CN102849699A - Preparation method of europium phosphate nano-wires - Google Patents
Preparation method of europium phosphate nano-wires Download PDFInfo
- Publication number
- CN102849699A CN102849699A CN2012103127452A CN201210312745A CN102849699A CN 102849699 A CN102849699 A CN 102849699A CN 2012103127452 A CN2012103127452 A CN 2012103127452A CN 201210312745 A CN201210312745 A CN 201210312745A CN 102849699 A CN102849699 A CN 102849699A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- nano wire
- mixed liquor
- europium
- acid europium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Luminescent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a preparation method of europium phosphate nano-wires. The preparation method comprises the following steps: respectively preparing an Eu<3+> salt solution and a PO4<3-> salt solution; adding the PO4<3-> salt solution to the Eu<3+> salt solution under continuous stirring to obtain a mixed solution I; stirring the mixed solution I, and adjusting the pH value of the mixed solution I to 0.5-9.0 to obtain a mixed solution II; and ageing the mixed solution II at 4-95DEG C under an environmental pressure for above 1h to obtain the europium phosphate nano-wires. The preparation method can be implemented through adopting simple and cheap equipment under the environmental pressure, so it is convenient for realizing the industrialized production; and there is no need to add a template in the preparation process, so the environmental influence possibly brought by a waste liquid is avoided.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of phosphoric acid europium nano wire.
Background technology
Rare earth element comprises the lanthanon of ordination number 57 to 71 and scandium and yttrium of the same clan.These elements not only have similar physicochemical property, and because its outer electronic structure (4f
0-145d
0-16S
2) characteristics, determined that they have higher chemical reactivity.Europium is No. 63 element in the periodic table of elements, belongs to light rare earths.Europium be in the light rare earths in the earth's crust the minimum element of content, and europium plays an important role in modern industry.It is mainly used is as luminescent material, from trichromoscope to the PDP plasma panel, from graphoscope to the rare-earth trichromatic energy saving lamp, as one of component of redness or blue emitting material, europium provides high brightness, high-contrast and high definition for the world.At medical science, biochemical field, the intensity of the fluorescence that europium has and life length are applied to utilizing the immunoassay of antigen antibody reaction.Because can carry out high-precision mensuration, need as an alternative special facility radioactive substance method and get most of the attention.
Research and development along with nano material it is found that, compare with body phase material, and nano particle, especially low-dimensional nano structure material have numerous specific performances aspect chemistry and the physics.For example, one-dimensional nano structure material is limited system on two dimensions, shows the characteristic that is different from three-dimensional limited system nano particle, such as characteristics such as switching effect, wire grid polarization effect, field emission effect, piezoelectric effects.Utilize these new functional performances, can design nano structure device of new generation or nano-functional material.
RE phosphate is a series of materials with excellent properties, is widely used in the aspects such as laser apparatus, pottery, sensor, fluorescent material, hot resistance material.And one dimension rare earth phosphate nano material demonstrates application potential in increasing field.For example, the aspects such as photoelectron nano-device, biological fluorescent labelling, special conductor material, ion-exchange and catalytic material.At present, and applied research synthetic for the control of one dimension rare earth phosphate nano material structure, pattern and size has been reported.Its preparation method mainly adopts direct precipitation method, microemulsion method and hydrothermal synthesis method.Wherein, hydrothermal synthesis method is generally adopted.This method is included in the stainless steel closed reactor that is lined with tetrafluoroethylene, add rare earths salt, ortho-phosphoric acid root salts solution or phosphoric acid and template and water etc., form mixed solution system, heat this mixed solution system by comparatively high temps, it is approached or reach supercritical state, after certain reaction times, obtain the rare earth phosphate nano line that degree of crystallinity is higher, be evenly distributed.Yet the drawback that this hydrothermal synthesis method exists is: to conversion unit have relatively high expectations, cost is higher, output is few, is difficult to realize suitability for industrialized production; Template is generally the organic macromolecule compound, and such as phosphorous-containing surfactants, some can cause water pollution, and some evaporates in the air easily, destroys ecotope.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective on the prior art, a kind of with low cost, environmental protection is provided and is convenient to the preparation method of the phosphoric acid europium nano wire of suitability for industrialized production.
