CN103043699A - Preparation method of NaNdF4 luminous nanorod powder - Google Patents

Preparation method of NaNdF4 luminous nanorod powder Download PDF

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CN103043699A
CN103043699A CN2012105289339A CN201210528933A CN103043699A CN 103043699 A CN103043699 A CN 103043699A CN 2012105289339 A CN2012105289339 A CN 2012105289339A CN 201210528933 A CN201210528933 A CN 201210528933A CN 103043699 A CN103043699 A CN 103043699A
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preparation
solution
reaction
nandf
nanometer rod
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陶锋
王志俊
孙宇峰
朱贵春
陶硕
胡从荣
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Anhui Polytechnic University
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Anhui Polytechnic University
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Abstract

The invention relates to a preparation method of NaNdF4 luminous nanorod powder, wherein Nd3+ and H2EDTA2+ are subjected to chelation reaction before being added into a reaction kettle, and then a chelating agent in the reaction kettle releases Nd3+, so that the ion reacts with NaF to generate the NaNdF4. The preparation method has the following characteristics: a needed device is simple, the cost is low, the environment is not polluted, the preparation method belongs to environment-friendly preparation, the operation process is convenient, NaNdF4 rare earth fluoride can be prepared at a rather low temperature by regulating the pH value of the reaction system, the molar ratio of initial reactants, the reaction temperature and the reaction time, and the phase and the appearance size of the product can be controlled precisely.

Description

A kind of NaNdF 4The preparation method of nanometer rod luminescent powder
Technical field
The present invention relates to the rare earth luminescent material preparing technical field, relate in particular to a kind of NaNdF 4The preparation method of nanometer rod luminescent powder.
Background technology
Study of Nanoscale Rare Earth Luminescent Materials refers to that size of particles is at the luminescent material of 1-100nm.The small-size effect of nano material, quantum size effect, surface effects and macroscopical tunnel effect make it present the characteristic different from conventional material, basic metal rare earth fluoride nano material (AReF at aspects such as optics, calorifics, electricity, magnetic properties 4A=Li, Na, K, the singularity of the aspects such as the level structure Re=rare earth element), transmission ofenergy and spectral quality, with and the luminescent material of preparation have the characteristics such as high brightness, high stability, epigranular, narrowly distributing, make it be widely used in the fields such as luminous, demonstration, optical transmission of information, biomarker, laser.Yet, adopt traditional high temperature and high pressure method to prepare basic metal rare earth fluorine energy consumption height, complicated operation, equipment requirements height.Therefore, seek the preparation method who under mild reaction conditions, synthesizes the fluoride nano crystal of pattern, size homogeneous and become inevitable trend.At present, the novel method that some synthetic alkali metal rare earth fluoride nano materials occurred; Adopt the mechanochemistry method such as people such as Zhang, utilize alkaline metal fluoride cpd powder and rare earth fluorine powdered reaction to prepare the basic metal Rare earth fluoride complex; The people such as Yan utilize Na(CF 3COO) and Re(CF 3COO) 3Common pyrolysis prepared NaReF 4(Re=Pr, Lu, Y) is nanocrystalline.The people such as Cui are with Nd(C 3H 7COO) 3Phen and Nd(NO 3) 3Phen is precursor aqueous solution, has synthesized NaNdF with gentle hydrothermal method 4Nanocrystalline.But these methods need anhydrous and oxygen-free environment mostly, long reaction time, temperature of reaction is high, a large amount of organic substances such as oleic acid, oleyl amine and tri octyl phosphine etc. have also been used in addition in the preparation process, thermal decomposition product is usually poisonous after heat-treated, postprocessing working procedures is complicated, and can cause environmental pollution etc.
 
