CN103923656B - A kind of preparation method of gadolinium oxide coated ferroferric oxide magnetic fluorescence nano hollow ball - Google Patents
A kind of preparation method of gadolinium oxide coated ferroferric oxide magnetic fluorescence nano hollow ball Download PDFInfo
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Abstract
A kind of preparation method of gadolinium oxide coated ferroferric oxide magnetic fluorescence nano hollow ball, it utilizes hard template method, with the silicon dioxide of different inner diameters as template, precipitate ferric hydroxide on the gel of silicon dioxide and carry out coated rare-earth element gadolinium again as template, thus obtain particle diameter Gd not of uniform size
2o
3parcel Fe
3o
4magnetic fluorescence nano hollow ball.Present invention process is easy, cost is low, reproducible, suitability for scale production, and avoid reuniting the impact brought because of magnetic-particle.Obtained hollow ball has relatively large specific area; The adjustable extent of particle size is larger, has widened the size adjustable field of hollow ball; There is magnetic and fluorescence property simultaneously, add its orientation of Magnetic control and the pharmaceutical carrier of perspective optical property can intuitively can understand the trend of medicine, and be easy to broken under the effect of external force or disturbance, can be used for contrast agent and biomarker, Magnetic resonance imaging (MRI), biological and biomedical imaging.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to a kind of Gd
2o
3parcel Fe
3o
4the preparation method of magnetic fluorescence nano hollow ball.
Background technology
In recent years, along with the development of technology, it is found that, compared with block materials, the hollow ball of corresponding same material is owing to having high-specific surface area, better infiltration and low-density, very important application [(a) C.N.R.Rao is had in a lot of field such as catalysis, encapsulation, cell separation, chemical reactor, drug delivery, light material, opto-electronic device, A.Govindaraj, G.Gundiah, S.R.C.Vivekchand, Chem.Eng.Sci.2004,59,4665.(b) F.Caruso, Top.Curr.Chem.2003,227,145.].Therefore, the research with the tiny balloon of different composition causes people to pay close attention to widely, particularly has the multi-functional tiny balloon of optics and magnetic, can be positioned at a specific region for drug delivery and fluorescence imaging with external magnetic field.Because these performances, contrast agent and biomarker are successfully used to, for magnetic resonance imaging (MRI), biological and biomedical imaging.In numerous optical material, due to rare earth material height luminescence generated by light (PL) quantum yield, emission wavelength is tunable, low phonon energy, chemical stability and thermal stability high and enjoy favor.Many researchers have prepared by the different route of design the tiny balloon that this type of has crystalline state or amorphous nano structure ball wall.In the article reported, the preparation of tiny balloon mainly through template, namely with ɑ-Fe
2o
3, Fe
3o
4and β-FeOOH particle is template, by sluggish precipitation, layer upon layer electrostatic self-assembly method, sol-gal process etc., inorganic matter is coated in template, then by pyrolysis or dissolving removing template, thus obtains corresponding nucleocapsid structure.Template is divided into again hard template method and soft template method.Because soft template is by a series of supramolecular aggregation formed by amphipathic molecule, when system environment changes to some extent, its pattern may change, and is unfavorable for preparing single dispersing and the structure of rule.And the control that hard template method can be realized hollow ball size and homogeneity by the size of control hard template, do not change its pattern in reaction system and precipitation process simultaneously, thus the control to ball wall thickness and composition can be realized.Therefore at present about the preparation of tiny balloon, be mostly to utilize hard template technology, and adopt Gd
2o
3parcel Fe
3o
4the preparation method of magnetic fluorescence nano hollow ball have not been reported.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the gadolinium oxide coated ferroferric oxide magnetic fluorescence nano hollow ball that a kind of technique is simple, handling safety, cost are low, solve the particle aggregation problem brought as template by magnetic-particle, thus reach the object simplifying experiment and be stranded.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of gadolinium oxide coated ferroferric oxide magnetic fluorescence nano hollow ball, is characterized in that comprising the steps:
