CN102849712A - Preparation method of one-dimensional dysprosium phosphate nano-materials - Google Patents
Preparation method of one-dimensional dysprosium phosphate nano-materials Download PDFInfo
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Abstract
The invention provides a preparation method of one-dimensional dysprosium phosphate nano-materials. The preparation method comprises the following steps: respectively preparing a Dy<3+> salt solution and a PO4<3-> salt solution; adding the PO4<3-> salt solution to the Dy<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 0.5-3.0 to obtain a mixed solution II; and ageing the mixed solution II at 20-95DEG C under an environmental pressure for above 1h to obtain the one-dimensional dysprosium phosphate nano-materials (comprising nano-wires, nano-rods and nano-fibers). The preparation method can be implemented by adopting simple and cheap equipment under the environmental pressure, so the realization of industrialized production is convenient; and there is no need to add a template in the preparation process, so environmental influences possibly brought by a waste liquid can be avoided.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of one dimension dysprosium phosphate preparations of nanomaterials method.
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.Dysprosium is No. 66 element in the periodic table of elements, belongs to heavy rare earth element.It is mainly used in graphoscope and electricity-saving lamp etc. as rare earth luminescent material; As rare earth ultra-magnetostriction material, be widely used in the systems such as sonar, hydraulic pressure, aircraft fuel, seismic surveys, active vibration control, most typical application is the transverter of sonar probe in the underwater communication.Dysprosium is at the industrial magneto-optical recorder that also can be used for, and magnetic is freezing, magnetic biasing is oblique etc.
It is that nanoscale, length are the novel nano structured material of macro-scale that one-dimensional nano structure material refers at two-dimensional direction, generally includes nanometer rod, nano wire, nanofiber, nanotube, nano belt and coaxial nano cable etc.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 one dimension rare earth phosphate nano material 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 one dimension dysprosium phosphate preparations of nanomaterials method of suitability for industrialized production.
The present invention is achieved in that a kind of one dimension dysprosium phosphate preparations of nanomaterials method, and it comprises the steps:
Prepare respectively Dy
3+Salts solution and PO
4 3-Salts solution;
Under constantly stirring to described Dy
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～3.0, get mixed liquor I I;
Under environmental stress, described mixed liquor I I more than 1 hour, is obtained described one dimension dysprosium phosphate nano material 20 ℃～95 ℃ ageings.
One dimension dysprosium phosphate preparations of nanomaterials method provided by the invention, preparation condition is gentle, be in 0.5～3.0 scope in 20 ℃～95 ℃ of lower temperature and pH value, namely can obtain one dimension dysprosium phosphate nano material (comprising nano wire, nanometer rod, nanofiber).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 dysprosium phosphate nanometer rod that makes of the embodiment of the invention 1;
Fig. 2 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 2;
Fig. 3 is the XRD figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 2;
Fig. 4 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 3 and nanofiber;
Fig. 5 is the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 3 and the XRD figure of nanofiber;
Fig. 6 is the SEM figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 4;
Fig. 7 is the XRD figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 4;
Fig. 8 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 5;
Fig. 9 is the XRD figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 5;
Figure 10 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 6 and nano particle;
Figure 11 is the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 6 and the XRD figure of nano particle;
Figure 12 is the SEM figure of the dysprosium phosphate nano wire that makes of the embodiment of the invention 7;
Figure 13 is the XRD figure of the dysprosium phosphate nano wire that makes of the embodiment of the invention 7;
Figure 14 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 8;
Figure 15 is the XRD figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 8;
Figure 16 is the SEM figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 9;
Figure 17 is the XRD figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 9;
Figure 18 is the SEM figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 10;
Figure 19 is the SEM figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 10;
Figure 20 is the XRD figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 10;
Figure 21 is the SEM figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 11;
Figure 22 is the XRD figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 11;
Figure 23 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 12;
Figure 24 is the XRD figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 12;
Figure 25 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 13;
Figure 26 is the XRD figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 13;
Figure 27 is the SEM figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 14;
Figure 28 is the XRD figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 14;
Figure 29 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 15;
Figure 30 is the XRD figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 15;
Figure 31 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 16;
Figure 32 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 16;
Figure 33 is the XRD figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 16;
Figure 34 is the SEM figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 17;
Figure 35 is the SEM figure of the dysprosium phosphate nano wire that makes of the embodiment of the invention 18;
Figure 36 is the SEM figure of the dysprosium phosphate nanometer rod that makes of the embodiment of the invention 19;
Figure 37 is the SEM figure of the dysprosium phosphate nanofiber that makes of the embodiment of the invention 20;
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.
A kind of one dimension dysprosium phosphate preparations of nanomaterials method of the embodiment of the invention comprises the steps:
S01: prepare respectively Dy
3+Salts solution and PO
4 3-Salts solution;
S02: under constantly stirring to described Dy
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～3.0, get mixed liquor I I;
S04: under environmental stress, described mixed liquor I I more than 1 hour, is obtained described one dimension dysprosium phosphate nano material 20 ℃～95 ℃ ageings.
