CN102849713A - Preparation method of praseodymium phosphate nano-wires - Google Patents
Preparation method of praseodymium phosphate nano-wires Download PDFInfo
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- CN102849713A CN102849713A CN2012103128084A CN201210312808A CN102849713A CN 102849713 A CN102849713 A CN 102849713A CN 2012103128084 A CN2012103128084 A CN 2012103128084A CN 201210312808 A CN201210312808 A CN 201210312808A CN 102849713 A CN102849713 A CN 102849713A
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Abstract
The invention provides a preparation method of praseodymium phosphate nano-wires. The preparation method comprises the following steps: respectively preparing a Pr<3+> salt solution and a PO4<3-> salt solution; adding the PO4<3-> salt solution to the Pr<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 praseodymium 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 praseodymium phosphate 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.Praseodymium is No. 59 element in the periodic table of elements, belongs to light rare earths.Praseodymium usage quantity in rare earth element is larger, and in a lot of functional materialss, praseodymium forms as it, is playing the part of important role.As: coloured material of alloy material, catalytic material, permanent magnet material, grinding and polishing material, fiber optic materials, architectural pottery, domestic ceramics, glass etc., the miniature atomic battery made from praseodymium, volume is minimum, can also avoid outside temperature, pressure influence.
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 praseodymium phosphate nano wire of suitability for industrialized production.
The present invention is achieved in that a kind of preparation method of praseodymium phosphate nano wire, and it comprises the steps:
Prepare respectively Pr
3+Salts solution and PO
4 3-Salts solution;
Under constantly stirring to described Pr
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 praseodymium phosphate nano wire 4 ℃～95 ℃ ageings.
The preparation method of praseodymium phosphate nano wire provided by the invention, preparation condition is gentle, in (4 ℃～95 ℃), the wider pH value scope (pH0.5～9.0), can obtain the praseodymium phosphate 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 praseodymium phosphate nano wire that makes of the embodiment of the invention 1;
Fig. 2 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 1;
Fig. 3 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 2;
Fig. 4 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 2;
Fig. 5 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 3;
Fig. 6 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 3;
Fig. 7 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 4;
Fig. 8 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 4;
Fig. 9 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 5;
Figure 10 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 5;
Figure 11 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 6;
Figure 12 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 6;
Figure 13 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 7;
Figure 14 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 7;
Figure 15 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 8;
Figure 16 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 8;
Figure 17 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 9;
Figure 18 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 9;
Figure 19 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 10;
Figure 20 is the XRD figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 10;
Figure 21 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 11;
Figure 22 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 12;
Figure 23 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 13;
Figure 24 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 14;
Figure 25 is the SEM figure of the praseodymium phosphate nano wire that makes of the embodiment of the invention 15;
Figure 26 is the SEM figure of the praseodymium phosphate 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 praseodymium phosphate nano wire of the embodiment of the invention comprises the steps:
S01: prepare respectively Pr
3+Salts solution and PO
4 3-Salts solution;
S02: under constantly stirring to described Pr
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 praseodymium phosphate nano wire 4 ℃～95 ℃ ageings.
Among the step S01, this Pr
3+Salts solution and PO
4 3-Salts solution is respectively with this area solubility Pr commonly used
3+Salt and solubility ortho-phosphoric acid PO
4 3-Salt is solute, take water as solvent.For example, this solubility Pr
3+Salt can be praseodymium nitrate, praseodymium chloride etc., also comprises by Pr
2O
3The solubility Pr 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 Pr
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 Pr
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 Pr
3+Salts solution in case with described PO
4 3-Salt solution mix (preparation mixed liquor I) namely generates green precipitate, and this is the praseodymium phosphate precipitation.Its reaction formula is:
Pr
3++PO
4 3-→PrPO
4↓
For making praseodymium phosphate crystal grain be monodisperse status, and particle diameter is even, needs the limit at the uniform velocity stir this Pr
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 Pr
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 praseodymium phosphate nano wire of crystalline form integrity degree, Pr 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 Pr in the mixed liquor I
3+Salts solution and PO
4 3-The concentration of salts solution is all 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.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 Pr
3+And PO
4 3-Molar concentration rate change.Comparative study shows, in the scope that described pH value is regulated, and Pr
3+And PO
4 3-The change of molar concentration rate, the pattern of praseodymium phosphate nano wire produced substantial effect.Pr in described mixed liquor I
3+And PO
4 3-Molar concentration rate be preferably 1～0.2.
