispersed into absolute ethanol to obtain nano-dioxide Silicon dispersion liquid, the concentration of which is 0.2g/mL-0.8g/mL; (2) Synthesis of rare earth core-shell microspheres by dipping-hydrothermal method: mixing at least two water-soluble salts of rare earth metals, and then Grinding with the nano-silica dispersion in step (1) until a granular mixture is produced, and drying at high temperature to obtain a product. The invention also relates to silica colloid composite rare earth core-shell microspheres and uses thereof.
Description
Technical field
The present invention relates to a kind of silicon dioxide colloid compound rare-earth core-shell type microballoons and preparation method thereof.
Background technique
Colloid rare-earth fluorescent microballoon is in terms of photoelectric material, drug delivery, heterogeneous catalysis, biomarker, photochemical induction
It has a wide range of applications.Monodisperse silica colloidal spheres have spherical configuration and narrow size distribution, therefore very square
Just it modifies.The price is very expensive for rare earth oxide, therefore using cheap silica as core, in a small amount of rare earth of its surface modification
Oxide, the nucleocapsid structure of formation, is greatly reduced rare-earth usage, reduces material price.The composition of this core-shell structure,
Size, shell thickness can be achieved controlledly synthesis, thus assign the magnetism of material, mechanicalness, Thermodynamically stable, electric property,
Photochemistry and catalytic property etc., and the combination of function and the improvement of performance can be realized according to the demand of people.Silica gel microball at present
The preparation method of upper supported rare earth mainly has sol-gel method (sol-gel), coordination method, homogeneous precipitation method etc..The above method closes
At material be required to carry out in the solution, therefore that there are reagent dosages is more, modification not exclusively, the problems such as separation is time-consuming.
Therefore, it is still necessary to new method is researched and developed, to meet the needs of market.
Summary of the invention
The present invention provides a kind of preparation methods of silicon dioxide colloid compound rare-earth core-shell type microballoon, it is characterised in that
It the described method comprises the following steps:
(1) synthesis of nano silica core: by dehydrated alcohol, tetraalkyl orthosilicate (such as ethyl orthosilicate), ammonium hydroxide
It is mixed with water according to volume ratio 100:5-15:5-10:20-30, obtains nanometer silicon dioxide particle, after washing to neutrality, dispersion
Into dehydrated alcohol, nano silicon dioxide dispersion, concentration 0.2g/mL-0.8g/mL, preferably 0.3g/mL-0.6g/ are obtained
ML, more preferable 0.3g/mL-0.5g/mL；
(2) synthesis of dipping-hydro-thermal method rare earth core-shell type microballoon is used: by the water solubility of at least two rare earth metals
Salt mixing, and it is dissolved in the degree that a small amount of water has dissolved just to it, it is ground later with the nano silicon dioxide dispersion of step (1)
Until generating granular mixture, high temperature drying obtains product.
The invention further relates to a kind of silicon dioxide colloid compound rare-earth core-shell type microballoons prepared by the above method；Wherein
The microballoon is by SiO2Nanoparticle core and the SiO2The surface coated one layer of rare earth ion layer of core is constituted, the rare earth from
Sublayer is the Gd that two kinds of rare earth elements are formed2O3:M3+Rare earth ion layer, described rare earth element M one kind selected from the following: Tb, Ru,
Tb, Dy, Sm, Yb, Er, Ho or Eu, preferably Gd2O3:Eu 3+Rare earth ion layer.
The invention further relates to the silicon dioxide colloid compound rare-earth core-shell type microballoons to be used as the new identification of preparation and fluorescence
The purposes of the nano print microballoon of quantitative pesticide.
Present invention employs dipping-hydrothermal synthesis methods to prepare silica compound rare-earth core-shell microspheres, present invention synthesis
There are method easy to operate, materials to save, environmental pollution is small, it is quick, do not need to be separated, the clean feature of product.