Among the step S01, this Dy
3+Salts solution and PO
4 3-Salts solution is respectively with this area solubility Dy commonly used
3+Salt and solubility ortho-phosphoric acid PO
4 3-Salt is solute, take water as solvent.For example, this solubility Dy
3+Salt can be Dysprosium trinitrate, Dysprosium trichloride etc., also comprises by Dy
2O
3The solubility Dy 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 solubility Dy
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 Dy
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 Dy
3+Salts solution in case with described PO
4 3-Salt solution mix (preparation mixed liquor I) namely generates white precipitate, and this is the dysprosium phosphate precipitation.Its reaction formula is:
Dy
3++PO
4 3-→DyPO
4↓
For making made dysprosium phosphate crystal grain be monodisperse status, and particle diameter is even, needs the limit at the uniform velocity stir this Dy
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 Dy
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 one dimension dysprosium phosphate nano material of crystalline form integrity degree, Dy 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 Dy 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～3.0 get mixed liquor I I under constantly stirring.Regulating 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 Dy 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 Dy
3+And PO
4 3-The change of molar concentration rate, the pattern of dysprosium phosphate product produced substantial effect.Dy in the mixed liquor I
3+And PO
4 3-Molar concentration rate be preferably 1～0.2.
The adjusting of the pH value of mixed liquor I is the important factor that affects one dimension dysprosium phosphate appearance of nano material.When Aging Temperature is 60 ℃～90 ℃ or is higher than 90 ℃, the pH value of mixed liquor I is less than or equal at 1.4 o'clock, can make dysprosium phosphate nanometer rod or nano wire; When the pH of mixed liquor I value in 1.4～2.8 scopes, can make the dysprosium phosphate nanofiber.When the pH of mixed liquor I value in 1.50～2.70 scopes, can make the larger dysprosium phosphate nanofiber of crystal volumetric expansion; When the pH of mixed liquor I value greater than 2.8 the time, can make the dysprosium phosphate nanometer rod.When Aging Temperature is lower than 60 ℃, made dysprosium phosphate product mainly is nanometer rod or nano wire.
In order to control preferably the pH value of mixed liquor I, when regulating the pH value, should look the size of the acidity that will regulate, acid solution or the alkaline solution of the different concns that selection is prepared.For example, if the acidity that will regulate is not very big, the rarer acid solution of concentration that should select to prepare is regulated.If the acid solution that working concentration is larger is regulated, then might add 1, just make the acidity of mixed liquor I surpass the pH value that will regulate.
After regulating pH, add a certain amount of deionized water, to control the concentration of this mixed liquor I I.Form after the mixed liquor I I, can continue to stir.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 20 ℃～95 ℃ ageings 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 material crystallization of one dimension dysprosium phosphate and process of growth, for guaranteeing the growth of dysprosium phosphate nano material 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 one dimension dysprosium phosphate nano material at 20 ℃～95 ℃.When Aging Temperature very low (being less than or equal to 60 ℃), the proper extension digestion time can obtain the larger one dimension dysprosium phosphate nano material of length-to-diameter ratio.When Aging Temperature is higher (60 ℃～95 ℃), then through relatively short period of time ageing, can obtain the larger one dimension dysprosium phosphate nano material of length-to-diameter ratio.Preferably, Aging Temperature is 60 ℃～95 ℃.If Aging Temperature higher (60 ℃～95 ℃) then takes out mixed solution after the ageing and should 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 dysprosium phosphate nano material 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.
One dimension dysprosium phosphate preparations of nanomaterials method 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, is 0.5～3.0 in 20 ℃～95 ℃ of lower temperature and pH value, the concentration of mixed solution is in 0.005～0.1 mol/L scope, namely can implement.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 one dimension dysprosium phosphate nano material 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 one dimension dysprosium phosphate nano material (comprising nano wire, nanometer rod, nanofiber) is described.
Embodiment 1:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described Dysprosium trinitrate 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 Dysprosium trinitrate solution.Continue to stir 1 hour, during to adopt dilution be that 20% positive acid solution is regulated the pH value to 1.10 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 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 dysprosium phosphate product that as seen the SEM phenogram makes is little nanometer rod (Fig. 1).
Embodiment 2:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described Dysprosium trinitrate 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 Dysprosium trinitrate solution.Continue to stir 1 hour, during to adopt dilution be that 20% positive acid solution is regulated the pH value to 1.20 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 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 dysprosium phosphate product that as seen the SEM phenogram makes is little nanometer rod; The XRD phenogram shows that made dysprosium phosphate nanometer rod is hexagonal crystal phase (Fig. 2, Fig. 3).
Embodiment 3:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 380 rev/mins rotating speed, while stirring 25 milliliters of described diammonium phosphate aqueous solution is splashed in the described Dysprosium trinitrate aqueous solution.Continue to stir 1 hour.Add during this time 10 milliliters of the positive acid solutions of 0.6mol/L, and add a certain amount of deionized water, make the pH value to 1.40 of mixing solutions, cumulative volume is 80 milliliters of (Dy in this mixing solutions
3+And PO
4 3-Molar concentration rate be 0.3).After stopping to stir, the Erlenmeyer flask that this mixing solutions 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 mass.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The dysprosium phosphate product that as seen the SEM phenogram makes is nanometer rod (wherein containing nanofiber), and the XRD phenogram shows that made dysprosium phosphate product is hexagonal crystal phase (Fig. 4, Fig. 5).