Be the pattern of the praseodymium phosphate 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 praseodymium phosphate 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 praseodymium phosphate 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 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 crystallization of praseodymium phosphate nano wire and process of growth, and for guaranteeing praseodymium phosphate nano wire crystal growth 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 the praseodymium phosphate nano wire at 4 ℃～95 ℃.During Aging Temperature very low (being lower than 60 ℃), the proper extension digestion time can obtain the larger praseodymium phosphate 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 praseodymium phosphate nano wire of length-to-diameter ratio.Preferably, Aging Temperature is 60 ℃～95 ℃.If mixed liquor I I is more than or equal to 4 ℃ of ageings during less than 60 ℃, can be when abovementioned steps S02 prepares mixed liquor I heated and stirred, be about to described Pr
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 ageing under the very low temperature (under room temperature).Can pass through at low temperatures suitable digestion time like this, obtain preferably praseodymium phosphate 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 praseodymium phosphate 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 praseodymium phosphate 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 preparation mixed liquor I and mixed liquor I I process, then at a lower temperature ageing (under room temperature), and control digestion time namely can prepare preferably praseodymium phosphate nano wire of crystallization at low temperatures.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 the praseodymium phosphate 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 praseodymium phosphate nano wire is described.
Embodiment 1:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium nitrate solution.Continue to stir 1 hour, during to adopt dilution be that 20% positive acid solution is regulated the pH value to 1.2 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Fig. 1, Fig. 2).
Embodiment 2:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium nitrate 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 1.58, 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 24 hours under environmental stress, and centrifugation obtains the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Fig. 3, Fig. 4).
Embodiment 3:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium nitrate solution.Continue to stir 1 hour.Adopting during this time dilution is that 25% positive acid solution is regulated this mixing solutions pH value to 1.0, 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 (23.3 ℃ of medial temperatures, the temperature difference ± 3.3 ℃), ageing is after 4 days under environmental stress, and centrifugation obtains the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Fig. 5, Fig. 6).
Embodiment 4:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described praseodymium nitrate 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 praseodymium nitrate solution.Continue to stir 1 hour, during to adopt dilution be that 20% positive acid solution is regulated the pH value to 1.30 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 12 hours under environmental stress, and afterwards centrifugation obtains the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Fig. 7, Fig. 8).
Embodiment 5:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [Na
2HPO
412H
2O], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described praseodymium nitrate solution is placed Erlenmeyer flask, put into electric heater, 60 ℃ of thermostatically heating, and the employing magnetic stirring apparatus splashes into described disodium phosphate soln in the described praseodymium nitrate solution while stirring with 400 rev/mins rotating speed stirring.Stirred 90 minutes 60 ℃ of lower lasting thermostatically heating, 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 1.5, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed placed under the room temperature cool off, then place 30 ℃ of (temperature difference ± 1 ℃) waters bath with thermostatic control, ageing is 12 hours under environmental stress, and centrifugation obtains the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Fig. 9, Figure 10).
Embodiment 6:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [(Na
2HPO
412H
2O], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the Sodium phosphate dibasic aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium nitrate solution.At room temperature continue to stir 90 minutes, 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 1.5, cumulative volume is 80 milliliters.After stopping to stir, the Erlenmeyer flask that this mixing solutions is housed is positioned in 30 ℃ of (temperature difference ± 1 ℃) waters bath with thermostatic control, ageing is after 12 hours under environmental stress, and centrifugation obtains the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Figure 11, Figure 12).
