CN106479480A - A kind of Nano microsphere preparation method with core/shell type composite construction - Google Patents

Abstract

The present invention relates to a kind of Nano microsphere preparation method with core/shell type composite construction for improving ternary rare earth complex material thermoluminescence strength stability, Re (L)₃Phen coordination compound has higher dissolubility in acetone soln, but in ethanol solution dissolubility relatively low it is easy to separate out.Using the difference of the two dissolubility, the inventive method is to make Re (L) first₃Phen coordination compound solute, in acetone soln, then slowly to entering in ethanol solution, adjusts pH value, forms rare earth beta-diketone complex nanocluster colloid solution, recycles teos hydrolysis to generate SiO₂Method, at Re (L)₃The outside growth SiO of phen coordination compound cluster₂Shell.The present invention in biological tracing, photonic crystal, luminous with the multiple fields such as display, microcavity laser, data storage, nano-sensor, there is potential using value.

Description

A kind of Nano microsphere preparation method with core/shell type composite construction

Technical field

The present invention relates to nanoelectronics device material field, more particularly to a kind of Nano microsphere preparation method with core/shell type composite construction for improving ternary rare earth complex material thermoluminescence strength stability.

Background technology

The development process of nanosecond science and technology can be seen, from research nanoparticle, the structure of nano block and characteristic, to energetically for the purpose of directly applying the excavation light of nano composite material, electricity, magnetic, mechanics, biology etc. aspect functional characteristic, and then the scope of nano materials research is expanded constantly.Further, built using microcosmic primitive, assemble the new nano structural material with specific function so as to be used in nano electron device and extensive device are integrated.

Due to the small-size effect of nano-particle, surface should with quantum size effect all in action simultaneously, they are often difficult to distinguish to the contribution of material a certain kind performance, power, it is favourable effect, or unfavorable effect is more difficult to judge, this brings difficulty not only to the explanation of a certain phenomenon, brings very big difficulty also to design novel nano structure simultaneously.How to control the impact to nano ZnO for these effects；A kind of impact of effect how is controlled to draw the impact of another kind of effect；How to synthesize with specific dimensions, and epigranular is distributed the nano material of soilless sticking, this is all nano materials research problem demanding prompt solution.

From the viewpoint of physicss, the surface of condensed state matter has symmetry and free energy different from body phase：When something is reduced to mesoscopic size by macro-size, the impact to its physics, chemical property for the surface will can not be ignored.Therefore, the surface of nanoparticle is designed and controls, necessarily become the key of standby new material.In the world nearly one or two years, a very main aspect of nano materials research is exactly the modifying surface to nano-particle.Specific substance cladding and the modification on surface are done by the surface in nanoparticle, to change the physicochemical properties of nano grain surface electriferous state, surface texture and nano-particle, to the characteristic required for obtaining.

The shell of core-shell type nano composite material has several functions, for example：Reduce the surface energy state of nanoparticle, eliminate the surface charge of particle, increase stability, increase nanoparticle and other interface binding powers, improve nanoparticle dispersibility, change the optically and electrically performance of core, increase ruggedness, there is provided supporting network structure for core, and when some composites form the nanostructured of periodic arrangement as elementary cell it is ensured that the even size distribution of elementary cell.Formed different according to Shell Materials, the nano composite material with nucleocapsid structure can be roughly divided into two classes：One class has polymeric shell；Another kind of have inorganic material shell.Our invention is mainly for the nano-complex with inorganic material shell.

In collochemistry, silicon dioxide colloid has very high stability in aqueous solution and other medium.During the course of the reaction, silicon dioxide colloid morphology controllable, deposition process are easily-controllable（Shell thickness is controlled）, and its presoma is cheap, be readily obtained.Meanwhile, as a kind of traditional host material, silicon dioxide but also with many excellent properties, including optical transparence, chemical inertness, bio-compatibility etc..Using these characteristics of silicon dioxide, people can be modified to nano-material surface property in the case of keeping the original physics of core nano material, chemical property substantially constant and be cut out.SiO is formed by coating function₂Environmental stability and the compatibility of core material after shell, can be effectively improved.