Embodiment 4:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described Dysprosium trinitrate 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 Dysprosium trinitrate solution.Continue to stir 1 hour, during to adopt dilution be that 10% ammonia soln is regulated the pH value to 1.80 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 positioned in 90 ℃ 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 dysprosium phosphate product that as seen the SEM phenogram makes is nanofiber; The XRD phenogram shows that made dysprosium phosphate nanofiber is hexagonal crystal phase (Fig. 6, Fig. 7).
Embodiment 5:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate 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 Dysprosium trinitrate 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 1.30, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 90 ℃ of waters 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 visible made dysprosium phosphate product of SEM phenogram is nanometer rod; The XRD phenogram shows that made dysprosium phosphate nanometer rod is hexagonal crystal phase (Fig. 8, Fig. 9).
Embodiment 6:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate 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 Dysprosium trinitrate 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 1.20, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 90 ℃ the water bath with thermostatic control, ageing after 36 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 visible made dysprosium phosphate product of SEM phenogram is rhombus nanometer rod and nano particle; The XRD phenogram shows that made dysprosium phosphate product belongs to hexagonal crystal phase (Figure 10, Figure 11).
Embodiment 7:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate 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 Dysprosium trinitrate 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 0.50, 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 is after 12 hours under environmental stress, and room temperature is cooled off, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The visible made dysprosium phosphate product of SEM phenogram is nano wire; The dysprosium phosphate nano wire that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 12, Figure 13).
Embodiment 8:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 300 rev/mins rotating speed, while stirring described disodium phosphate soln is splashed in the described Dysprosium trinitrate solution.Continue to stir 1 hour.Adopting during this time dilution is that 20% positive acid solution is regulated this mixing solutions pH value to 1.35, and adds a certain amount of deionized water, and the cumulative volume that makes mixing solutions 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 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 visible made dysprosium phosphate product of SEM phenogram is nanometer rod; The dysprosium phosphate nanometer rod that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 14, Figure 15).
Embodiment 9:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 300 rev/mins rotating speed, while stirring described disodium phosphate soln is splashed in the described Dysprosium trinitrate solution.Continue to stir 1 hour.Adopt during this time the positive acid solution of 0.6mol/L to regulate this mixing solutions pH value to 1.50, 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 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 visible made dysprosium phosphate product of SEM phenogram is nanofiber; The dysprosium phosphate nanofiber that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 16, Figure 17).
Embodiment 10:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 350 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described Dysprosium trinitrate solution.Continue to stir 1 hour, during be the pH value of 10% ammonia soln accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 2.00, 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 visible made dysprosium phosphate product of SEM phenogram is nanofiber; The dysprosium phosphate nanofiber that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 18, Figure 19, Figure 20).
Embodiment 11:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 350 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described Dysprosium trinitrate solution.Continue to stir 1 hour, during be the pH value of 20% ammonia soln accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 2.50, 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 visible made dysprosium phosphate product of SEM phenogram is nanofiber; The dysprosium phosphate nanofiber that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 21, Figure 22).
Embodiment 12:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 350 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described Dysprosium trinitrate 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 3.00, 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 visible made dysprosium phosphate product of SEM phenogram is nanometer rod; The dysprosium phosphate nanometer rod that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 23, Figure 24).
Embodiment 13:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 350 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described Dysprosium trinitrate 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 1.40, 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 is after 2 hours under environmental stress, and room temperature is cooled off, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The visible made dysprosium phosphate product of SEM phenogram is nanometer rod; The dysprosium phosphate nanometer rod that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 25, Figure 26).
Embodiment 14:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 350 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described Dysprosium trinitrate solution.Continue to stir 1 hour, during transfer the pH value of mixing solutions with the positive acid solution of 0.6mol/L, and add a certain amount of deionized water, the pH value that makes mixing solutions is 1.50, 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 dysprosium phosphate product that as seen the SEM phenogram makes is nanofiber; The visible made dysprosium phosphate nanofiber of XRD phenogram is hexagonal crystal phase (Figure 27, Figure 28).
Embodiment 15:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [(Na
2HPO
412H
2O], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described Dysprosium trinitrate 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 Dysprosium trinitrate solution.Continue to stir 90 minutes, 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 1.00, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 30 ℃ of waters bath with thermostatic control, ageing is 12 hours under environmental stress, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The visible made dysprosium phosphate product of SEM phenogram is nanometer rod; The dysprosium phosphate nanometer rod that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 29, Figure 30).
Embodiment 16:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the Dysprosium trinitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described Dysprosium trinitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 400 rev/mins rotating speed, while stirring described 25 milliliters of disodium phosphate solns is splashed in the described Dysprosium trinitrate solution.Continue to stir 1 hour.Adopting during this time dilution is that 20% positive acid solution is regulated this mixing solutions pH value to 1.10, and adds a certain amount of deionized water, and the cumulative volume that makes mixing solutions is 80 milliliters.After stopping to stir, Erlenmeyer flask that this mixing solutions is housed with bottleneck on the preservative film cover, is positioned under the room temperature condition (20.5 ℃ of medial temperatures, the temperature difference ± 2.8 ℃), ageing is after 5 days under environmental stress, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The visible made dysprosium phosphate product of SEM phenogram is little rhombus nanometer rod; The dysprosium phosphate nanometer rod that as seen the XRD phenogram makes is hexagonal crystal phase (Figure 31, Figure 32, Figure 33).