Embodiment 7:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium 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 0.5, 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Figure 13, Figure 14).
Embodiment 8:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium 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 3.0, 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Figure 15, Figure 16).
Embodiment 9:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Figure 17, Figure 18).
Embodiment 10:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire; The XRD phenogram shows that made praseodymium phosphate nano wire is hexagonal crystal phase (Figure 19, Figure 20).
Embodiment 11:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and Sodium phosphate dibasic [(Na
2HPO
412H
2O], be mixed with the praseodymium 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 praseodymium 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 praseodymium nitrate solution while stirring.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 1.58, cumulative volume is 80 milliliters of (Pr 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire (Figure 21).
Embodiment 12:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with the praseodymium 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 praseodymium 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 praseodymium 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 1.5, cumulative volume is 80 milliliters of (Pr 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire (Figure 22).
Embodiment 13:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with the praseodymium 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 praseodymium 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 praseodymium 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 1.5, cumulative volume is 80 milliliters of (Pr 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 was taken out Erlenmeyer flask after 12 hours under environmental stress, the room temperature cooling, and centrifugation obtains the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire (Figure 23).
Embodiment 14:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described praseodymium nitrate 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 praseodymium 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire (Figure 24).
Embodiment 15:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described praseodymium nitrate solution is placed Erlenmeyer flask, and the employing magnetic stirring apparatus stirs with 460 rev/mins rotating speed, while stirring described diammonium phosphate solution is splashed in the described praseodymium 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 12 hours under environmental stress, took out Erlenmeyer flask, the room temperature cooling, and centrifugation obtains the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire (Figure 25).
Embodiment 16:
Take by weighing the praseodymium nitrate [Pr (NO of certain mass
3)
36H
2O] and diammonium phosphate [(NH
4)
2HPO
4], be mixed with each 25 milliliters of the praseodymium nitrate aqueous solution that concentration is 0.1 mol/L and the diammonium phosphate aqueous solution with deionized water respectively.Described praseodymium 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 praseodymium 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 1.46, 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 the green precipitate thing.Use respectively deionized water and absolute ethanol washing secondary, 70 ℃ of oven dry.The praseodymium phosphate product that as seen the SEM phenogram makes is nano wire (Figure 26).
Praseodymium phosphate product pattern and structural characterization
See also Fig. 1～Fig. 8, the embodiment of the invention 1～4, respectively (23.3 ℃ of medial temperatures) ageing (Fig. 5, Fig. 6) and the 4 ℃ of lower ageings 12 hours (Fig. 7, Fig. 8) in 4 days under 90 ℃ of bath temperature ageings 12 hours (Fig. 1, Fig. 2), 60 ℃ of bath temperature ageings 24 hours (Fig. 3, Fig. 4), room temperature of described mixing solutions, the praseodymium phosphate product that makes.The SEM phenogram illustrates, and made praseodymium phosphate product is nano wire under 4 ℃～90 ℃ Aging Temperature conditions, and along with Aging Temperature raises, the length-to-diameter ratio of made praseodymium phosphate nano wire (ratio of length and diameter) increases gradually; The XRD phenogram shows, the diffraction peak of the praseodymium phosphate product that under 4 ℃～90 ℃ Aging Temperature conditions, makes all with hexagonal crystal phase praseodymium phosphate characteristic diffraction peak (JCPDS 20-0966) position consistency.Particularly, be the characteristic diffraction peak that 14.629 °, 20.073 °, 25.354 °, 29.355 °, 31.509 °, 41.663 °, 42.297 °, 48.761 °, 52.196 °, 53.377 °, 54.405 ° diffraction peak corresponds respectively to hexagonal crystal phase praseodymium phosphate (100), (101), (110), (200), (102), (211), (003), (212), (203), (302), (221) crystal face at 2 θ.This shows that the embodiment of the invention 1～4 made praseodymium phosphate product is hexagonal crystal phase (JCPDS 20-0966), and degree of crystallinity along with raising, Aging Temperature strengthens gradually.Please consult simultaneously Figure 26, the embodiment of the invention 16 is 95 ℃ of bath temperature ageings 1.5 hours, the praseodymium phosphate nano wire that makes.As seen, under 4 ℃～95 ℃ temperature condition, according to said method, take water as reaction medium, mixed solution all can make the praseodymium phosphate nano wire through after a while ageing.