The present invention is achieved in that a kind of preparation method of phosphoric acid europium nano wire, and it comprises the steps:
Prepare respectively Eu
3+Salts solution and PO
4 3-Salts solution;
Under constantly stirring to described Eu
3+Add described PO in the salts solution
4 3-Salts solution gets mixed liquor I;
Stir described mixed liquor I, regulate the pH value to 0.5 of described mixed liquor I～9.0, get mixed liquor I I;
Under environmental stress, described mixed liquor I I more than 1 hour, is obtained described phosphoric acid europium nano wire 4 ℃～95 ℃ ageings.
The preparation method of phosphoric acid europium nano wire provided by the invention, preparation condition is gentle, in (4 ℃～95 ℃) and the wider pH value scope (pH0.5～9.0), can obtain phosphoric acid europium nano wire in lower temperature range.This preparation method adopts simple, cheap equipment to implement under environmental stress, need not to add template, has environment friendly, can greatly reduce production costs, and is convenient to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 1;
Fig. 2 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 1;
Fig. 3 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 2;
Fig. 4 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 2;
Fig. 5 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 3;
Fig. 6 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 3;
Fig. 7 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 4;
Fig. 8 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 4;
Fig. 9 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 5;
Figure 10 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 5;
Figure 11 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 6;
Figure 12 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 6;
Figure 13 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 7;
Figure 14 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 7;
Figure 15 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 8;
Figure 16 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 8;
Figure 17 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 9;
Figure 18 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 9;
Figure 19 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 10;
Figure 20 is the XRD figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 10;
Figure 21 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 11;
Figure 22 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 12;
Figure 23 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 13;
Figure 24 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 14;
Figure 25 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 15.
Figure 26 is the SEM figure of the phosphoric acid europium nano wire that makes of the embodiment of the invention 16.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The preparation method of a kind of phosphoric acid europium nano wire of the embodiment of the invention comprises the steps:
S01: prepare respectively Eu
3+Salts solution and PO
4 3-Salts solution;
S02: under constantly stirring to described Eu
3+Add described PO in the salts solution
4 3-Salts solution gets mixed liquor I;
S03: stir described mixed liquor I, regulate the pH value to 0.5 of described mixed liquor I～9.0, get mixed liquor I I;
S04: under environmental stress, described mixed liquor I I more than 1 hour, is obtained described phosphoric acid europium nano wire 4 ℃～95 ℃ ageings.
Among the step S01, this Eu
3+Salts solution and PO
4 3-Salts solution is respectively with this area soluble E u commonly used
3+Salt and solubility ortho-phosphoric acid PO
4 3-Salt is solute, take water as solvent.For example, this soluble E u
3+Salt can be europium nitrate, Europium trichloride etc., also comprises by Eu
2O
3The soluble E u that generates with acid-respons (such as nitric acid etc.)
3+Salt.This solubility ortho-phosphoric acid PO
4 3-Salt can be sodium phosphate class, ammonium phosphate type or potassiumphosphate class etc., such as diammonium phosphate, Sodium phosphate dibasic, primary ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, dipotassium hydrogen phosphate or potassium primary phosphate.Especially, also can directly select ortho-phosphoric acid.For improving product precision, preferred commercially available analytical pure level soluble E u
3+Salt and solubility PO
4 3-Salt, preferred solvent are deionized water.The configuration of this salts solution can be carried out in any open container such as beaker or Erlenmeyer flask.For making subsequent reactions carry out fully this Eu
3+Salts solution and this PO
4 3-The concentration of salts solution should equate, or this PO
4 3-The concentration of salts solution is higher than the former.
Among the step S02, described Eu
3+Salts solution in case with described PO
4 3-Salt solution mix (preparation mixed liquor I) namely generates white precipitate, and this is phosphoric acid europium precipitation.Its reaction formula is:
Eu
3++PO
4 3-→EuPO
4↓
For making phosphoric acid europium crystal grain be monodisperse status, and particle diameter is even, needs the limit at the uniform velocity stir this Eu
3+The salts solution limit adds this PO in it
4 3-Salts solution.Preferably, adopt dropping funnel PO
4 3-The salts solution average rate splashes into Eu
3+In the salts solution.This stirring can be adopted magnetic stirring apparatus or DC electrodeless speed governing agitator, and the control rotating speed is at 200～460 rev/mins.For obtaining the high phosphoric acid europium nano wire of crystalline form integrity degree, Eu in the mixed liquor I
3+Salts solution and PO
4 3-The concentration of salts solution all should be between 0.005～0.1 mol/L, preferably, and Eu in the mixed liquor I
3+Salts solution and PO
4 3-The concentration of salts solution is between 0.02～0.07 mol/L.