Embodiment 17:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [(Na
2HPO
412H
2O], be mixed with the Dysprosium trinitrate 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 Dysprosium trinitrate aqueous solution and be diluted to 25 milliliters with deionized water, place Erlenmeyer flask, the employing magnetic stirring apparatus stirs with 250 rev/mins rotating speed, and the Sodium phosphate dibasic aqueous solution with 4 milliliters of described 0.1 mol/L splashes in the described Dysprosium trinitrate solution while stirring.Continue to stir 1 hour, during be the pH value of 20% ammonia soln accent mixing solutions with dilution, and add a certain amount of deionized water, the pH value that makes mixing solutions is 2.70, cumulative volume is 80 milliliters of (Dy 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 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 dysprosium phosphate product that as seen the SEM phenogram makes is nanofiber (Figure 34).
Embodiment 18:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [(Na
2HPO
412H
2O], be mixed with the Dysprosium trinitrate 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 Dysprosium trinitrate aqueous solution and be diluted to 25 milliliters with deionized water, place Erlenmeyer flask, the employing magnetic stirring apparatus stirs with 250 rev/mins rotating speed, and the Sodium phosphate dibasic aqueous solution with 4 milliliters of described 0.1 mol/L splashes in the described Dysprosium trinitrate 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 0.90, cumulative volume is 80 milliliters of (Dy 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 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 dysprosium phosphate product that as seen the SEM phenogram makes is nano wire (Figure 35).
Embodiment 19:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with the Dysprosium trinitrate 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 Dysprosium trinitrate aqueous solution, place Erlenmeyer flask, the employing magnetic stirring apparatus stirs with 460 rev/mins rotating speed, while stirring 28 milliliters of described diammonium phosphate aqueous solution is splashed in the described Dysprosium trinitrate 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 1.40, cumulative volume is 80 milliliters of (Dy 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 is after 12 hours under environmental stress, and room temperature is cooled off, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The dysprosium phosphate product that as seen the SEM phenogram makes is nanometer rod (Figure 36).
Embodiment 20:
Take by weighing the Dysprosium trinitrate [Dy (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with the Dysprosium trinitrate 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 Dysprosium trinitrate aqueous solution, place Erlenmeyer flask, the employing magnetic stirring apparatus stirs with 460 rev/mins rotating speed, while stirring 26.7 milliliters of described diammonium phosphate aqueous solution is splashed in the described Dysprosium trinitrate aqueous solution.Continue to stir 1 hour, and add a certain amount of deionized water.The pH value of this mixing solutions is 1.60, and cumulative volume is 80 milliliters of (Dy 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 60 ℃ of waters bath with thermostatic control, ageing is after 12 hours under environmental stress, and room temperature is cooled off, and centrifugation obtains white depositions.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The dysprosium phosphate product that as seen the SEM phenogram makes is nanofiber (Figure 37)
Dysprosium phosphate product pattern and structural characterization
See also Fig. 1～Figure 11, the embodiment of the invention 1～6, that described mixing solutions is all 90 ℃ of bath temperature ageings 12 hours, its pH value is respectively pH1.10, pH1.20, pH1.40, pH1.80(Fig. 1～Fig. 7, embodiment 1～4) and mixing solutions in 90 ℃ of bath temperature ageings 1.5 hours (Fig. 8～Fig. 9, embodiment 5) and at the made dysprosium phosphate product of 90 ℃ of bath temperature ageings 36 hours (Figure 10～Figure 11, embodiment 6).The SEM phenogram illustrates, 90 ℃ of bath temperature ageings 12 hours, and when the pH value is 1.10 (Fig. 1, embodiment 1), made dysprosium phosphate product pattern is nanometer rod; (Fig. 2 when the pH value is 1.20, embodiment 2), made dysprosium phosphate product pattern also is nanometer rod, but the pattern of described dysprosium phosphate nanometer rod is slightly different, and along with the pH value increases, the pattern of nanometer rod becomes elongated by short and thick, and when the pH value is 1.40 (Fig. 4, embodiment 3), made dysprosium phosphate product pattern is long nanometer rod, and wherein is mixed with nanofiber.Same 90 ℃ of bath temperature ageings 12 hours, when the pH value is 1.80 (Fig. 6, embodiment 4), made dysprosium phosphate product pattern is long nanofiber, and a branch of bundle of nanofiber coalesces together.And ageing 1.5 hours under 90 ℃ of bath temperatures, the pH value is 1.30 o'clock (Fig. 8, embodiment 5), made dysprosium phosphate product pattern also is nanometer rod; Equally ageing 36 hours under 90 ℃ of bath temperatures, the pH value is 1.20 o'clock (Figure 10, embodiment 6), made dysprosium phosphate product pattern is rhombus nanometer rod and nano particle.