Summary of the invention
For solving problems of the prior art, the object of the present invention is to provide a kind of NaNdF 4The preparation method of nanometer rod luminescent powder, its required equipment is simple, operating procedure is convenient, can realize rare earth fluorine NaNdF by the pH value of conditioned reaction system, mol ratio, temperature of reaction and the reaction times of initial reactant etc. 4Phase and appearance and size accurately control.
The technical solution adopted in the present invention: a kind of NaNdF 4The preparation method of nanometer rod luminescent powder adopts Neodymium trioxide (Nd 2O 3), nitric acid (HNO 3), Sodium Fluoride (NaF), disodium ethylene diamine tetraacetate (Na 2H 2EDTA), ammoniacal liquor (NH 4OH), dehydrated alcohol (C 2H 5OH) be raw material, carry out according to following steps:
(1) HNO of usefulness 10mol/L 3Dissolving Nd 2O 3, heated and stirred continues to be heated to solution residue 8%-12% to the solution becomes clarification, namely make pre-reaction material Nd(NO 3) 3Solution;
(2) preparation sequestrant Na 2H 2EDTA solution, under the magnetic agitation condition with pre-reaction material Nd(NO 3) 3Solution mixes, and makes Nd in the solution 3+And Na 2H 2The mol ratio of EDTA is 1:(0.5-2), stirring reaction 5-30min;
(3) add an amount of NaF solution to reaction soln, so that Nd in the solution 3+And F -Mol ratio be 1:(6-10), use HNO 3Regulate mixing solutions pH value to 2-4, stir 5-30min, namely get the mixing solutions of the muddy thing of adularescent;
(4) mixing solutions is joined in the water heating kettle liner, be filled to 80% of liner volume, airtight water heating kettle carries out hydrothermal treatment consists, is incubated 12-48h under 160-200 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, after the centrifugal collection of reaction product, with dehydrated alcohol and distilled water repetitive scrubbing, in loft drier, dry 5-10h, bake out temperature 50-100 ℃, namely get NaNdF 4The nanometer rod luminescent powder.
Beneficial effect of the present invention:
Preparation method of the present invention is simple to operate, with low cost, environmentally safe, belongs to the environmental type preparation.Only by Nd before the dress still 3+With Na 2H 2The EDTA chelatropic reaction; Inner complex discharges again Nd gradually in reactor 3+React with NaF, generate NaNdF 4The present invention adopts hydrothermal method, has realized preparing NaNdF under lower temperature 4Nanocrystalline.The in the past conditions such as the required high temperature of preparation method, high pressure have been overcome.The method can control effectively artificially to nanocrystalline phase and the appearance and size that makes.
 
