CN1255507C - Super fine fusiform fluorescent paramagnetic rare-earth granular material and its preparing method - Google Patents
Super fine fusiform fluorescent paramagnetic rare-earth granular material and its preparing method Download PDFInfo
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- CN1255507C CN1255507C CN 200410065232 CN200410065232A CN1255507C CN 1255507 C CN1255507 C CN 1255507C CN 200410065232 CN200410065232 CN 200410065232 CN 200410065232 A CN200410065232 A CN 200410065232A CN 1255507 C CN1255507 C CN 1255507C
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Abstract
The present invention relates to a super fine fusiform fluorescent paramagnetic rare-earth granular material and a preparing method thereof. The method is a preparation method of chemical material. The material grain forms the shape of a porous or a hollow structure and has a fusiform configuration, a 100-150 nm of short diameter, and a 300 nm-500 nm of long diameter. The present invention is made of oxyfluoride or oxysulfide which comprises one or more elements in yttrium, samarium, europium and praseodymium. The preparation method comprises the following steps: generating rare earth sulfide or nanometer particles of fluoride; adding urea and adding in reaction liquid during rapid mixing; placing the reaction liquid in a high-pressure reaction vessel to carry out high-temperature high-pressure reaction; filtering, washing, drying and storing samples; obtaining the form of hydration sulfide or hydration fluoride of the super fine fusiform fluorescent paramagnetic rare-earth granular material; obtaining the mode of oxysulfide or oxyfluoride of the super fine fusiform fluorescent paramagnetic rare-earth granular material at 300 to 800 DEG C. of temperature by calcination for one to seven hours. The material has the advantage of large specific surface area, and the fluorescence and the paramagnetism of the material are not influenced.
Description
Technical field
The present invention is a kind of preparation method of chemical material, and especially a kind of paramagnetic rare-earth granular material and preparation method thereof belongs to the technical field that material is made.
Background technology
Material is one of the pillar of social development and power, and wherein the design of material is one of frontier development of materialogy.The nano material of porous material (micropore, mesoporous, macropore) and numerous kinds such as nano particle, nanotube, nano wire, nano rod, nanometer ridge, and a peacekeeping multidimensional Ordered Materials that forms by assembling is the model that material successfully designs.Generally speaking, the material with strong fluorescent signal mostly is organic fluorescent dye, and organic fluorescent dye is easily by optical quenching; Magneticsubstance mostly is inorganic metal and oxide compound thereof, and these materials do not produce fluorescence; Although the people is arranged at present at research organic polymer magneticsubstance, these organic materialss do not possess strong fluorescence radiation performance at present.The material of only forming that has superparamagnetism and fluorescence simultaneously by rare earth element.Rare earth material is newer a kind of in the material, the compound that the characteristics of out-shell electron configuration make rare earth element form presents changeable electricity, magnetics, optics and nulcear properties, these character can be widely used at catalyzer, laser, semi-conductor, phosphor material, glass polishing agent, high-efficiency ceramic, in recent years, the application of these materials in chemical detection and medical diagnosis also had increasing research.Rare earth oxide and hydrate thereof are existence forms the most stable in the rare earth compound.At present, nano particle, the nanotube of rare earth oxide are all succeeded in developing, and super fine fusiform fluorescent paramagnetic rare-earth granular material does not see that as yet report is arranged at present.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of super fine fusiform fluorescent paramagnetic rare-earth material and preparation method thereof, this material has strong fluorescent signal and superparamagnetism.
Technical scheme: super fine fusiform fluorescent paramagnetic rare-earth granular material of the present invention, structurally this material granule is the shape of porous or hollow structure, and profile is a fusiform, and minor axis is 100-150nm, and major diameter is 300nm-500nm; Material is oxyfluoride or the oxysulfide that contains one or more elements in yttrium, samarium, europium, the praseodymium.