As fully visible, under 90 ℃ of temperature condition, the pH value of mixing solutions and digestion time all exert an influence to dysprosium phosphate product pattern.The pH value of mixing solutions (pH1.10～1.80) in narrower scope changes, and dysprosium phosphate product pattern but changes larger.When the pH value less than 1.40 the time, made dysprosium phosphate product pattern is nanometer rod; When the pH value equaled 1.40, made dysprosium phosphate product also was nanometer rod, but the nanometer rod particle becomes large, and begin to have nanofiber occur (when pH value is about 1.40, the nanometer rod volumetric expansion, particle becomes greatly, its diameter dimension is about 0.1 micron.As: Fig. 4, Figure 14, Figure 25, Figure 36); When the pH value greater than 1.40 the time, made dysprosium phosphate product pattern is nanofiber.As seen, the excessive adding of phosphate aqueous solution in the mixing solutions makes its pH value be in strongly-acid scope (the pH value is less than 1.40), is conducive to the formation of dysprosium phosphate nanometer rod, and inhibited to the formation of dysprosium phosphate nanofiber.
Please consult simultaneously Fig. 2 and Figure 10, Aging Temperature is 90 ℃ in the embodiment of the invention 2 and embodiment 6, two examples, and mixing solutions pH value is 1.20, but digestion time is different.Along with the prolongation of digestion time, extend to 36 hours by 12 hours, made dysprosium phosphate product pattern becomes rhombus nanometer rod and mixture of nanoparticles by the elongated shape nanometer rod.Please consult simultaneously Fig. 3 and Figure 11, XRD phenogram (Fig. 3, Figure 11) shows that under 90 ℃ of bath temperatures, 12 hours made dysprosium phosphate nanometer rod degree of crystallinity outlines of ageing are better than 36 hours dysprosium phosphate nanometer rod of ageing and the degree of crystallinity of nano particle.Illustrate that digestion time extends to a certain degree, to dysprosium phosphate nanometer rod crystalline growth or certain restraining effect is arranged.
XRD phenogram (Fig. 3, Fig. 5, Fig. 7, Fig. 9, Figure 11, embodiment 1～6) shows, the diffraction peak that under described temperature condition, makes the dysprosium phosphate product all with hexagonal crystal phase dysprosium phosphate characteristic diffraction peak (JCPDS 21-0316) position consistency.Particularly, be the characteristic diffraction peak that 15.264 °, 20.835 °, 26.346 °, 30.420 °, 32.436 °, 39.063 °, 43.166 °, 48.512 °, 50.166 °, 53.716 ° diffraction peak corresponds respectively to hexagonal crystal phase dysprosium phosphate (100), (101), (110), (200), (102), (112), (003), (301), (212), (203) crystal face at 2 θ.As seen, the embodiment of the invention 1～6 made dysprosium phosphate nanometer rod is hexagonal crystal mutually (JCPDS 21-0316) with nanofiber.
See also Figure 12～Figure 24, the embodiment of the invention 7～12, be described mixing solutions all under 12 hours conditions of 60 ℃ of bath temperature ageings, its pH value is respectively pH0.50, pH1.35, pH1.50, pH2.00, pH2.50, during pH3.00, made dysprosium phosphate product.The SEM phenogram illustrates, and mixing solutions pH value is 0.50 o'clock (Figure 12, embodiment 7), and made dysprosium phosphate product is nano wire; The pH value is 1.35 o'clock (Figure 14, embodiment 8), and made dysprosium phosphate product is nanometer rod; The pH value is 1.50 o'clock (Figure 16, embodiment 9), and made dysprosium phosphate product is nanofiber; The pH value is that 2.00 o'clock (Figure 18～19, embodiment 10) and pH value are 2.50 o'clock (Figure 21, embodiment 11), and made dysprosium phosphate product is nanofiber; And the pH value is 3.00 o'clock (Figure 23, embodiment 12), and made dysprosium phosphate product is nanometer rod.
XRD phenogram (Figure 13, Figure 15, Figure 17, Figure 20, Figure 22, Figure 24, embodiment 7～12) show, ageing is 12 hours under 60 ℃ of bath temperatures, and the pH value is in 0.5～3.0 scope, and made dysprosium phosphate product is hexagonal crystal phase (JCPDS 21-0316).