Description of drawings
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the NaNdF to the present invention's preparation 4The X-ray diffractogram of nanometer rod luminescent powder (XRD);
Fig. 3 is the NaNdF to the present invention's preparation 4The token image of the scanning electronic microscope of nanometer rod luminescent powder (FESEM) and transmission electron microscope (TEM);
Fig. 4 is the NaNdF that the present invention prepares 4The energy spectrogram (EDS) of nanometer rod luminescent powder;
Fig. 5 is NaNdF 4The emmission spectrum of nanometer rod luminescent powder, the emmission spectrum highest peak is corresponding to 1059nm.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Embodiment one
As shown in Figure 1, NaNdF 4The preparation process of nanometer rod luminescent powder is:
(1) HNO of usefulness 10mol/L 3Dissolving Nd 2O 3, heated and stirred continues to be heated to solution residue 10% to the solution becomes clarification, namely make pre-reaction material Nd(NO 3) 3Solution;
(2) preparation sequestrant Na 2H 2EDTA solution, under the magnetic agitation condition with pre-reaction material Nd(NO 3) 3Solution mixes, and makes Nd in the solution 3+And Na 2H 2The mol ratio of EDTA is 1:1, stirring reaction 10min;
(3) add an amount of NaF solution to reaction soln, so that Nd in the solution 3+And F -Mol ratio be 1:7.5, use HNO 3Regulate mixing solutions pH value to 2, stir 5min, namely get the mixing solutions of the muddy thing of adularescent;
(4) mixing solutions is joined in the water heating kettle liner, be filled to 80% of liner volume, airtight water heating kettle carries out hydrothermal treatment consists, is incubated 24h under 180 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, after the centrifugal collection of reaction product, with dehydrated alcohol and distilled water repetitive scrubbing, dry 10h in loft drier, 60 ℃ of bake out temperatures namely get NaNdF 4Nanometer rod.
The product that makes is characterized with Phillips D8 type X-ray diffractometer, and the X-ray diffraction spectrogram (such as Fig. 2) that obtains, the product that makes as can be known are six side's phase NaNdF 4To the product that makes with the S-4800 of Hitachi type field emission scanning electron microscope (FESEM) and JEM-200CX type transmission electron microscope (TEM), from stereoscan photograph (as Fig. 3 a), the NaNdF for preparing as can be known the selected area electron diffraction figure (such as Fig. 3 d) of transmission electron microscope photo (such as Fig. 3 b), single crystal transmission electron microscope photo (such as Fig. 3 c), single crystal and the single crystal high resolution transmission electron microscopy photo (such as Fig. 3 e) 4, pattern is single, uniform hexa-prism nanometer rod, and the end face of rod is hexagon, and end face diameter is about 100nm, length is about 650nm; The spot of diffraction can be expressed as respectively six side's phase NaNdF 4(112), (111) and (
Figure 376233DEST_PATH_IMAGE001
) crystal face; The SAED style shows that this crystal is one and grows reasonable monocrystalline, product NaNdF 4Six prismatic nanocrystallinely formed by single grain; The adjacent spacing of nanometer rod is 0.371nm, corresponding to NaNdF 4(
Figure 45111DEST_PATH_IMAGE001
) crystal face, show nanometer rod be along (
Figure 225426DEST_PATH_IMAGE001
) the direction growth; By product can spectrogram (such as Fig. 4) as can be known nanometer rod consist of Na, Nd and F, its content ratio meets its stoichiometric ratio.Luminescent spectrum figure (such as Fig. 5) under the room temperature shows that there is the strongest emission peak in this sample at the 1059nm place.
Embodiment two
As shown in Figure 1, NaNdF 4The preparation process of nanometer rod luminescent powder is:
(1) HNO of usefulness 10mol/L 3Dissolving Nd 2O 3, heated and stirred continues to be heated to solution residue 8% to the solution becomes clarification, namely make pre-reaction material Nd(NO 3) 3Solution;
(2) preparation sequestrant Na 2H 2EDTA solution, under the magnetic agitation condition with pre-reaction material Nd(NO 3) 3Solution mixes, and makes Nd in the solution 3+And Na 2H 2The mol ratio of EDTA is 1:0.5, stirring reaction 30min;
(3) add an amount of NaF solution to reaction soln, so that Nd in the solution 3+And F -Mol ratio be 1:6, use HNO 3Regulate mixing solutions pH value to 3, stir 10min, namely get the mixing solutions of the muddy thing of adularescent;
(4) mixing solutions is joined in the water heating kettle liner, be filled to 80% of liner volume, airtight water heating kettle carries out hydrothermal treatment consists, is incubated 12h under 200 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, after the centrifugal collection of reaction product, with dehydrated alcohol and distilled water repetitive scrubbing, dry 8h in loft drier, 70 ℃ of bake out temperatures namely get NaNdF 4Nanometer rod.
 
Embodiment three
As shown in Figure 1, NaNdF 4The preparation process of nanometer rod luminescent powder is:
(1) HNO of usefulness 10mol/L 3Dissolving Nd 2O 3, heated and stirred continues to be heated to solution residue 12% to the solution becomes clarification, namely make pre-reaction material Nd(NO 3) 3Solution;
(2) preparation sequestrant Na 2H 2EDTA solution, under the magnetic agitation condition with pre-reaction material Nd(NO 3) 3Solution mixes, and makes Nd in the solution 3+And Na 2H 2The mol ratio of EDTA is 1:2, stirring reaction 5min;
(3) add an amount of NaF solution to reaction soln, so that Nd in the solution 3+And F -Mol ratio be 1:10, use HNO 3Regulate mixing solutions pH value to 4, stir 20min, namely get the mixing solutions of the muddy thing of adularescent;
(4) mixing solutions is joined in the water heating kettle liner, be filled to 80% of liner volume, airtight water heating kettle carries out hydrothermal treatment consists, is incubated 48h under 160 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, after the centrifugal collection of reaction product, with dehydrated alcohol and distilled water repetitive scrubbing, dry 6h in loft drier, 60 ℃ of bake out temperatures namely get NaNdF 4Nanometer rod.
 