Its preparation method is:
A, the trivalent that will contain one or more elements in yttrium, samarium, europium, the praseodymium add 5%～20% rare nitric acid and are stirred to the solution clarification, under vigorous stirring, add Sodium Fluoride or sodium sulfide solution, precipitate, generate rare-earth sulfide or fluoride nano granule;
B, in the solution of above step a, splash into sodium hydroxide solution to the pH value of solution value to 0-2, weighing is excessive, the 10-50 that participates in the total mole number of the trivalent rare earth oxide compound that reacts doubly is the mole number of required urea, the molecular weight that is multiplied by urea obtains the quality of required urea, add urea, under stirring fast, directly add in the mixed reaction solution;
C, above reaction solution is put into autoclave, l10-160 ℃ of reaction 3-12 hour down;
D, to be cooled to the room temperature after-filtration, washing, drying is preserved sample, then obtains the hydration sulfide or the hydration fluorochemical form of super fine fusiform fluorescent paramagnetic rare-earth granular material,
E, again through 300-800 ℃ down calcining then obtained the oxysulfide or the oxyfluoride form of super fine fusiform fluorescent paramagnetic rare-earth granular material in 1-7 hour.
The method for preparing the ferromagnetism nano particle of this material is:
A, the trivalent that will contain one or more elements in yttrium, samarium, europium, the praseodymium add trivalent iron salt, add 5%～20% rare nitric acid again and be stirred to the solution clarification, under vigorous stirring, add Sodium Fluoride or sodium sulfide solution, precipitate, generate rare-earth sulfide or fluoride nano granule;
B, in the solution of above step a, splash into sodium hydroxide solution to the pH value of solution value to 0-2, participating in the trivalent rare earth oxide compound of reaction and the 10---50 of ferric total mole number doubly is the mole number of required urea, the molecular weight that is multiplied by urea obtains the quality of required urea, add urea, directly add in the mixed reaction solution under stirring;
C, above reaction solution is put into autoclave, 110-160 ℃ of reaction 3-12 hour down;
D, to be cooled to the room temperature after-filtration, washing, drying is preserved sample, then obtains the hydration oxysulfide or the hydration oxyfluoride form of ferromagnetism super fine fusiform fluorescent paramagnetic rare-earth granular material;
E, again through 300-800 ℃ down calcining then obtained the oxysulfide or the oxyfluoride of ferromagnetic super fine fusiform fluorescent paramagnetic rare-earth granular material in 1-7 hour.
Described trivalent rare earth oxide compound is a yttrium oxide, erbium oxide, praseodymium sesquioxide, samarium sesquioxide, a kind of in the europiumsesquioxide.
Beneficial effect: the fusiform superfine rare-earth material that is synthesized through above-mentioned route has good superparamagnetism (seeing accompanying drawing 5) and fluorescence property (seeing accompanying drawing 6), because its porous surface (is seen accompanying drawing 2,3,4) more favourable for coupled other reagent of catalyzed reaction and surface, therefore can be used for biomarker and chemical catalysis.From photo, except macropore, the surface of material also has the aperture about the about nanometer of many diameters.Specific surface area is bigger, the fluorescence spectrum figure of the compound fusiform material that generates by erbium and europium from Fig. 6 as can be seen, the maximum excitation light of this material and radiative wavelength are respectively about 400 nanometers and 560 nanometers, but also excite and emitting fluorescence to still existing 520 nanometers in 420 nanometers as can be seen from excitation spectrum and emission spectrum.Therefore under fluorescent microscope, all rare earth fusiform materials all demonstrate fluorescence under UV-light, ruddiness and blue light.
Description of drawings
Fig. 1 generates the transmission electron microscope photo of the fusiform rare earth material of (still without the muffle furnace calcining) after through high-temperature water thermal treatment, and scale shown in the figure is 0.5 micron.
Fig. 2 is the transmission electron microscope photo through the fusiform rare earth material of retort furnace calcining after 3-5 hour.Scale is 0.5 micron shown in the wherein left figure.