In addition please consult simultaneously Fig. 4, the embodiment of the invention 3 is that mixing solutions pH value is 1.40 o'clock, 12 hours made dysprosium phosphate nanometer rod of 90 ℃ of bath temperature ageings and nanofiber; Please consult simultaneously Fig. 6 in addition, the embodiment of the invention 4 is that mixing solutions pH value is 1.80,90 ℃ of bath temperature ageings 12 hours, made dysprosium phosphate nanofiber; Please consult simultaneously Figure 27 in addition, the embodiment of the invention 14 is that mixing solutions pH value is 1.50, and ageing is 48 hours under 60 ℃ of bath temperatures, made dysprosium phosphate nanofiber; Please consult simultaneously Figure 34 in addition, the embodiment of the invention 17 is that mixing solutions pH value is 12 hours (Dy in the mixing solutions of 2.70,60 ℃ of bath temperature ageings
3+And PO
4 3+Concentration is 0.005 mol/L) made dysprosium phosphate nanofiber; Please consult simultaneously Figure 37 in addition, the embodiment of the invention 20 is that mixing solutions pH value is 12 hours (Dy in the mixing solutions of 1.60,60 ℃ of bath temperature ageings
3+And PO
4 3+Concentration is 0.1 mol/L) made dysprosium phosphate nanofiber.As fully visible, the ageing regular hour under 60 ℃～90 ℃ (or being higher than 90 ℃) bath temperatures, described mixing solutions pH value is 1.40～2.70 or be slightly larger than 2.70(according to made product morphology analysis, think that pH value to 2.8 is more suitable), be the pH value in 1.40～2.80 scopes, all can make the dysprosium phosphate nanofiber.SEM phenogram (Fig. 6, Figure 27, Figure 34, Figure 37) it can also be seen that under 60 ℃～90 ℃ bath temperatures, mixing solutions pH value is in 1.50～2.70 scopes, and the volumetric expansion of made dysprosium phosphate nanofiber crystal is larger.
In addition please consult simultaneously Fig. 1～Fig. 2, the embodiment of the invention 1～2, be mixing solutions pH value be 1.10 and the pH value be 1.20 o'clock, 12 hours made dysprosium phosphate nanometer rod of 90 ℃ of bath temperature ageings; Please consult simultaneously Fig. 8 in addition, the embodiment of the invention 5 is that mixing solutions pH value is 1.30 o'clock, 1.5 hours made dysprosium phosphate nanometer rod of 90 ℃ of bath temperature ageings; In addition please consult simultaneously Figure 35, the embodiment of the invention 18 is that mixing solutions pH value is 0.90 o'clock, 60 ℃ of bath temperature ageings 12 hours, made dysprosium phosphate nano wire; Please consulting simultaneously Figure 12, Figure 14, Figure 23 in addition, is respectively the embodiment of the invention 7, embodiment 8 and embodiment 12, and described mixing solutions is all in 60 ℃ of bath temperature ageings 12 hours, and the pH value is respectively pH0.5, pH1.35 and pH3.0.The SEM phenogram as seen, made dysprosium phosphate product is nano wire or nanometer rod.As fully visible, described mixing solutions is the ageing certain hour under 60 ℃～90 ℃ (or being higher than 90 ℃) bath temperatures, and when the pH value was less than or equal to 1.4, made dysprosium phosphate product was nano wire or nanometer rod; When the pH value greater than 2.8, made dysprosium phosphate product is nanometer rod.
See also Figure 25～Figure 26, the embodiment of the invention 13 is that described mixing solutions pH value is 1.40 o'clock, and ageing is 2 hours in 60 ℃ of water-baths, the dysprosium phosphate product that makes.The SEM phenogram as seen, made dysprosium phosphate product is nanometer rod.Please consult simultaneously Fig. 4～Fig. 5 in addition, the embodiment of the invention 3 is that mixing solutions pH value is 1.40 o'clock, and ageing is 12 hours in 90 ℃ of water-baths, made dysprosium phosphate nanometer rod (wherein containing nanofiber).As seen, under identical pH value condition, mixing solutions is in the relatively long time (12 hours) of the lower ageing of higher bath temperature (90 ℃), the length-to-diameter ratio of made dysprosium phosphate nanometer rod, obviously greater than under low bath temperature (60 ℃), the time (2 hours) that ageing is short, the length-to-diameter ratio of made dysprosium phosphate nanometer rod.And ageing is 12 hours under 90 ℃ of bath temperatures, contains nanofiber in the made dysprosium phosphate nanometer rod.This shows, in higher bath temperature (such as 90 ℃) the lower ageing regular hour, more be conducive to the crystalline growth of dysprosium phosphate nanometer rod or nanofiber.XRD phenogram (Fig. 5, Figure 26) as seen, the degree of crystallinity of 12 hours made dysprosium phosphate nanometer rod of ageing is better than the degree of crystallinity of 2 hours made dysprosium phosphate nanometer rod of ageing in 60 ℃ of water-baths in 90 ℃ of water-baths, both are hexagonal crystal phase (JCPDS 21-0316).
See also Figure 27～Figure 28, the embodiment of the invention 14 is that described mixing solutions pH value is 1.50 o'clock, and ageing is 48 hours in 60 ℃ of water-baths, the dysprosium phosphate product that makes.The SEM phenogram as seen, made dysprosium phosphate product is nanofiber.Please consult simultaneously Figure 16～Figure 17 in addition, the embodiment of the invention 9 is that mixing solutions pH value is 1.50 o'clock, and ageing is 12 hours in 60 ℃ of water-baths, made dysprosium phosphate nanofiber.As seen, under identical pH value (pH1.50) and identical bath temperature (60 ℃), because digestion time is different, made dysprosium phosphate nanofiber pattern is also different.Under 60 ℃ of bath temperatures, along with the prolongation (extending to 48 hours by 12 hours) of digestion time, made dysprosium phosphate nanofiber major diameter is than becoming large.48 hours made nanofibers of ageing in 60 ℃ of water-baths, not only length-to-diameter ratio is large, and crystalline growth is even.XRD phenogram (Figure 28, Figure 17) as seen, the degree of crystallinity of 48 hours made dysprosium phosphate nanofibers of ageing is better than the degree of crystallinity of 12 hours made dysprosium phosphate nanofibers of ageing in 60 ℃ of water-baths in 60 ℃ of water-baths, and both are hexagonal crystal phase (JCPDS21-0316).