Detailed description of the invention
The SiO of Fig. 1 sol-gel method preparation2@Gd2O3:Eu3+The tem analysis image of microballoon
The SiO of Fig. 2 urea precipitation method preparation2@Gd2O3:Eu3+The tem analysis figure of microballoon
Fig. 3 is SiO of the present invention2@Gd2O3:Eu3+The tem analysis image of microballoon
Fig. 4 is SiO of the present invention2@Gd2O3:Eu3+The infrared analysis map of microballoon
Fig. 5 is SiO of the present invention2@Gd2O3:Eu3+Fluorescence analysis map (the e of microballoonx=257nm；Sample is dispersed to anhydrous
In ethyl alcohol, concentration 0.15mg/mL)；The upper right corner is the cathodoluminescence figure of sample powder.
Specific embodiment
The present invention provides a kind of preparation methods of silicon dioxide colloid compound rare-earth core-shell type microballoon, it is characterised in that
It the described method comprises the following steps:
(1) synthesis of nano silica core: by dehydrated alcohol, tetraalkyl orthosilicate (such as ethyl orthosilicate), ammonium hydroxide
It is mixed with water according to volume ratio 100:5-15:5-10:20-30, obtains nanometer silicon dioxide particle, after washing to neutrality, dispersion
Into dehydrated alcohol, nano silicon dioxide dispersion, concentration 0.2g/mL-0.8g/mL, preferably 0.3g/mL-0.6g/ are obtained
ML, more preferable 0.3g/mL-0.5g/mL；
(2) synthesis of dipping-hydro-thermal method rare earth core-shell type microballoon is used: by the water solubility of at least two rare earth metals
Salt mixing, and it is dissolved in the degree that a small amount of water has dissolved just to it, it is ground later with the nano silicon dioxide dispersion of step (1)
Until generating granular mixture, high temperature drying obtains product.
In one embodiment of the invention, dehydrated alcohol mass concentration is 95%, ammoniacal liquor mass concentration 25%.
In one embodiment of the invention, wherein at least one of two kinds of rare earth metals are Gd, at least another
Metal M is selected from Gd, Eu, Tb, Y, Sm or Er.
In one embodiment of the invention, preferably two kinds of rare earth metals, wherein the molar ratio of Gd and M is 4.5-4:1,
It is preferred that 4.2-4:1.
In one embodiment of the invention, wherein mole of the silica in Gd and nano silicon dioxide dispersion
Than for 1:20-60, preferably 1:25-50, more preferable 1:25-35.
In one embodiment of the invention, the water soluble salt of rare earth metal be chloride salt, sulfate, nitrate,
Preferably nitrate.
In one embodiment of the invention, the wherein grinding in step (2) so that raw mixture by emulsion form →
Half paste → dough → graininess；Gained granular mixture is 3 hours dry or more at 105-120 DEG C, obtains product；
The additional amount and drying temperature of the water soluble salt of water and rare earth metal wherein in mol meet following relationship:
Additional amount * (T/298.15)/water additional amount≤5.05 of the water soluble salt of 3.65≤rare earth metal,
It is preferred that additional amount * (T/298.15)/water additional amount≤4.9 of the water soluble salt of 4.2≤rare earth metal,
Wherein T is the drying temperature in step (2), is 400K-420K, preferably 408K-420K.
Without being bound by any theory, under conditions of meeting above-mentioned relation formula in step (2), obtains and be not required to be separately separated step
And clean silicon dioxide colloid compound rare-earth core-shell type microballoon.
In one embodiment of the invention, product of the invention is prepared as follows:
Synthesize the SiO of uniform particle diameter2Nano particle is as nano silica core: by 95% ethyl alcohol of 100.0mL, 5-
25% ammonium hydroxide of 15mL, the high purity water of 20-30mL are added in the single necked round bottom flask of 250.0mL, ultrasonic 5min, magnetic agitation
10min is uniformly mixed above-mentioned solution.It is then quickly added into the ethyl orthosilicate of 5-10mL.At being 30 DEG C in temperature quickly
Even magnetic agitation 17h.By being collected by centrifugation, product is repeatedly washed with dehydrated alcohol the silica of synthesis, centrifugation, until upper layer
Centrifugate reaches neutral, and silicon dioxide granule is dispersed in dehydrated alcohol, obtains the nanometer that concentration is 0.2g/mL-0.8g/mL
Silica dispersions are placed in spare in 4 DEG C of refrigerators.