See also Fig. 9～Figure 12, the embodiment of the invention 5 and 6, that described pH of mixed value is at 1.50 o'clock, continuous heating stirred 90 minutes under 60 ℃ of constant temperature respectively, then, ageing 12 hours and at room temperature lasting stirring are 90 minutes under 30 ℃ of bath temperatures, then, and ageing 12 little 2 o'clock made praseodymium phosphate products under 30 ℃ of bath temperatures.SEM phenogram (Fig. 9, Figure 11) as seen, continuous heating stirs the praseodymium phosphate nano wire made in 90 minutes under 60 ℃ of constant temperature, its length-to-diameter ratio is greater than the length-to-diameter ratio that continues to stir the praseodymium phosphate nano wire that made in 90 minutes under the room temperature.Can find out also that from the diffraction peak of XRD phenogram (Figure 10, Figure 12) degree of crystallinity that continuous heating stirs the praseodymium phosphate nano wire that made in 90 minutes under 60 ℃ of constant temperature is better than the degree of crystallinity that continues to stir the praseodymium phosphate nano wire that made in 90 minutes under the room temperature; Both are hexagonal crystal phase (JCPDS 20-0966).
See also Figure 13～Figure 20, the embodiment of the invention 7～10, be described mixed solution all 60 ℃ of bath temperature ageings 12 hours, and the pH value is respectively under pH0.5, pH3.0, pH6.0, the pH9.0 condition, the praseodymium phosphate product that makes.SEM phenogram (Figure 13, Figure 15, Figure 17, Figure 19) illustrates, and in pH 0.5～9.0 scope, the praseodymium phosphate product that makes is nano wire, and diminishes along with the pH value increases praseodymium phosphate nano wire crystal grain; XRD phenogram (Figure 14, Figure 16, Figure 18, Figure 20) shows that made praseodymium phosphate nano wire is hexagonal crystal phase (JCPDS 20-0966), and along with the pH value increases, the degree of crystallinity variation of praseodymium phosphate nano wire.Please consult simultaneously Fig. 1 and Fig. 2 in addition, the embodiment of the invention 1 is that the pH of mixed value is 1.20,90 ℃ of bath temperature ageings 12 hours, the praseodymium phosphate nano wire that makes; Please consult simultaneously Figure 21 in addition, the embodiment of the invention 11 is that the pH of mixed value is 12 hours (Pr in the described mixed solution of 1.58,60 ℃ of bath temperature ageings
3+And PO
4 3-Concentration be 0.005 mol/L), the praseodymium phosphate nano wire that makes; Please consult simultaneously Fig. 5 and Fig. 6 in addition, the embodiment of the invention 3 is that the pH of mixed value is 1.0, and (23.3 ℃ of medial temperatures) ageing is 4 days at ambient temperature, the praseodymium phosphate nano wire that makes.As seen, described pH of mixed value is under 0.5～9.0 condition, all can make the praseodymium phosphate nano wire.And in the pH 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 the praseodymium phosphate nano wire preferably.