Step S03 is specially, and the pH value to 0.5 of the described mixed liquor I of adjusting～9.0 get mixed liquor I I under constantly stirring.Regulate the pH value, can select to adopt ortho-phosphoric acid, sodium hydroxide, aqueous hydrochloric acid or the ammoniacal liquor of different concns to regulate.When the ortho-phosphoric acid of selecting different concns is regulated the pH value of described mixed liquor I, the pH value of mixed liquor I is reduced when (acidity enhancing), also increased PO in the mixed liquor I
4 3-Concentration, cause Eu in the mixed liquor I
3+And PO
4 3-Molar concentration rate change.Comparative study shows, in the scope that described pH value is regulated, and Eu
3+And PO
4 3-The change of molar concentration rate, the pattern of phosphoric acid europium nano wire produced substantial effect.Eu in described mixed liquor I
3+And PO
4 3-Molar concentration rate be preferably 1～0.2.
Be the pattern of the phosphoric acid europium nano wire that makes in 0.5～9.0 scope from the pH value of mixed liquor I, when the pH value in stronger acid range, the length-to-diameter ratio of made phosphoric acid europium nano wire is larger, and degree of crystallinity is better.Along with the pH value increases, the acidity of mixed liquor I weakens, and alkalescence strengthens, and the length-to-diameter ratio of made phosphoric acid europium nano wire diminishes, and degree of crystallinity relatively relatively poor (especially working as the pH value in alkaline range).Preferably, the pH value is adjusted to 0.5～3.0 in the mixed liquor I.
After regulating pH, can continue to stir, and add a certain amount of deionized water, to control the concentration of described mixed liquor I I.Prepare mixed liquor I from step S02 and begin to stir, continue later on to stir to forming described mixed liquor I I or forming described mixed liquor I I, total churning time is all could in 0.3～2 hour.
Step S04 is specially, and will the container of this mixed liquor I I be housed in placing 4 ℃～95 ℃ ageings of room temperature more than 1 hour under the environmental stress.Preferably, select water bath with thermostatic control control temperature.This water-bath is the water-bath that generally adopt this area.In addition, ageing process is the nano wire crystallization of phosphoric acid europium and process of growth, for guaranteeing the growth of phosphoric acid europium nano wire crystal evenly, this mixed liquor I I can not be stirred, in the water-bath fluctuating temperature preferably be controlled at ± 1.5 ℃ in, for preventing that dirt such as dust from falling into mixed liquor I I, can select preservative film or other lids to cover vessel port.The visual water-bath Aging Temperature of digestion time and to the quality requirements of product and determine that Aging Temperature all can make phosphoric acid europium nano wire 4 ℃～95 ℃ of room temperatures.During Aging Temperature very low (being lower than 60 ℃), the proper extension digestion time can obtain the larger phosphoric acid europium nano wire of length-to-diameter ratio; When Aging Temperature is higher (60 ℃～95 ℃), then through relatively short period of time ageing, can obtain the larger phosphoric acid europium nano wire of length-to-diameter ratio.Preferably, Aging Temperature is 60 ℃～95 ℃.When Aging Temperature more than or equal to 4 ℃ during less than 60 ℃, can be when abovementioned steps S02 prepares mixed liquor I heated and stirred, be about to described Eu
3+The salts solution thermostatically heating is to the temperature that is higher than follow-up ageing and be lower than or equal 70 ℃, splashes into this PO in it while stirring
4 3-Salts solution, and pH value and the concentration of accent mixed liquor I continue thermostatically heating after stirring for some time, and the mixed liquor I I that makes is positioned over lower temperature (such as room temperature) lower ageing for some time.Can obtain at low temperatures so preferably phosphoric acid europium nano wire of crystallization.If Aging Temperature higher (60 ℃～95 ℃) then after the ageing, takes out mixed solution and need be positioned over naturally cooling under the envrionment temperature.Preferably, with this mixed solution in water-bath with the water-bath naturally cooling, like this, can make mixed solution slowly and evenly cooling, obtain the better and higher phosphoric acid europium nano wire of degree of crystallinity of growth.Behind this mixed solution naturally cooling, will precipitate from waste liquid centrifugation and out use respectively deionized water and absolute ethanol washing 2 times, in natural drying at room temperature or 70 ℃ of oven dry, described oven dry can be selected a conventional oven or vacuum-drying.