Fig. 3 is the amplification to Fig. 2 sample, and scale shown in the figure is 200 nanometers.
Fig. 4 is the high-resolution electron microscope photo without retort furnace incinerating fusiform material.Scale shown in the figure is 200 nanometers.
Fig. 5 is that scale length wherein is 20 nanometers through the high resolution electron microscope (HREM) photo of the fusiform material end after the retort furnace calcining,
Fig. 6 is that this material presents superparamagnetism as seen from the figure by the magnetic hysteresis loop figure of the compound fusiform material of erbium and europium generation.
Fig. 7 is the fluorescence spectrum figure of the compound fusiform material that generated by erbium and europium, and this collection of illustrative plates is surveyed by the LS-55 fluorescence spectrophotometer, and wherein the spectral line on the left side is an excitation spectrum, the right be emmission spectrum.
Embodiment
Embodiment 1:
Nitric acid 30-60 milliliter with yttrium oxide 0.5 gram adding 10%, on electric furnace, be heated to the solution clarification, under stirring fast, add sodium sulphite 1.3 grams (carrying out in the stink cupboard), sodium hydroxide with 15% with moderate speed's titration to pH be 1 o'clock, add urea 3-8 gram,, filter 125 ℃ of following high pressure hydro-thermals 5 hours, wash, can obtain the hydration sulphur compound of super fine fusiform yttrium.Calcined 3 hours down at 300-800 ℃, then obtain the porous material shown in Fig. 2 and 4.
Embodiment 2:
Nitric acid 30-60 milliliter with erbium oxide 0.8 gram adding 10%, on electric furnace, be heated to the solution clarification, under stirring fast, add Sodium Fluoride 0.465 gram, sodium hydroxide with 10% with moderate speed's titration to pH be 1 o'clock, add urea 3-8 gram,, filter 125 ℃ of following high pressure hydro-thermals 5 hours, washing can obtain the hydration fluorochemical as Fig. 3 super fine fusiform erbium.
Embodiment 3:
Nitric acid 30-60 milliliter with samarium sesquioxide 0.9 gram adding 10%, on electric furnace, be heated to the solution clarification, under stirring fast, add Sodium Fluoride 0.465 gram, sodium hydroxide with 10% with the moderate speed relegate a high offi fixed to pH be 1 o'clock, add urea 3-8 gram,, filter 125 ℃ of following high pressure hydro-thermals 5 hours, wash, can obtain the hydration fluorine cpd of super fine fusiform samarium.
Embodiment 4:
With yttrium oxide 0.5 gram, europiumsesquioxide 0.05 gram, the nitric acid 30-60 milliliter of adding 20% is heated to the solution clarification on electric furnace, add Sodium Fluoride 0.465 and restrain under stirring fast, sodium hydroxide with 10% with moderate speed's titration to pH be 1 o'clock, add urea 3--8 gram,, filter 120--140 ℃ of following high pressure hydro-thermal 3-5 hour, washing can obtain the yttrium hydration fluorochemical that super fine fusiform is mixed europium.
Embodiment 5:
With erbium oxide 0.86 gram, europiumsesquioxide 0.03 gram, the nitric acid 30-60 milliliter of adding 15% is heated to the solution clarification on electric furnace, add Sodium Fluoride 0.465 and restrain under stirring fast, sodium hydroxide with 10% with moderate speed's titration to pH be 1 o'clock, add urea 3-8 gram,, filter 125 ℃ of following high pressure hydro-thermals 5 hours, washing can obtain the yttrium hydration fluorochemical that super fine fusiform is mixed europium.