Using dipping-hydro-thermal method synthesizing rare-earth core-shell type microballoon: by M (NO3)3(such as Eu (NO3)3·6H2O and Gd
(NO3)3·6H2O is dissolved in a small amount of distilled water, and sufficiently oscillation is to just having dissolved.Nano silica is added in the agate mortar
Dispersion liquid grinding, after being fully ground, mixture is by emulsion form → half paste → dough → graininess, and wherein emulsion form → half pastes
It when shape, needs to be fully ground, is uniformly mixed it, ventilation is then placed within, until half paste；When half paste → dough, after
It is continuous sufficiently to be ground in the direction of the clock until dough；When dough → graininess, when grinding, particle will be ground in sample sets
Shape, final granule shape mixture is 3 hours dry or more at high temperature drying, such as 105-120 DEG C, preferably 110-120 DEG C, obtains
Product.For example, (can wherein be put into advance in an oven by granular mixture and hold the glass dish of KOH, to absorb the NO generated
And NO2) dry.
The invention further relates to a kind of silicon dioxide colloid compound rare-earth core-shell type microballoons, wherein the microballoon is by SiO2It receives
Rice grain core and the SiO2The surface coated one layer of rare earth ion layer of core is constituted, and the rare earth ion layer is two kinds of rare earth members
The Gd that element is formed2O3:M3+Rare earth ion layer, described rare earth element M one kind selected from the following: Tb, Ru, Tb, Dy, Sm, Yb, Er,
Ho or Eu, preferably Gd2O3:Eu 3+。
The partial size of the microballoon is 50-80nm nanometers, and preferably 60-75nm is easier to be separated into stabilization in solution medium
Microemulsion.
The invention further relates to the silicon dioxide colloid compound rare-earth core-shell type microballoons to be used as the new identification of preparation and fluorescence
The purposes of the nano print microballoon of quantitative pesticide, wherein pesticide molecule trace polymerization nitride layer is formed on microballoon through the invention, and
Form nano print microballoon.
In the present invention, if without opposite explanation, operation is carried out in room temperature, condition of normal pressure.
In the present invention, unless otherwise stated, otherwise all numbers, percentage is in mass.
In the present invention, substance used is known substance, commercially available or synthesized by known method.
In the present invention, equipment therefor or equipment are conventional equipment known to the field or equipment, commercially available.
The present invention is described in detail by the following examples, embodiment is only used for understanding technical solution of the present invention,
The range being not intended to be limiting of the invention.
Instrument used in the present invention and reagent are as follows:
HYS-A type Cathodoluminescence (Beijing Heng Yuanhuajian scientific & technical corporation)；ZEISS SUPRA 55VP transmission electron microscope (Germany
Zeiss)；Prestige-21 Fourier transformation infrared spectrometer (Japanese Shimadzu)；F4600 type Fluorescence Spectrometer (Japan
HITACHI)。
Gd(NO3)3·6H2O (>=95%), M (NO3)3·6H2O (>=95%) (M=Eu3+、Tb3+、Y3+Sm3+Or Er3+)
It is purchased from Shanghai Mike's woods biochemical reagents company；Ethyl orthosilicate (>=95%) is purchased from Tianjin recovery fine chemistry industry research institute；KOH
(>=99%) is purchased from Tianjin Fu Yu Fine Chemical Co., Ltd；Dehydrated alcohol (AR) is purchased from Tianjin all generations Chemical Co., Ltd..
Distilled water comes from U.S. MiLi-Q pure water system system.
Embodiment
(1) synthesize nano silica core: by 95% ethyl alcohol of 100.0mL, 25% ammonium hydroxide of 6.0mL, 20.0mL height
Pure water is added in the single necked round bottom flask of 250.0mL, ultrasonic 5min, magnetic agitation 10min, is uniformly mixed above-mentioned solution.So
The ethyl orthosilicate of 8.0mL is rapidly joined afterwards.The Quick uniform magnetic agitation 17h at 30 DEG C.The silica of synthesis by from
The heart is collected, and product is repeatedly washed with dehydrated alcohol, is centrifuged.Until upper layer, centrifugate reaches neutral, and silicon dioxide granule is dispersed
Into dehydrated alcohol, the nano silicon dioxide dispersion that concentration is 0.3g/mL is obtained, is placed in spare in 4 DEG C of refrigerators.