1) get nano SiO 2 particle 1.2 ~ 1.6g, add 10 ~ 25ml distilled water, obtained silica colloid solution; Getting nine water ferric nitrate 0.200 ~ 0.268g and urea 0.200 ~ 0.300g is dissolved in 20 ~ 25ml distilled water, obtained A mixed liquor;
2) by above-mentioned obtained silica colloid solution and the mixing of A mixed liquor, obtained B mixed liquor, adds 40 ~ 80ml distilled water, stir 4 ~ 6 hours under 80 ~ 95 DEG C of temperature conditions, obtain bronzing homogeneous system, cooling, obtain red-brownish coloured particles precipitation, complete particle outer coated for the first time;
3) by after above-mentioned red-brownish coloured particles precipitation cleaning-drying, get 1.0 ~ 1.5g, add 10 ~ 25ml distilled water, obtained homogeneous colloids solution; Getting six water gadolinium nitrate 0.200 ~ 0.310g and urea 0.200 ~ 0.300g is dissolved in 20 ~ 25ml distilled water, obtained C mixed liquor;
4) the homogeneous colloids solution prepared by step 3) and the mixing of C mixed liquor, obtained D mixed liquor, adds 40 ~ 80ml distilled water, stir 4 ~ 6 hours under 80 ~ 95 DEG C of temperature conditions, obtain red homogeneous system, cooling, obtain red granules precipitation, complete the outer second time of particle coated;
5) get above-mentioned coated after red granules carry out core etching, get bottom red granules precipitation;
6) the dried powder hydrogen reducing obtained after the red granules of bottom precipitation cleaning-drying can be obtained the Gd of required preparation
2o
3parcel Fe
3o
4magnetic fluorescence nano hollow ball.
Above the quality of each material or volume with nano SiO 2 particle 1.2 ~ 1.6g for benchmark.
As improvement, the cleaning-drying in described step 3) obtains red-brownish coloured particles, then vacuumize by distilled water cleaning red-brownish coloured particles precipitation, and baking temperature remains on 30 ~ 60 DEG C, obtains dried powder.
As improvement, the core etching in described step 5) in red granules, adds the immersion of 0.5 ~ 2.0mol/LNaOH solution carry out core etching, and soak time is 3 ~ 6 hours.
Improve, the cleaning-drying in described step 6) obtains red granules, then vacuumize by distilled water cleaning red granules precipitation, and baking temperature remains on 30 ~ 60 DEG C, obtains dried powder again.
Finally, the technique of the hydrogen reducing in described step 6) is: the air velocity of hydrogen is 40 ~ 60mL/min, and heating and temperature control, at 450 ~ 550 DEG C, keeps this steady temperature and hydrogen flow rate 2 ~ 3 hours.
Compared with prior art, the invention has the advantages that: adopt wet method injection process to prepare the technique of iron/silicon dioxide: and with iron/silicon dioxide for template outer cladding Gd
2o
3, reduced and obtained metal Fe
3o
4@Gd
2o
3multifunctional nano hollow ball; Compare at magnetic-particle outsourcing SiO
2and carry out Zeng Frequency experiment as template, preparation method's technique of the present invention is simple, handling safety, cost are low, reproducible, suitability for scale production; Obtained hollow ball good dispersion, evenly coated; Surface has loose structure, there is relatively large specific area and stronger magnetic, be easy to realize controlling, there is very high application potential in medical science, can be used for contrast agent and biomarker, Magnetic resonance imaging (MRI), biological and biomedical imaging; And by using the template of different size, the Fe of different inner diameters size can be synthesized on demand in a large number
3o
4@Gd
2o
3multifunctional nano hollow ball.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of iron nano-hollow ball in embodiment 1;
Fig. 2 is the electron scanning micrograph of iron in embodiment 1-gadolinium composite material nanometer hollow ball;
Fig. 3 is the elementary analysis photo of iron in embodiment 1-gadolinium composite material nanometer hollow ball;
Fig. 4 is the electron scanning micrograph of iron in embodiment 2-gadolinium composite material nanometer hollow ball;
Fig. 5 is Fe in embodiment 1
3o
4@Gd
2o
3x-ray diffractogram (the Fe of nano-hollow ball
3o
4: JCPDS CardNo.89-6466);
Fig. 6 is Fe in embodiment 1
3o
4@Gd
2o
3the magnetic hysteresis loop figure of nano-hollow ball.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
1. get the Nano microsphere 1.5g that silicon dioxide particle diameter is 500nm, add 10ml distilled water, ultrasonic to homogeneous colloids solution.
2. weigh six water ferric nitrate 0.268g and urea 0.290g respectively, be dissolved in 20ml distilled water after both are mixed, add in three-neck flask.