The preparation method of phosphoric acid europium nano wire provided by the invention adopts simple, cheap equipment, be open container, agitator, common water-bath, under environmental stress, can implement, very easy, need not needs to carry out in special stainless steel cauldron such as prior art, and preparation condition is gentle, in very low temperature (4 ℃～95 ℃), wider pH value scope (pH0.5～9.0) and wider concentration range (0.005 ~ 0.1 mol/L), can implement.Particularly as long as suitable thermostatically heating stirs in the process of preparation mixed liquor I and mixed liquor I I, then at a lower temperature ageing (under room temperature), and control digestion time namely can obtain preferably phosphoric acid europium nano wire of crystallization.This preparation method not only is convenient to suitability for industrialized production but also greatly reduce production cost.In addition, adopt method provided by the invention to prepare phosphoric acid europium nano wire and need not to add template, thereby avoided the waste liquor contamination environment, be beneficial to environment protection.
Below by concrete preparation method's embodiment the preparation method of above-mentioned phosphoric acid europium nano wire is described.
Embodiment 1:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 380 rev/mins rotating speed, while stirring described disodium phosphate soln is splashed in the described europium nitrate solution.Continue to stir 1 hour, during to adopt dilution be that 20% positive acid solution is regulated the pH value to 1.57 of this mixed solution, and add a certain amount of deionized water, the cumulative volume that makes mixed solution is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixed solution is housed is positioned in 90 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask and is positioned over naturally cooling under the envrionment temperature after 12 hours under environmental stress, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Fig. 1, Fig. 2).
Embodiment 2:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 380 rev/mins rotating speed, while stirring described disodium phosphate soln is splashed in the described europium nitrate solution.Continue to stir 1 hour.Adopting during this time dilution is that 20% positive acid solution is regulated the pH value to 1.57 of this mixed solution, and adds a certain amount of deionized water, and the cumulative volume that makes mixed solution is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixed solution is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask and is positioned over naturally cooling under the envrionment temperature after 12 hours under environmental stress, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Fig. 3, Fig. 4).
Embodiment 3:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 460 rev/mins rotating speed, while stirring described disodium phosphate soln is splashed in the described europium nitrate solution.Continue to stir 1 hour.Adopting during this time dilution is that 25% positive acid solution is regulated this pH of mixed value to 1.0, and adds a certain amount of deionized water, and the cumulative volume that makes mixed solution is 80 milliliters.After stopping to stir, Erlenmeyer flask that this mixed solution is housed with bottleneck on the preservative film cover, is positioned under the room temperature condition (23.3 ℃ of medial temperatures, the temperature difference ± 3.3 ℃), ageing is after 4 days under environmental stress, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Fig. 5, Fig. 6).
Embodiment 4:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 300 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during to adopt dilution be that 20% positive acid solution is regulated the pH value to 1.60 of this mixing solutions, and add a certain amount of deionized water, the cumulative volume that makes mixing solutions is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is sealed bottleneck with preservative film, be positioned over set temperature and be in 4 ℃ the refrigerator, ageing is after 12 hours under environmental stress, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Fig. 7, Fig. 8).
Embodiment 5:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, put into electric heater, 65 ℃ of thermostatically heating, and the employing magnetic stirring apparatus splashes into described disodium phosphate soln in the described europium nitrate solution while stirring with 400 rev/mins rotating speed stirring.Stirred 90 minutes 65 ℃ of lower lasting thermostatically heating, during be the pH value of 20% positive acid solution accent mixed solution with dilution, and add a certain amount of deionized water, the pH value that makes mixed solution is 1.6, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixed solution is housed is placed 60 ℃ of (temperature difference ± 1 ℃) waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 2 hours under environmental stress, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Fig. 9, Figure 10).
Embodiment 6:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [(Na
2HPO
412H
2O], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 400 rev/mins rotating speed, while stirring described disodium phosphate soln is splashed in the described europium nitrate solution.At room temperature continue to stir 90 minutes, during be the pH value of 20% positive acid solution accent mixed solution with dilution, and add a certain amount of deionized water, the pH value that makes mixed solution is 1.6, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixed solution is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 2 hours under environmental stress, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Figure 11, Figure 12).
Embodiment 7:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 400 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during be the pH value of 25% positive acid solution accent mixed solution with dilution, and add a certain amount of deionized water, the pH value that makes mixed solution is 0.5, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixed solution is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 12 hours under environmental stress, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Figure 13, Figure 14).
Embodiment 8:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 400 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during be the pH value of 25% ammonia soln accent mixed solution with dilution, and add a certain amount of deionized water, the pH value that makes mixed solution is 3.0, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixed solution is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 12 hours under environmental stress, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Figure 15, Figure 16).