Embodiment 6:
With yttrium oxide 0.5 gram, erbium oxide 0.02 gram, europiumsesquioxide 0.02 gram, 50 milliliters in the nitric acid of adding 15%, on electric furnace, be heated to the solution clarification, add Sodium Fluoride 0.48 gram under stirring fast, the sodium hydroxide with 10% is 1.5 o'clock with moderate speed's titration to pH, adding urea 3-8 gram, 125 ℃ of following high pressure hydro-thermals 5 hours, filter, washing can obtain the yttrium hydration fluorochemical that super fine fusiform is mixed europium and erbium.
Embodiment 7:(ferromagnetism particle)
With yttrium oxide 0.5 gram, europiumsesquioxide 0.025 gram, ferric sulfate 0.6 gram, the nitric acid 50-80 milliliter of adding 10%, on electric furnace, be heated to the solution clarification, add Sodium Fluoride 0.47 gram under stirring fast, the sodium hydroxide with 10% is 1.5 o'clock with moderate speed's titration to pH, adding urea 3-8 gram, 120-140 ℃ of following high pressure hydro-thermal 3-9 hour, filter, washing can obtain the yttrium hydration fluorochemical that super fine fusiform is mixed europium and iron.Obtain the fusiform material after the calcining, just more refinement and point of the two ends of its spindle.The magnetic that added the spindle material that ferric ion obtains after testing is more much better than than what do not add.
This material granule is the shape of porous or hollow structure, and profile is a fusiform, and minor axis is 100-150nm, and major diameter is 300nm-500nm; Material is oxyfluoride or the oxysulfide that contains one or more elements in yttrium, samarium, europium, the praseodymium.
Claims (3)
1, a kind of super fine fusiform fluorescent paramagnetic rare-earth granular material is characterized in that this material granule is the shape of porous or hollow structure, and profile is a fusiform, and minor axis is 100-150nm, and major diameter is 300nm-500nm; Material is oxyfluoride or the oxysulfide that contains one or more elements in yttrium, samarium, europium, the praseodymium.
2, a kind of preparation method of super fine fusiform fluorescent paramagnetic rare-earth granular material as claimed in claim 1 is characterized by:
A, the trivalent that will contain one or more elements in yttrium, samarium, europium, the praseodymium add 5%～20% rare nitric acid and are stirred to the solution clarification, under vigorous stirring, add Sodium Fluoride or sodium sulfide solution, precipitate, generate rare-earth sulfide or fluoride nano granule;
B, in the solution of above step a, splash into sodium hydroxide solution to the pH value of solution value to 0-2, the excessive urea of weighing, the 10---50 that promptly participates in the total mole number of the trivalent rare earth oxide compound that reacts is the mole number of required urea doubly, and the molecular weight that is multiplied by urea obtains the quality of required urea; Add urea, under stirring fast, directly add in the mixed reaction solution;
C, above reaction solution is put into autoclave, 110-160 ℃ of reaction 3-12 hour down;
D, to be cooled to the room temperature after-filtration, washing, drying is preserved sample, then obtains the hydration sulfide or the hydration fluorochemical form of super fine fusiform fluorescent paramagnetic rare-earth granular material,
E, again through 300--800 ℃ down calcining then obtained the oxysulfide or the oxyfluoride form of super fine fusiform fluorescent paramagnetic rare-earth granular material in 1-7 hour.
3, the preparation method of super fine fusiform fluorescent paramagnetic rare-earth granular material according to claim 2 is characterized by: described trivalent rare earth oxide compound is a yttrium oxide, praseodymium sesquioxide, samarium sesquioxide, a kind of in the europiumsesquioxide.
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| CN103923656B (en) * | 2013-01-14 | 2015-08-26 | 宁波大学 | A kind of preparation method of gadolinium oxide coated ferroferric oxide magnetic fluorescence nano hollow ball |
| CN106905968B (en) * | 2017-02-24 | 2019-05-24 | 温州医科大学 | The preparation method of magnetic fluorescence material |
| CN109574063B (en) * | 2019-01-14 | 2021-03-16 | 东北大学 | Preparation method of low-wavelength low-transmittance rare earth sulfur oxide composite compound |
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