Embodiment four
As shown in Figure 1, NaNdF 4The preparation process of nanometer rod luminescent powder is:
(1) HNO of usefulness 10mol/L 3Dissolving Nd 2O 3, heated and stirred continues to be heated to solution residue 10% to the solution becomes clarification, namely make pre-reaction material Nd(NO 3) 3Solution;
(2) preparation sequestrant Na 2H 2EDTA solution, under the magnetic agitation condition with pre-reaction material Nd(NO 3) 3Solution mixes, and makes Nd in the solution 3+And Na 2H 2The mol ratio of EDTA is 1:1.5, stirring reaction 20min;
(3) add an amount of NaF solution to reaction soln, so that Nd in the solution 3+And F -Mol ratio be 1:8, use HNO 3Regulate mixing solutions pH value to 3, stir 30min, namely get the mixing solutions of the muddy thing of adularescent;
(4) mixing solutions is joined in the water heating kettle liner, be filled to 80% of liner volume, airtight water heating kettle carries out hydrothermal treatment consists, is incubated 36h under 170 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, after the centrifugal collection of reaction product, with dehydrated alcohol and distilled water repetitive scrubbing, dry 10h in loft drier, 50 ℃ of bake out temperatures namely get NaNdF 4Nanometer rod.

Claims (3)

1. NaNdF 4The preparation method of nanometer rod luminescent powder is characterized in that: may further comprise the steps:
(1) with the nitric acid dissolve Neodymium trioxide of 10mol/L, heated and stirred continues to be heated to solution residue 8%-12% to the solution becomes clarification, namely make pre-reaction material neodymium nitrate solution;
(2) preparation sequestrant disodium ethylene diamine tetra-acetic acid solution mixes with pre-reaction material neodymium nitrate solution, makes that the mol ratio of neodymium ion and disodium ethylene diamine tetraacetate is 1:(0.5-2 in the solution), stirring reaction 5-30min;
(3) add Fluorinse to reaction soln, so that the mol ratio of neodymium ion and fluorion is 1:(6-10 in the solution), regulate mixing solutions pH value to 2-4, stir 5-30min, namely get the mixing solutions of the muddy thing of adularescent;
(4) mixing solutions is joined the water heating kettle liner, be filled to 80% of liner volume, airtight water heating kettle carries out hydrothermal treatment consists;
(5) water heating kettle is naturally cooled to room temperature, after the centrifugal collection of reaction product, with dehydrated alcohol and distilled water repetitive scrubbing, in loft drier, dry, namely get NaNdF 4The nanometer rod luminescent powder.
2. NaNdF according to claim 1 4The preparation method of nanometer rod luminescent powder is characterized in that: in the described step (4), the temperature of hydrothermal treatment consists is 160-200 ℃, and the time is 12-48h.
3. NaNdF according to claim 1 4The preparation method of nanometer rod luminescent powder is characterized in that: in the described step (5), drying temperature is 50-100 ℃, time of drying 5-10h.
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Cited By (1)

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KR20170066559A (en) * 2014-10-08 2017-06-14 지이 라이팅 솔루션스, 엘엘씨 Materials and optical components for color filtering in a lighting apparatus

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Patent Citations (1)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10861690B2 (en) 2014-10-07 2020-12-08 Consumer Lighting (U.S.), Llc LED apparatus employing neodymium-fluorine materials
KR20170066559A (en) * 2014-10-08 2017-06-14 지이 라이팅 솔루션스, 엘엘씨 Materials and optical components for color filtering in a lighting apparatus
JP2017533462A (en) * 2014-10-08 2017-11-09 ジーイー・ライティング・ソルーションズ，エルエルシー Color filter materials and optical components for lighting devices
US10663143B2 (en) 2014-10-08 2020-05-26 Consumer Lighting (U.S.), Llc Materials and optical components for color filtering in a lighting apparatus
KR102339134B1 (en) * 2014-10-08 2021-12-15 커런트 라이팅 솔루션즈, 엘엘씨 Materials and optical components for color filtering in a lighting apparatus

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Application publication date: 20130417