3. being added in three-neck flask 2. by mixed solution 1., add 70ml distilled water, is red homogeneous colloids solution.
4. three-neck flask is put into Water Tank with Temp.-controlled, stir, regulating thermostatic bath temperature at 95 DEG C, after system temperature reaches 95 DEG C, Keep agitation 4h.
5. by centrifugal for above-mentioned mixed liquor, with redistilled water cleaning, more centrifugal, obtain red brown solid precipitation.
6. above step is the complete process of carrying out primary particle outer cladding, can need to proceed coated rare-earth element gadolinium on the basis of this product according to preparation.Get the above-mentioned Nano microsphere 1.5g prepared, add 10ml distilled water, ultrasonic to homogeneous colloids solution.
7. weigh six water gadolinium nitrate 0.310g and urea 0.290g respectively, be dissolved in 20ml distilled water after both are mixed, add in three-neck flask.Three-neck flask is put into Water Tank with Temp.-controlled, stir, regulating thermostatic bath temperature at 95 DEG C, after system temperature reaches 95 DEG C, Keep agitation 4h.
8. by centrifugal for above-mentioned mixed liquor, with redistilled water cleaning, more centrifugal, obtain red solid precipitation.
9. soaking adding 0.8mol/L NaOH solution in red solid powder, soaking 4h, upper solution is poured out, obtain bottom red solid precipitation.Red solid precipitation is repeatedly washed with distilled water, by the powder of washes clean in vacuum drying chamber, 60 DEG C of vacuumizes.
10. take a morsel above-mentioned dried powder, is placed in little quartz boat, puts into quartz glass tube.Pass into pure hydrogen 60mL/min, keep constant hydrogen gas velocity, adopt temperature programming, in 45 minutes, be warming up to 450 DEG C, after keeping this steady temperature and hydrogen flow rate 2h, stop heating, allow burner hearth and quartz ampoule naturally cool to normal temperature state, still keep constant hydrogen air-flow 12h around here.Now can open quartz ampoule, carefully quartz boat be taken out, rapidly powder be loaded vacuum in little reagent bottle and preserve.
As shown in Figure 2, as can be seen from SEM (Scanning Electron Microscopy scanning electron microscopy) figure, the Fe in the present embodiment
3o
4@Gd
2o
3nano-hollow ball has spherical and hollow structure, and good dispersion, uniform particle sizes, surface has strip projection, and about about the 50nm of coated outer casing thickness, surface exists aperture.
Embodiment 2
Constant by the dosage in the method for above-described embodiment 1, with silicon dioxide particle diameter 180nm as kernel, carry out coated, then etch away kernel with NaOH 0.5mol/L, with hydrogen reducing, reduction temperature remains on 450 DEG C, other conditions are identical with embodiment 1, obtain Fe
3o
4@Gd
2o
3nano-hollow ball.As can be seen from the SEM of Fig. 4, integral coating is relatively even, single dispersing and regular.
In a word, the present invention reports one and utilizes hard template method, with the silicon dioxide of different inner diameters as template, synthesizes by hydrolytic process the metal Fe that particle internal diameter size is approximately 500nm and 180nm
3o
4@Gd
2o
3nano-hollow ball.Reduced after we adopt wet method injection process, obtained metal Fe
3o
4@Gd
2o
3nano-hollow ball.
The hollow ball obtained in this patent has relatively large specific area; The adjustable range of particle size is larger, has widened the size adjustable field of hollow ball; Fe
3o
4@Gd
2o
3nano-hollow ball has fluorescence and magnetic, its orientation of Magnetic control can be added, the pharmaceutical carrier of perspective optical property can intuitively can understand the trend of medicine, and this porous hollow sphere is easy to broken under the effect of external force or disturbance, this is in medical science, can have very high potential using value as pharmaceutical carrier later.This kind of material with fluorescence and magnetic property, has now been successfully used to contrast agent and biomarker at present, Magnetic resonance imaging (MRI), biological and biomedical imaging.