See also Figure 29～Figure 30, the embodiment of the invention 15 is that described mixing solutions pH value is 1.00 o'clock, and ageing is 12 hours in 30 ℃ of water-baths, the dysprosium phosphate product that makes.The SEM phenogram as seen, made dysprosium phosphate product is nanometer rod.The XRD phenogram as seen, made dysprosium phosphate nanometer rod is hexagonal crystal phase (JCPDS 21-0316).In addition please consult simultaneously Figure 31～33, the embodiment of the invention 16 is that mixing solutions pH value is 1.10 o'clock, under room temperature (20.5 ℃ of medial temperatures, the temperature difference ± 2.8 ℃) condition, and ageing 5 days, made dysprosium phosphate nanometer rod.As seen, under low temperature very (being lower than 60 ℃), mixing solutions pH value is less than 1.40, and made dysprosium phosphate product is nanometer rod.
See also Figure 31～Figure 33, the embodiment of the invention 16 is that mixing solutions pH value is 1.10 o'clock, under room temperature (20.5 ℃ of medial temperatures) condition, and ageing 5 days, made dysprosium phosphate product.The SEM phenogram as seen, the pH value is 1.10 o'clock, under room temperature (20.5 ℃ of the medial temperatures) condition, ageing 5 days, made dysprosium phosphate product is the nanometer rod (Figure 31, Figure 32) of little rhombus.In addition please consult simultaneously Fig. 1, the embodiment of the invention 1 is that the pH value is 1.10 o'clock, 90 ℃ of bath temperature ageings 12 hours, made dysprosium phosphate nanometer rod.As seen, be that the pH value is 1.10 o'clock equally, 12 hours made dysprosium phosphate nanometer rod of 90 ℃ of water-bath ageings are little stubby shape, and under the room temperature, ageing 5 days, made dysprosium phosphate nanometer rod is rhombus.In addition please consult simultaneously Figure 10, the embodiment of the invention 6 is that the pH value is 1.20 o'clock, 90 ℃ of bath temperature ageings 36 hours, made dysprosium phosphate nanometer rod and nano particle.Wherein the dysprosium phosphate nanometer rod is little rhombus.This shows, prolong digestion time to certain limit, can form little rhombus nanometer rod.XRD phenogram (Figure 33) as seen, formed rhombus nanometer rod degree of crystallinity is not fine.Illustrate to prolong digestion time to certain limit, maybe can restraining effect be arranged to dysprosium phosphate nanometer rod crystalline growth.
See also Figure 34～Figure 37, the embodiment of the invention 17～20 all is under 12 hours conditions of 60 ℃ of bath temperature ageings, Dy in the described mixing solutions
3+And PO
4 3+Concentration when being 0.005～0.1 mol/L respectively, the dysprosium phosphate product that makes.SEM phenogram (Figure 34～35, embodiment 17～18) illustrates, and two examples all are Dy in the mixing solutions
3+And PO
4 3+Concentration is 0.005 mol/L, and because the pH value of mixing solutions is different, made dysprosium phosphate product pattern is also different.The pH value is 2.70 o'clock, and made dysprosium phosphate product is nanofiber (Figure 34), and the pH value is 0.90 o'clock, and made dysprosium phosphate product is nano wire (Figure 35).SEM phenogram (Figure 36, embodiment 19) illustrates Dy in the mixing solutions
3+And PO
4 3+Concentration is 0.07 mol/L, and mixing solutions pH value is 1.40 o'clock, and made dysprosium phosphate product is nanometer rod (Figure 36).SEM phenogram (Figure 37, embodiment 20) illustrates Dy in the mixing solutions
3+And PO
4 3+Concentration is 0.1 mol/L, and mixing solutions pH value is 1.60 o'clock, and made dysprosium phosphate product is nanofiber (Figure 37).As seen, Dy in the mixing solutions
3+And PO
4 3+Concentration is under 0.005～0.1 mol/L condition, and the pH value of control mixing solutions by 60 ℃ of bath temperature ageings 12 hours, can be prepared respectively dysprosium phosphate nanometer rod, nano wire or nanofiber within the specific limits.
Please consult simultaneously Fig. 4 in addition, the embodiment of the invention 3 is that the pH value is 1.40 o'clock, 12 hours (Dy in the described mixed solution of 90 ℃ of bath temperature ageings
3+And PO
4 3+Concentration is 0.03 mol/L), made dysprosium phosphate nanometer rod.Fig. 4 and Figure 36 (embodiment 19) are compared, and as seen, ageing is 12 hours in 90 ℃ of water-baths, and made dysprosium phosphate nanometer rod is thinner, and nanofiber wherein occurred.The analysis-by-synthesis influence factor, when mixing solutions pH value was identical, then the impact of Aging Temperature was greater than the mixing solutions concentration as influencing factor.Ageing under relatively high bath temperature more is conducive to the crystalline growth of dysprosium phosphate nanofiber or nanometer rod.