Embodiment 9:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 400 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during be the pH value of 25% ammonia soln accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 6.0, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 12 hours under environmental stress, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Figure 17, Figure 18).
Embodiment 10:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 400 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during with the pH value of the ammonia soln accent mixing solutions of 4 mol/L, and add a certain amount of deionized water, the pH value that makes mixing solutions is 9.0, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 12 hours under environmental stress, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made phosphoric acid europium nano wire is hexagonal crystal phase (Figure 19, Figure 20).
Embodiment 11:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [(Na
2HPO
412H
2O], be mixed with the europium nitrate aqueous solution and the Sodium phosphate dibasic aqueous solution that concentration is 0.1 mol/L with deionized water respectively.Get 4 milliliters of the described europium nitrate aqueous solution and be diluted to 25 milliliters with deionized water, place Erlenmeyer flask, the employing magnetic stirring apparatus stirs with 200 rev/mins rotating speed, and the Sodium phosphate dibasic aqueous solution with 4 milliliters of described 0.1 mol/L splashes in the described europium nitrate solution while stirring.Continue to stir 1 hour, during be the pH value of 25% positive acid solution accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 1.0, cumulative volume is 80 milliliters of (Eu in the described mixing solutions
3+And PO
4 3-Concentration be 0.005 mol/L).After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 12 hours under environmental stress, was positioned over naturally cooling under the envrionment temperature, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire (Figure 21).
Embodiment 12:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with the europium nitrate aqueous solution and the diammonium phosphate aqueous solution that concentration is 0.2 mol/L with deionized water respectively.Get 28 milliliters of the described europium nitrate aqueous solution, place Erlenmeyer flask, the employing magnetic stirring apparatus stirs with 450 rev/mins rotating speed, while stirring 28 milliliters of described diammonium phosphate aqueous solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during be the pH value of 25% positive acid solution accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 1.0, cumulative volume is 80 milliliters of (Eu in the described mixing solutions
3+And PO
4 3-Concentration be 0.07 mol/L).After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 12 hours under environmental stress, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire (Figure 22).
Embodiment 13:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with the europium nitrate aqueous solution and the diammonium phosphate aqueous solution that concentration is 0.3 mol/L with deionized water respectively.Get 26.7 milliliters of the described europium nitrate aqueous solution, place Erlenmeyer flask, the employing magnetic stirring apparatus stirs with 450 rev/mins rotating speed, while stirring 26.7 milliliters of described diammonium phosphate aqueous solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during be the pH value of 20% positive acid solution accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 1.6, cumulative volume is 80 milliliters of (Eu in the described mixing solutions
3+And PO
4 3-Concentration be 0.1 mol/L).After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 80 ℃ of waters bath with thermostatic control, ageing was taken out Erlenmeyer flask after 24 hours under environmental stress, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire (Figure 23)
Embodiment 14:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 380 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during be the pH value of 20% positive acid solution accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 1.55, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was turned off power supply after 48 hours under environmental stress, took out Erlenmeyer flask, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire (Figure 24).
Embodiment 15:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 380 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during be the pH value of 20% positive acid solution accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 1.55, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 60 ℃ of waters bath with thermostatic control, ageing was turned off power supply after 24 hours under environmental stress, took out Erlenmeyer flask, the room temperature cooling, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire (Figure 25).
Embodiment 16:
Take by weighing the europium nitrate [Eu (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the europium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described europium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 300 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described europium nitrate solution.Continue to stir 1 hour, during be the pH value of 20% positive acid solution accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 1.6, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 95 ℃ the water bath with thermostatic control, ageing after 1.5 hours under environmental stress, powered-down, room temperature is cooled to 45 ℃, takes out Erlenmeyer flask, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The phosphoric acid europium product that as seen the SEM phenogram makes is nano wire (Figure 26).