Rare earth beta-diketon phenanthroline complex Re (L)₃phen（Re: Eu³⁺, Tb³⁺；L:Beta-diketon class part；Phen：Phen）, such as Fig. 1, there is higher luminous intensity（See Fig. 3）, have potential using value in biomolecule identification, full-color display and field of organic electroluminescence, widely studied.But, when temperature is higher than 80 DEG C, degradation and decomposition phenomenon, luminous intensity is decreased obviously in its less stable when working long hours.How to improve the stability problem of rare earth compounding, always scientist's focus of attention.The heat stability of silicon dioxide is higher, is a kind of preferable host material.In this work, rare earth compounding is embedded in formation core-shell type complex microsphere in silicon dioxide microsphere and still can keep higher luminous intensity, its heat stability significantly improves simultaneously（As Fig. 4）.

Content of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art, a kind of cladding method for improving ternary rare earth complex material heat stability is provided, there is the Nano microsphere preparation method of core/shell type composite construction, it is kept also to have higher luminous intensity when temperature works long hours higher than 80 DEG C, heat stability significantly improves.

The object of the present invention is achieved like this,

Re(L)₃Phen coordination compound has higher dissolubility in acetone soln, but in ethanol solution dissolubility relatively low it is easy to separate out.Using the difference of the two dissolubility, the inventive method is to make Re (L) first₃Phen coordination compound solute, in acetone soln, then slowly to entering in ethanol solution, adjusts pH value, forms rare earth beta-diketone complex nanocluster colloid solution, recycles teos hydrolysis to generate SiO₂Method, at Re (L)₃The outside growth SiO of phen coordination compound cluster₂ Shell.

The comprising the following steps that of the method：

1）, reaction reagent prepare：

EuCl₃·6H₂O and TbCl₃·6H₂O（Analysis is pure）；

Dibenzoyl methane（DBM, analysis is pure）；

Pentanedione（AcAc）(analysis is pure)；

1,10- Phen (Phen, analysis is pure)；

NaOH（Analysis is pure）

Tetraethyl orthosilicate (analysis is pure)；

Hydrochloric acid (36%-38%, analysis is pure),

Dehydrated alcohol（Analysis is pure）、

Acetone (analysis is pure),

Ammonia (25%-28%, analysis is pure),

Deionized water.

2）, NaOH alcohol sodium solution preparation

Take 10 g amount sodium hydroxide（Excessive）Put into 500 In ml dehydrated alcohol, after fully dissolving, take supernatant.

3）, the Eu (DBM) that glows₃Phen coordination compound synthesizes

A. 0.673 g dibenzoyl methane (DBM) and 0.198 g 1 are taken, 10- Phen (Phen) successively puts into 40 In mL dehydrated alcohol, stirring and dissolving becomes settled solution；

B. take 0.366 g EuCl again₃·6H₂O puts in 40 mL dehydrated alcohol, and stirring and dissolving becomes settled solution;

C. stir the solution of lower combining step a and b；

D. use step 2）The NaOH ethanol solution of middle preparation slowly instills step 3 under agitation）In c solution, adjust pH between 6～7, then precipitation 4-6 h at room temperature, precipitate is with after absolute ethanol washing 2-3 time, putting in baking oven 80⁰Obtain final product after 2-3 h is dried under C.

4）, the Tb (AcAc) of green light₃Phen coordination compound synthesizes

A. 0.3 g pentanedione (AcAc) and 0.198 g 1 are taken, 10- Phen (Phen) successively puts into 40 Dissolve in mL dehydrated alcohol；

B. take 0.373gTbCl again₃·6H₂O puts into step 4）It is dissolved to clarification in solution in a;

C. use step 2）The NaOH ethanol solution of middle preparation, slowly instills step 4 under agitation）In the solution of b, adjust pH between 6～7（With the test of pH reagent paper）, then, precipitation 4-6 h at room temperature, centrifugation obtains sediment and with absolute ethanol washing precipitate 1-2 time.It is centrifuged and puts in baking oven 80⁰1 h is dried under C obtain final product.