(2) dipping-hydrothermal synthesis method prepares SiO2The Gd of load2O3: M (M=Eu3+、Tb3+、Y3+Or Sm3+、Er3+) microballoon
0.12mmol M(NO3)3(such as Eu (NO3)3·6H2O, 0.0535g) and 0.48mmol Gd (NO3)3˙6H2O
(0.217g) is dissolved in 3mL distilled water；The nano silicon dioxide dispersion of the silica containing 1.5g is added in the agate mortar, into
Row grinding, is finally graininess from rice paste to dough after being fully ground, whole process about time-consuming 3h or so.It will finally grind
Alms bowl is put into 110 DEG C of baking ovens dry 3h and (is put into the glass dish for holding KOH in baking oven, in advance to absorb the NO and NO that generate2), it puts
Enter cooling constant weight in drying basin, obtains silicon dioxide colloid compound rare-earth core-shell type microballoon, partial size is about 70nm nanometers.
The characterization of material
1.TEM analysis
Fig. 1-3 is respectively the saturating of sol-gel method, urea precipitation method and dipping of the present invention-hydrothermal synthesis method preparation product
Penetrate electron microscope.
To the SiO using experimental method of the present invention synthesis2-Gd2O3:Eu3+Material and use art methods sol-gel
Method is (referring specifically to G.Z.Li, et al., Sol-gel fabrication and photoluminescence properties
of SiO2@Gd2O3:Eu3+core-shell particles.J.Nanosci.Nanotechnol.,2006,6,1416-1422.
And L.A.Rocha, et al., Eu3+-doped SiO2-Gd2O3prepared by the sol-gel process:
Structural and optical properties.J.Sol-gel.Sci.Technol, 2015,76,260-270) and urine
The plain precipitation method are (referring specifically to G.X.Liu, et al., Synthesis and characterization of SiO2/Gd2O3:
Eu core-shell luminescent materials.J.Coll.Inter.Sci., 2004,278,133-138) synthesis
SiO2-Gd2O3:Eu3+Material has carried out transmission electron microscope (TEM) pattern and has compared.As shown in Figure 1-3, three kinds of methods obtain spherical junctions
Structure.Fig. 1 is prepared according to sol-gel method (citric acid-polyethylene glycol), it can be observed that having between resulting microballoon stronger viscous
Glutinous phenomenon.Fig. 2 is the preparation of urea precipitation method, but product is repeatedly washed through water, ethyl alcohol, after centrifugation, still occurs white in centrifugate
Floccule.Electron microscopic picture is observed that floccule, may some Eu through speculating3+It is changed into Eu (OH)3.Fig. 3 is used
Experimental method of the present invention obtains microballoon good dispersion, uniform particle sizes, and product is very clean.
2.IR analysis
Fig. 4 is dipping of the present invention-hydrothermal synthesis method preparation SiO2-Gd2O3:Eu3+IR spectrogram.Fig. 4 is as it can be seen that 3430cm-1For the stretching vibration of-OH group of the Si-OH group and absorption water of material surface；1097cm-1It is pointed out as Si-O-Si group
Antisymmetric stretching vibration, 802cm-1It is then the stretching vibration peak of the group.540cm-1It is neighbouring then usually pointed out as Gd-O
Key, because of Gd and SiO2With chemical bonds between core.
3. fluorescence analysis
Fig. 5 is that dipping of the present invention-hydrothermal synthesis method prepares SiO2-Gd2O3:Eu3+Fluorescence pattern (ex=257nm；Sample
It is dispersed in dehydrated alcohol, concentration 0.15mg/mL)；The upper right corner is the cathodoluminescence figure of sample powder.
Fig. 5 is that dipping of the present invention-hydrothermal synthesis method prepares SiO2-Gd2O3:Eu3+Fluorescence pattern.When excitation wavelength is
When 257nm, most strong emission peak is attributed to Eu near 610nm3+'s5D0→7F2Transition peak.This is Eu3+In Gd2O3Deng vertical
Characteristic fluorescence in prismatic crystal phase oxide parent lattice.The upper right corner Fig. 3 is that sample powder issues under cathode-ray (CR) excitation
Pink fluorescence.