Phosphoric acid europium product pattern and structural characterization
See also Fig. 1～Fig. 8, the embodiment of the invention 1～4, respectively (Fig. 7, Fig. 8) ageing 12 hours under 90 ℃ of bath temperatures (Fig. 1, Fig. 2) and 60 ℃ of bath temperatures (Fig. 3, Fig. 4) ageing 12 hours, at room temperature (23.3 ℃ of medial temperatures) (Fig. 5, Fig. 6) ageing 4 days and 4 ℃ of described mixing solutions, made phosphoric acid europium product.The SEM phenogram illustrates, and made phosphoric acid europium product pattern is nano wire under 4 ℃～90 ℃ Aging Temperatures, and along with Aging Temperature raises, the length-to-diameter ratio of made phosphoric acid europium nano wire (ratio of length and diameter) increases gradually; The XRD phenogram shows, the diffraction peak of the phosphoric acid europium product that under described Aging Temperature condition, makes all with hexagonal crystal phase phosphoric acid europium characteristic diffraction peak (JCPDS 20-1044) position consistency.Particularly, be the characteristic diffraction peak that 14.678 °, 20.352 °, 25.802 °, 29.776 °, 31.959 °, 38.438 °, 42.611 °, 47.807,49.468 ° diffraction peak corresponds respectively to hexagonal crystal phase phosphoric acid europium (100), (101), (110), (200), (102), (112), (003), (301), (212) crystal face at 2 θ.As seen, the embodiment of the invention 1～4 made phosphoric acid europium product is hexagonal crystal phase (JCPDS 20-1044), and degree of crystallinity strengthens gradually along with Aging Temperature raises.Please consult simultaneously Figure 26, the embodiment of the invention 16 is 1.5 hours made phosphoric acid europium nano wires of 95 ℃ of bath temperature ageings.As seen, under 4 ℃～95 ℃ temperature condition, take water as reaction medium, according to said method, through after a while ageing, all can make phosphoric acid europium nano wire.
See also Fig. 9～Figure 12, the embodiment of the invention 5 and 6, that described mixing solutions pH value is at 1.6 o'clock, continuous heating stirred 90 minutes under 65 ℃ of constant temperatures respectively, then, ageing 2 hours (Fig. 9, Figure 10) and at room temperature continue to stir 90 minutes under 60 ℃ of bath temperatures, then, 2 hours (Figure 11, Figure 12) made phosphoric acid europium products of ageing under 60 ℃ of bath temperatures.SEM phenogram (Fig. 9, Figure 11) as seen, continuous heating stirs 90 minutes synthetic phosphoric acid europium nano wires under 65 ℃ of constant temperatures, its length-to-diameter ratio is greater than and continues under the room temperature condition to stir the length-to-diameter ratio of synthetic phosphoric acid europium nano wire 90 minutes.XRD phenogram (Figure 10, Figure 12) as seen, the degree of crystallinity that 65 ℃ of thermostatically heating stir synthetic phosphoric acid europium nano wire is better than the degree of crystallinity that stirs synthetic phosphoric acid europium nano wire under the room temperature; Both crystalline phases are hexagonal system (JCPDS 20-1044).
See also Figure 13～Figure 20, the embodiment of the invention 7～10 is ageings 12 hours under 60 ℃ of bath temperatures, and the pH value of mixing solutions is respectively under pH0.5, pH3.0, pH6.0, the pH9.0 condition, the phosphoric acid europium product that makes.SEM phenogram (Figure 13, Figure 15, Figure 17, Figure 19) illustrates, and in pH0.5～9.0 scopes, made phosphoric acid europium product is nano wire; XRD phenogram (Figure 14, Figure 16, Figure 18, Figure 20) shows that made phosphoric acid europium product is hexagonal crystal phase (JCPDS 20-1044).
Please consult simultaneously Fig. 1～Fig. 4 in addition, the embodiment of the invention 1～2 is that mixing solutions pH value is 1.57, descends ageing 12 hours, the phosphoric acid europium nano wire that makes at 90 ℃ of bath temperatures (Fig. 1) and 60 ℃ of bath temperatures (Fig. 3) respectively; Please consult simultaneously Fig. 5～Fig. 6 in addition, the embodiment of the invention 3 is that the pH of mixed value is 1.0 o'clock, at ambient temperature 4 days made phosphoric acid europium nano wires of (23.3 ℃ of medial temperatures) ageing; Please consult simultaneously Fig. 7～Fig. 8 in addition, the embodiment of the invention 4 is that the pH of mixed value is 1.6 o'clock, at 12 hours made phosphoric acid europium nano wires of 4 ℃ of lower ageings.As seen, be under 0.5～9.0 condition in the pH of mixed value, all can make phosphoric acid europium nano wire.And in the pH of mixed value was the acid range of 0.5～the last 3.0, it was larger to make length-to-diameter ratio, and degree of crystallinity is phosphoric acid europium nano wire preferably.