See also Figure 21～23, the embodiment of the invention 11～13 is Pr in the described mixed solution
3+And PO
4 3+Concentration is respectively under 0.005～0.1 mol/L condition, the praseodymium phosphate product that makes.SEM phenogram (Figure 21～23) as seen, the praseodymium phosphate product that (0.005～0.1 mol/L) makes in this concentration range is nano wire.Please consult simultaneously Fig. 3～4 in addition, the embodiment of the invention 2 and Figure 15～16, the embodiment of the invention 8, this two example is Pr in the made mixed solution
3+And PO
4 3+Concentration is 0.03 mol/L.As seen, mixed liquid concentration is controlled under 0.005～0.1 mol/L condition in the preparation process, and the praseodymium phosphate product that makes is the praseodymium phosphate nano wire.
See also Figure 24～26, the embodiment of the invention 14～16 is respectively 60 ℃ of bath temperature ageings 48 hours (Figure 24), 60 ℃ of bath temperature ageings 12 hours (Figure 25) and 1.5 hours (Figure 26) made praseodymium phosphate nano wires of 95 ℃ of bath temperature ageings.SEM phenogram (Figure 24, Figure 25) as seen, under 60 ℃ of bath temperatures, described pH of mixed value is 1.55 o'clock, digestion time extended to 48 hours by 12 hours, made praseodymium phosphate nano wire length-to-diameter ratio (ratio of length and diameter) increases.As seen, when Aging Temperature was not bery high, the proper extension digestion time was conducive to make the larger praseodymium phosphate nano wire of length-to-diameter ratio.
Please consult simultaneously Fig. 5 in addition, the embodiment of the invention 3 is praseodymium phosphate nano wires that (23.3 ℃ of medial temperatures) ageing made in 4 days under the room temperature; SEM phenogram (Figure 24, Figure 25, Figure 26, Fig. 5) as seen, under relatively lower temp, praseodymium phosphate nanowire-junction crystals growth is slow, the proper extension digestion time can obtain the relatively large praseodymium phosphate nano wire of length-to-diameter ratio; And praseodymium phosphate nanowire-junction crystals growth is very fast in comparatively high temps (95 ℃) water-bath, and ageing can obtain the larger praseodymium phosphate nano wire of length-to-diameter ratio in 1.5 hours.Preferably, Aging Temperature is 60 ℃～95 ℃.
As fully visible, in the process of preparation, select suitable Aging Temperature and suitable digestion time, and the pH value of mixed solution, can control the crystal growth rate of praseodymium phosphate nano wire, the moderate praseodymium phosphate nano wire of acquisition length-to-diameter ratio.
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 praseodymium phosphate nano wire is characterized in that, comprises the steps:
Prepare respectively Pr
3+Salts solution and PO
4 3-Salts solution;
Under constantly stirring to described Pr
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 praseodymium phosphate nano wire 4 ℃～95 ℃ ageings.
2. the preparation method of praseodymium phosphate nano wire as claimed in claim 1 is characterized in that, Pr 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 praseodymium phosphate nano wire as claimed in claim 2 is characterized in that, Pr in the described mixed liquor I
3+And PO
4 3-Concentration be 0.02～0.07 mol/L.
4. the preparation method of praseodymium phosphate nano wire as claimed in claim 1 is characterized in that, Pr in the described mixed liquor I
3+With PO
4 3-Molar concentration rate be 1～0.2.
5. the preparation method of praseodymium phosphate nano wire as claimed in claim 1 is characterized in that, described under constantly stirring to described Pr
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 praseodymium phosphate nano wire as claimed in claim 1 is characterized in that, under constantly stirring to described Pr
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. the preparation method of praseodymium phosphate 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 Pr
3+Add described PO in the salts solution
4 3-Salts solution is: under constantly stirring with described Pr
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 praseodymium phosphate 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 praseodymium phosphate 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 praseodymium phosphate nano wire of claim 1～9, it is characterized in that described praseodymium phosphate nano wire is further used deionized water and absolute ethanol washing, dry below 70 ℃ or 70 ℃.
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|---|---|---|---|---|
| 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 |
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| 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 |
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