Please consult simultaneously Figure 16～Figure 22 in addition, the embodiment of the invention 9～11 is Dy in the made mixed solution
3+And PO
4 3+Concentration is 0.03 mol/L, made dysprosium phosphate nanofiber.As seen, in the process of preparation one dimension dysprosium phosphate nano material, mixing solutions concentration all can make dysprosium phosphate nano wire, nanometer rod or nanofiber in 0.005～0.1 mol/L scope.
In sum, in preparation process, by pH value, Aging Temperature and the digestion time of control mixing solutions, can control the pattern of dysprosium phosphate product, obtain required product.
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. an one dimension dysprosium phosphate preparations of nanomaterials method is characterized in that, comprises the steps:
Prepare respectively Dy
3+Salts solution and PO
4 3-Salts solution;
Under constantly stirring to described Dy
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～3.0, get mixed liquor I I;
Under environmental stress, described mixed liquor I I more than 1 hour, is obtained described one dimension dysprosium phosphate nano material 20 ℃～95 ℃ ageings.
2. one dimension dysprosium phosphate preparations of nanomaterials method as claimed in claim 1 is characterized in that Dy 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. one dimension dysprosium phosphate preparations of nanomaterials method as claimed in claim 2 is characterized in that Dy in the described mixed liquor I
3+And PO
4 3-Concentration be 0.02～0.07 mol/L.
4. one dimension dysprosium phosphate preparations of nanomaterials method as claimed in claim 1 is characterized in that Dy in the described mixed liquor I
3+With PO
4 3-Molar concentration rate be 1～0.2.
5. one dimension dysprosium phosphate preparations of nanomaterials method as claimed in claim 1 is characterized in that, described under constantly stirring to described Dy
3+Add described PO in the salts solution
4 3-The speed of the stirring of salts solution is 200～460 rev/mins.
6. dysprosium phosphate preparations of nanomaterials method as claimed in claim 1 is characterized in that, under constantly stirring to described Dy
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 0.3～2.0 hour.
7. one dimension dysprosium phosphate preparations of nanomaterials method as claimed in claim 1 is characterized in that, the temperature of described ageing is 60 ℃～95 ℃.
8. one dimension dysprosium phosphate preparations of nanomaterials method as claimed in claim 1 is characterized in that, regulates the pH value to 1.4 of described mixed liquor I～2.8.
9. one dimension dysprosium phosphate preparations of nanomaterials method as claimed in claim 8 is characterized in that, regulates the pH value to 1.5 of described mixed liquor I～2.7.
10. such as the arbitrary described one dimension dysprosium phosphate preparations of nanomaterials method of claim 1～9, it is characterized in that described one dimension dysprosium phosphate nano material is further used deionized water and absolute ethanol washing, dry below 70 ℃ or 70 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104692351A (en) * | 2014-12-24 | 2015-06-10 | 中国科学院地球化学研究所 | Method for hydrothermally synthesizing rhombic dysprosium phosphate by virtue of CO2 enrichment |
| CN111747392A (en) * | 2020-07-17 | 2020-10-09 | 南昌航空大学 | Method for preparing semi-hydrated samarium phosphate rodlike nanocrystalline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006096936A1 (en) * | 2005-03-18 | 2006-09-21 | Advanced Nanotechnology Limited | Rare earth nanorods |
| CN101704543A (en) * | 2009-11-25 | 2010-05-12 | 深圳大学 | Method for preparing cerous phosphate nano wire |
| CN102517018A (en) * | 2011-11-10 | 2012-06-27 | 深圳大学 | Preparation method of nanowires of lanthanum phosphate activated by cerium and terbium |
-
2012
- 2012-08-29 CN CN2012103127471A patent/CN102849712A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006096936A1 (en) * | 2005-03-18 | 2006-09-21 | Advanced Nanotechnology Limited | Rare earth nanorods |
| CN101704543A (en) * | 2009-11-25 | 2010-05-12 | 深圳大学 | Method for preparing cerous phosphate nano wire |
| CN102517018A (en) * | 2011-11-10 | 2012-06-27 | 深圳大学 | Preparation method of nanowires of lanthanum phosphate activated by cerium and terbium |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104692351A (en) * | 2014-12-24 | 2015-06-10 | 中国科学院地球化学研究所 | Method for hydrothermally synthesizing rhombic dysprosium phosphate by virtue of CO2 enrichment |
| CN104692351B (en) * | 2014-12-24 | 2016-08-10 | 中国科学院地球化学研究所 | A kind of rich CO2the method of Hydrothermal Synthesis rhombus dysprosium phosphate |
| CN111747392A (en) * | 2020-07-17 | 2020-10-09 | 南昌航空大学 | Method for preparing semi-hydrated samarium phosphate rodlike nanocrystalline |
| CN111747392B (en) * | 2020-07-17 | 2023-03-14 | 南昌航空大学 | Method for preparing semi-hydrated samarium phosphate rod-shaped nanocrystalline |
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