See also Figure 21～Figure 23, the embodiment of the invention 11～13 is respectively Eu in the described mixed solution
3 +And PO
4 3+Concentration is respectively under 0.005～0.1 mol/L condition, the phosphoric acid europium product that makes.SEM phenogram (Figure 21～23) as seen, (0.005～0.1 mol/L) made phosphoric acid europium product is nano wire in this concentration range.Please consult simultaneously Fig. 9～Figure 12 in addition, the embodiment of the invention 5～6 is Eu in the made mixed solution
3+And PO
4 3+Concentration is 0.03 mol/L, the phosphoric acid europium nano wire that makes.As seen, mixed liquid concentration made phosphoric acid europium product under 0.005～0.1 mol/L condition is phosphoric acid europium nano wire in the preparation process.
See also Figure 24～Figure 25, the embodiment of the invention 14～15 is that the pH of mixed value is at 1.55 o'clock under 60 ℃ of bath temperatures, and digestion time is respectively 48 hours (Figure 24) and 24 hours (Figure 25); Made phosphoric acid europium nano wire.SEM phenogram (Figure 24～25) as seen, under 60 ℃ of identical bath temperatures when not bery high (be Aging Temperature), the proper extension digestion time is conducive to make the larger phosphoric acid europium nano wire of length-to-diameter ratio.
See also Figure 26, the embodiment of the invention 16 is 95 ℃ of bath temperature ageings 1.5 hours, and the pH of mixed value is 1.6 o'clock, the phosphoric acid europium nano wire that makes.Please consult simultaneously Fig. 7 in addition, the embodiment of the invention 4 is 4 ℃ of lower ageings 12 hours, and the pH of mixed value is 1.6 o'clock, the phosphoric acid europium nano wire that makes.SEM phenogram (Fig. 7, Figure 26) as seen, phosphoric acid europium nanowire-junction crystals growth is slow at a lower temperature, 4 ℃ of lower ageings 12 hours, made phosphoric acid europium nano wire is extremely short, and is the reunion shape; And very fast at the lower phosphoric acid europium nanowire-junction crystals growth of comparatively high temps (95 ℃), ageing can obtain the larger phosphoric acid europium nano wire of length-to-diameter ratio in 1.5 hours.So the length of digestion time should be looked bath temperature and the quality requirements of product is determined, prepares at a lower temperature phosphoric acid europium nano wire, needs relatively long digestion time, and under comparatively high temps, then can select the digestion time of relatively lacking.
The above only is embodiments of the invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a phosphoric acid europium nano wire is characterized in that, comprises the steps:
Prepare respectively Eu
3+Salts solution and PO
4 3-Salts solution;
Under constantly stirring to described Eu
3+Add described PO in the salts solution
4 3-Salts solution gets mixed liquor I;
Stir described mixed liquor I, regulate the pH value to 0.5 of described mixed liquor I～9.0, get mixed liquor I I;
Under environmental stress, described mixed liquor I I more than 1 hour, is obtained described phosphoric acid europium nano wire 4 ℃～95 ℃ ageings.
2. the preparation method of phosphoric acid europium nano wire as claimed in claim 1 is characterized in that, Eu in the described mixed liquor I
3+Concentration be 0.005～0.1 mol/L, PO
4 3-Concentration be 0.005～0.1 mol/L.
3. the preparation method of phosphoric acid europium nano wire as claimed in claim 2 is characterized in that, Eu in the described mixed liquor I
3+And PO
4 3-Concentration be 0.02～0.07 mol/L.
4. the preparation method of phosphoric acid europium nano wire as claimed in claim 1 is characterized in that, Eu in the described mixed liquor I
3+With PO
4 3-Molar concentration rate be 1～0.2.
5. the preparation method of phosphoric acid europium nano wire as claimed in claim 1 is characterized in that, described under constantly stirring to described Eu
3+Add described PO in the salts solution
4 3-The speed of the stirring of salts solution is 200～460 rev/mins.
6. the preparation method of phosphoric acid europium nano wire as claimed in claim 1 is characterized in that, under constantly stirring to described Eu
3+Add described PO in the salts solution
4 3-Salts solution gets mixed liquor I, continues to stir described mixed liquor I, and regulates the pH value of described mixed liquor I, continues later on to stir to forming mixed liquor I I or forming mixed liquor I I, and total churning time is 0.3～2 hour.
7. the preparation method of phosphoric acid europium nano wire as claimed in claim 1 is characterized in that, when Aging Temperature more than or equal to 4 ℃ during less than 60 ℃, described under constantly stirring to described Eu
3+Add described PO in the salts solution
4 3-Salts solution is: under constantly stirring with described Eu
3+Salts solution is heated above the temperature of follow-up ageing and is lower than or equals 70 ℃, and adds described PO
4 3-Salts solution.