5）, concrete cladding method be：

By step 3）The Eu (DBM) of preparation₃Phen coordination compound or step 4）The Tb (AcAc) of preparation₃Phen coordination compound adds in 100 ml acetone solns, stirs to clarify solution, adds the mixed solution of 50 ml ethanol and deionized water in clear liquor, the volume ratio of ethanol and deionized water is：Ethanol：Deionized water=5:1, ammonia is added to adjust pH value between 8-9, it is added dropwise over tetraethyl orthosilicate in the mixture, be hydrolyzed reaction, stop tetraethyl orthosilicate after all generating white precipitate and instill, after the white precipitate generating is filtered, fully soaked with dehydrated alcohol and acetone, multiple washing precipitate, wash unreacted material and impurity off, it is dried under room temperature, obtain white powder Eu (DBM)₃phen/SiO₂ Or Tb (AcAc)₃Phen/SiO₂Complex microsphere.

The present invention has the advantages that：

Re(L)₃Phen coordination compound has of a relatively high luminous intensity, has potential using value in full-color display and field of organic electroluminescence, is widely studied.But its less stable, when temperature is higher than 80 DEG C, works long hours and degradation and decomposition phenomenon occurs, luminous intensity is decreased obviously.How to improve Re (L)₃The stability of phen coordination compound, always scientist's focus of attention.The heat stability of silicon dioxide is higher, is a kind of preferable host material.In the present invention, rare earth compounding is embedded in formation core-shell type complex microsphere in silicon dioxide microsphere and can keep Re (L) at a relatively high temperature₃The stability of phen coordination compound luminous intensity.

Brief description

Fig. 1 is rare earth organic complex Eu (DBM) of the present invention₃The molecular structure of phen.

Fig. 2 is shell/caryogram Eu (DBM) 3phen/SiO of the present invention₂The electromicroscopic photograph figure of complex microsphere, wherein

（A）Multiple complex microspheres;（B）Single microsphere.

Fig. 3 is Eu of the present invention (DBM)₃Phen and Eu (DBM)₃phen/SiO₂Launching light spectrogram, wherein (a) Eu (DBM)₃phen；(b) Eu(DBM)₃phen/SiO₂Complex microsphere.

Fig. 4, it is Eu of the present invention (DBM)₃Phen and Eu (DBM)₃phen/SiO₂Aging curve at 80 DEG C, wherein（A）Eu(DBM)₃phen;（B）Eu(DBM)₃phen/SiO₂Complex microsphere.

Specific embodiment

The comprising the following steps that of the method：

1）, reaction reagent prepare：

EuCl₃·6H₂O and TbCl₃·6H₂O（Analysis is pure）；

Dibenzoyl methane（DBM, analysis is pure）；

Pentanedione（AcAc）(analysis is pure)；

1,10- Phen (Phen, analysis is pure)；

NaOH（Analysis is pure）

Tetraethyl orthosilicate (analysis is pure)；

Hydrochloric acid (36%-38%, analysis is pure),

Dehydrated alcohol（Analysis is pure）、

Acetone (analysis is pure),

Ammonia (25%-28%, analysis is pure),

Deionized water.

2）, NaOH alcohol sodium solution preparation

Take 10 g amount sodium hydroxide（Excessive）Put into 500 In ml dehydrated alcohol, after fully dissolving, take supernatant.

3）, the Eu (DBM) that glows₃Phen coordination compound synthesizes

A. 0.673 g dibenzoyl methane (DBM) and 0.198 g 1 are taken, 10- Phen (Phen) successively puts into 40 In mL dehydrated alcohol, stirring and dissolving becomes settled solution；

B. take 0.366 g EuCl again₃·6H₂O puts in 40 mL dehydrated alcohol, and stirring and dissolving becomes settled solution;

C. stir the solution of lower combining step a and b；

D. use step 2）The NaOH ethanol solution of middle preparation slowly instills step 3 under agitation）In c solution, adjust pH between 6～7, then precipitation 4-6 h at room temperature, precipitate is with after absolute ethanol washing 2-3 time, putting in baking oven 80⁰Obtain final product after 2-3 h is dried under C.

4）, the Tb (AcAc) of green light₃Phen coordination compound synthesizes

A. 0.3 g pentanedione (AcAc) and 0.198 g 1 are taken, 10- Phen (Phen) successively puts into 40 Dissolve in mL dehydrated alcohol；

B. take 0.373gTbCl again₃·6H₂O puts into step 4）It is dissolved to clarification in solution in a;

C. use step 2）The NaOH ethanol solution of middle preparation, slowly instills step 4 under agitation）In the solution of b, adjust pH between 6～7（With the test of pH reagent paper）, then, precipitation 4-6 h at room temperature, centrifugation obtains sediment and with absolute ethanol washing precipitate 1-2 time.It is centrifuged and puts in baking oven 80⁰1 h is dried under C obtain final product.