As it can be seen that having synthesized the SiO with good luminous performance using dipping-hydro-thermal method of the present invention2-Gd2O3:Eu3+Fluorescence
Powder.Tem analysis shows that the sample particle diameter of synthesis is evenly distributed, good dispersion, and forms the very smooth core-shell structure copolymer knot in surface
Structure.Fluorescence spectrum and cathode-ray exciting spectrogram show that the fluorescence property of the material is excellent.The dioxide/silica gel as a result,
Bluk recombination rare earth core-shell type microballoon is used as the purposes of the nano print microballoon of the new identification of preparation and fluorescent quantitation pesticide, such as knows
Other carbamate chemicals for agriculture, such as MTMC, Aldicarb, carbofuran, Mobucin, Aphox, Methomyl, carbaryl etc..With
Traditional sol-gel method is compared with the precipitation method, and there are this synthetic method easy to operate, materials to save, environmental pollution is small, is not required to point
From the clean feature of product.
Claims (10)
1. a kind of preparation method of silicon dioxide colloid compound rare-earth core-shell type microballoon, it is characterised in that the method includes with
Lower step:
(1) synthesis of nano silica core: by dehydrated alcohol, tetraalkyl orthosilicate (such as ethyl orthosilicate), ammonium hydroxide and water
It is mixed according to volume ratio 100:5-15:5-10:20-30, obtains nanometer silicon dioxide particle and be dispersed to nothing after washing to neutrality
In water-ethanol, nano silicon dioxide dispersion is obtained, concentration 0.2g/mL-0.8g/mL, preferably 0.3g/mL-0.6g/mL,
More preferable 0.3g/mL-0.5g/mL；
(2) it uses the synthesis of dipping-hydro-thermal method rare earth core-shell type microballoon: the water soluble salt of at least two rare earth metals is mixed
Close, and be dissolved in the degree that a small amount of water has dissolved just to it, later with the grinding of the nano silicon dioxide dispersion of step (1) until
Granular mixture is generated, high temperature drying obtains product.
2. preparation method described in claim 1, wherein dehydrated alcohol mass concentration is 95%, ammoniacal liquor mass concentration 25%.
3. preparation method described in claim 1, wherein at least one of two kinds of rare earth metals are Gd, at least another metal
M is selected from Gd, Eu, Tb, Y, Sm or Er.
4. preparation method described in claim 1, wherein it is preferred that two kinds of rare earth metals, wherein the molar ratio of Gd and M is 4.5-4:
1, preferably 4.2-4:1.
5. preparation method as claimed in claim 4, the wherein titanium dioxide in the water soluble salt and nano silicon dioxide dispersion of Gd
The molar ratio of silicon is 1:20-60, preferably 1:25-50, more preferable 1:25-35.
6. preparation method described in claim 1, wherein the water soluble salt of rare earth metal is chloride salt, sulfate, nitrate,
Preferably nitrate.
7. preparation method described in claim 1, the wherein grinding in step (2), so that raw mixture is by emulsion form → half
Paste → dough → graininess；Gained granular mixture is 3 hours dry or more at 105-120 DEG C, obtains product；
The additional amount and drying temperature of the water soluble salt of water and rare earth metal wherein in mol meet following relationship:
Additional amount * (T/298.15)/water additional amount≤5.05 of the water soluble salt of 3.65≤rare earth metal,
It is preferred that additional amount * (T/298.15)/water additional amount≤4.9 of the water soluble salt of 4.2≤rare earth metal,
Wherein T is the drying temperature in step (2), is 403K-420K, preferably 408K-420K.
8. a kind of silicon dioxide colloid compound rare-earth core-shell type microballoon is prepared by the method for any one of claim 1-7；Its
Described in microballoon by SiO2Nanoparticle core and the SiO2The surface coated one layer of rare earth ion layer of core is constituted, the rare earth
Sheath is the Gd that two kinds of rare earth elements are formed2O3:M3+Rare earth ion layer, described rare earth element M one kind selected from the following: Tb,
Ru, Tb, Dy, Sm, Yb, Er, Ho or Eu, preferably Gd2O3:Eu3+Rare earth ion layer.
9. silicon dioxide colloid compound rare-earth core-shell type microballoon according to any one of claims 8, wherein the partial size of the microballoon is 50-
80 nanometers.
10. silicon dioxide colloid compound rare-earth core-shell type microballoon according to any one of claims 8 is used as the new identification of preparation and fluorescent quantitation
The purposes of the nano print microballoon of pesticide.
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