Claims (4)
1. a preparation method for gadolinium oxide coated ferroferric oxide magnetic fluorescence nano hollow ball, is characterized in that comprising the steps:
1) get nano SiO 2 particle 1.2 ~ 1.6g, add 10 ~ 25ml distilled water, obtained silica colloid solution; Getting nine water ferric nitrate 0.200 ~ 0.268g and urea 0.200 ~ 0.300g is dissolved in 20 ~ 25ml distilled water, obtained A mixed liquor;
2) by above-mentioned obtained silica colloid solution and the mixing of A mixed liquor, obtained B mixed liquor, adds 40 ~ 80ml distilled water, stir 4 ~ 6 hours under 80 ~ 95 DEG C of temperature conditions, obtain bronzing homogeneous system, cooling, obtain red-brownish coloured particles precipitation, complete particle outer coated for the first time;
3) by after above-mentioned red-brownish coloured particles precipitation cleaning-drying, get 1.0 ~ 1.5g, add 10 ~ 25ml distilled water, obtained homogeneous colloids solution; Getting six water gadolinium nitrate 0.200 ~ 0.310g and urea 0.200 ~ 0.300g is dissolved in 20 ~ 25ml distilled water, obtained C mixed liquor;
4) by step 3) the homogeneous colloids solution prepared and the mixing of C mixed liquor, obtained D mixed liquor, adds 40 ~ 80ml distilled water, stir 4 ~ 6 hours under 80 ~ 95 DEG C of temperature conditions, obtain red homogeneous system, cooling, obtain red granules precipitation, complete the outer second time of particle coated;
5) get above-mentioned coated after red granules carry out core etching, get bottom red granules precipitation; Described core etching in red granules, adds the immersion of 0.5 ~ 2.0mol/L NaOH solution carry out core etching, and soak time is 3 ~ 6 hours;
6) the dried powder hydrogen reducing obtained after the red granules of bottom precipitation cleaning-drying can be obtained the Gd of required preparation
2o
3parcel Fe
3o
4magnetic fluorescence nano hollow ball;
Above the quality of each material or volume with nano SiO 2 particle 1.2 ~ 1.6g for benchmark.
2. preparation method according to claim 1, is characterized in that described step 3) in cleaning-drying be with distilled water cleaning red-brownish coloured particles precipitation obtain red-brownish coloured particles, then vacuumize, baking temperature remains on 30 ~ 60 DEG C, obtains dried powder.
3. preparation method according to claim 1, is characterized in that described step 6) in cleaning-drying be with distilled water cleaning red granules precipitation obtain red granules, then vacuumize, baking temperature remains on 30 ~ 60 DEG C, obtains dried powder.
4. preparation method according to claim 1, it is characterized in that described step 6) in the technique of hydrogen reducing be: the air velocity of hydrogen is 40 ~ 60mL/min, heating and temperature control, at 450 ~ 550 DEG C, keeps this steady temperature and hydrogen flow rate 2 ~ 3 hours.
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| CN104830323B (en) * | 2015-05-25 | 2016-08-31 | 广东工业大学 | A kind of Yb3+/ Er3+codope MnF2the preparation method of interior hollow ball |
| CN105482804B (en) * | 2016-01-11 | 2018-03-09 | 东北师范大学 | A kind of latent fingerprint detection probe and preparation method thereof |
| CN105950148A (en) * | 2016-04-29 | 2016-09-21 | 中国计量大学 | Preparation method for preparing ferroferric oxide hollow ball-based fluorescent magnetic composite material |
| CN106799233B (en) * | 2017-01-13 | 2019-05-21 | 河北科技大学 | A kind of hollow Nanometer Copper/rare earth catalyst and its preparation method and application for removing underwater trace hardly degraded organic substance |
| CN108919386B (en) * | 2018-06-20 | 2019-10-18 | 中山大学 | The method for preparing magnetic amorphous photonic crystal based on ferroso-ferric oxide/silicon dixoide nucleocapsid structure nano particles |
| CN109536448B (en) * | 2018-12-10 | 2020-01-10 | 济宁医学院 | Multifunctional tretinoin-loaded gadolinium-doped ferroferric oxide composite nanoparticle |
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| CN1616593A (en) * | 2004-11-03 | 2005-05-18 | 东南大学 | Super fine fusiform fluorescent paramagnetic rare-earth granular material and its preparing method |
| CN102198385A (en) * | 2011-05-23 | 2011-09-28 | 同济大学 | Preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres |
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| CN102198385A (en) * | 2011-05-23 | 2011-09-28 | 同济大学 | Preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres |
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