5）, concrete cladding method be：

By step 3）The Eu (DBM) of preparation₃Phen coordination compound or step 4）The Tb (AcAc) of preparation₃Phen coordination compound adds in 100 ml acetone solns, stirs to clarify solution, adds the mixed solution of 50 ml ethanol and deionized water in clear liquor, the volume ratio of ethanol and deionized water is：Ethanol：Deionized water=5:1, ammonia is added to adjust pH value between 8-9, it is added dropwise over tetraethyl orthosilicate in the mixture, be hydrolyzed reaction, stop tetraethyl orthosilicate after all generating white precipitate and instill, after the white precipitate generating is filtered, fully soaked with dehydrated alcohol and acetone, multiple washing precipitate, wash unreacted material and impurity off, it is dried under room temperature, obtain white powder Eu (DBM)₃phen/SiO₂ Or Tb (AcAc)₃Phen/SiO₂Complex microsphere.

Claims (1)

1. a kind of Nano microsphere preparation method with core/shell type composite construction it is characterised in that：The comprising the following steps that of the method：

1）, reaction reagent prepare：

EuCl₃·6H₂O and TbCl₃·6H₂O、

Dibenzoyl methane DBM,

Pentanedione AcAc,

1,10- Phen Phen,

NaOH

Tetraethyl orthosilicate,

36%-38% hydrochloric acid,

Dehydrated alcohol,

Acetone,

25%-28% ammonia,

Deionized water；

2）, NaOH alcohol sodium solution preparation：

Take the 10 g amount sodium hydroxide to put in 500 ml dehydrated alcohol, after fully dissolving, take supernatant；

3）, the Eu (DBM) that glows₃Phen coordination compound synthesizes：

A. take 0.673 g dibenzoyl methane DBM and 0.198 g 1,10- Phen Phen priority is put in 40 mL dehydrated alcohol, and stirring and dissolving becomes settled solution；

B. take 0.366 g EuCl again₃·6H₂O puts in 40 mL dehydrated alcohol, and stirring and dissolving becomes settled solution;

C. stir the solution of lower combining step a and b；

D. use step 2）The NaOH ethanol solution of middle preparation slowly instills step 3 under agitation）In c solution, adjust pH between 6～7, then precipitation 4-6 h at room temperature, precipitate is with after absolute ethanol washing 2-3 time, putting in baking oven 80⁰Obtain final product after 2-3 h is dried under C；

4）, the Tb (AcAc) of green light₃Phen coordination compound synthesizes：

A. take 0.3 g pentanedione AcAc and 0.198 g 1,10- Phen Phen priority puts into dissolving in 40 mL dehydrated alcohol；

B. take 0.373gTbCl again₃·6H₂O puts into step 4）It is dissolved to clarification in solution in a;

C. use step 2）The NaOH ethanol solution of middle preparation, slowly instills step 4 under agitation）In the solution of b, adjust pH between 6～7, then, precipitation 4-6 h at room temperature, centrifugation obtains sediment and with absolute ethanol washing precipitate 1-2 time.It is centrifuged and puts in baking oven 80⁰1 h is dried under C obtain final product；

5）, concrete cladding method be：

By step 3）The Eu (DBM) of preparation₃Phen coordination compound or step 4）The Tb (AcAc) of preparation₃Phen coordination compound adds in 100 ml acetone solns, stirs to clarify solution, adds the mixed solution of 50 ml ethanol and deionized water in clear liquor, the volume ratio of ethanol and deionized water is：Ethanol：Deionized water=5:1, ammonia is added to adjust pH value between 8-9, it is added dropwise over tetraethyl orthosilicate in the mixture, be hydrolyzed reaction, stop tetraethyl orthosilicate after all generating white precipitate and instill, after the white precipitate generating is filtered, fully soaked with dehydrated alcohol and acetone, multiple washing precipitate, wash unreacted material and impurity off, it is dried under room temperature, obtain white powder Eu (DBM)₃phen/SiO₂ Or Tb (AcAc)₃Phen/SiO₂Complex microsphere.