8. the preparation method of phosphoric acid europium nano wire as claimed in claim 1 is characterized in that, regulates the pH value to 0.5 of described mixed liquor I～3.0.
9. the preparation method of phosphoric acid europium nano wire as claimed in claim 1 is characterized in that, the temperature of described ageing is 60 ℃～95 ℃.
10. such as the preparation method of the arbitrary described phosphoric acid europium nano wire of claim 1～9, it is characterized in that described phosphoric acid europium nano wire is further used deionized water and absolute ethanol washing, dry below 70 ℃ or 70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103127452A CN102849699A (en) | 2012-08-29 | 2012-08-29 | Preparation method of europium phosphate nano-wires |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103127452A CN102849699A (en) | 2012-08-29 | 2012-08-29 | Preparation method of europium phosphate nano-wires |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102849699A true CN102849699A (en) | 2013-01-02 |
Family
ID=47396750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103127452A Pending CN102849699A (en) | 2012-08-29 | 2012-08-29 | Preparation method of europium phosphate nano-wires |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102849699A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456714A (en) * | 2003-05-22 | 2003-11-19 | 北京大学 | Method for preparing phosphoric acid rare earth monocrystalline nano-thread |
| CN101704543A (en) * | 2009-11-25 | 2010-05-12 | 深圳大学 | Method for preparing cerous phosphate nano wire |
-
2012
- 2012-08-29 CN CN2012103127452A patent/CN102849699A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456714A (en) * | 2003-05-22 | 2003-11-19 | 北京大学 | Method for preparing phosphoric acid rare earth monocrystalline nano-thread |
| CN101704543A (en) * | 2009-11-25 | 2010-05-12 | 深圳大学 | Method for preparing cerous phosphate nano wire |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101704543B (en) | Method for preparing cerous phosphate nano wire | |
| CN102517018B (en) | Preparation method of nanowires of lanthanum phosphate activated by cerium and terbium | |
| CN101591540B (en) | Method for preparing rare-earth vanadate LaVO4:Eu red fluorescent powder | |
| CN104371717A (en) | Preparation method for enhancing luminescence property of BiPO4:Eu fluorescent powder by shape regulation | |
| CN102849706A (en) | Preparation method of cerium phosphate nano-wires | |
| CN102079541B (en) | Method for preparing doping type hexagonal system nano ZnS at low temperature | |
| CN103131417A (en) | Eu doped YPO4 microballoon and preparation method thereof | |
| CN101538466B (en) | Molybdate luminescent powder doped with rare earth ion and reparation method thereof | |
| CN102849711A (en) | Preparation method of gadolinium phosphate nano-wires | |
| CN101591538B (en) | Method for preparing rare-earth phosphate LnPO4:Eu red fluorescent powder | |
| CN102320659B (en) | Method for synthesizing lanthanum-vanadate nano material by adopting microwave-radiation method | |
| CN102745747B (en) | Preparation method for rod-like Sc2W3O12 negative thermal expansion material | |
| CN102951624A (en) | Preparation method of neodymium phosphate nanowire | |
| CN110510592A (en) | The method that regulation preparation has the hydroxyapatite of superior cell compatibility | |
| CN105752957B (en) | Using the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method | |
| CN106986319A (en) | Terbium/strontium of green fluorescent label with high luminous intensity is co-doped with the preparation method of hydroxyapatite nano particle | |
| CN102849707A (en) | Preparation method of lanthanum phosphate nano-wires | |
| CN102849699A (en) | Preparation method of europium phosphate nano-wires | |
| CN102849710A (en) | Preparation method of samarium phosphate nano-wires | |
| CN102849712A (en) | Preparation method of one-dimensional dysprosium phosphate nano-materials | |
| CN102849714A (en) | Preparation method for rare earth phosphate nanometer material | |
| CN102849713A (en) | Preparation method of praseodymium phosphate nano-wires | |
| CN103979515A (en) | YPO4 nano particle synthesized by assist of surfactant cetyltrimethyl ammonium bromide (CTAB) and preparation method of YPO4 nano particle | |
| CN101591539B (en) | Preparation method of a rare earth phosphate LnPO4: ce, tb Green fluorescent powder | |
| CN102849708B (en) | Preparation method of holmium phosphate nano-materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130102 |