CN110423614A - A kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder and its preparation method and application - Google Patents
A kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder and its preparation method and application, are related to luminescent material technical field.The preparation method includes that the mixed liquor containing calcium salt, at least two rare earth metal salts, phosphate and surfactant is placed under microwave condition to carry out hydro-thermal reaction, reaction solution is separated by solid-liquid separation after reaction, rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is made in drying.The preparation method is simple, makes hydro-thermal reaction more complete by the way that microwave is added, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder product pattern prepared is single, good dispersion.It can be widely applied in biological fluorescent labelling.
Description
Technical field
The present invention relates to luminescent material technical fields, in particular to a kind of rear-earth-doped 1-dimention nano hydroxy-apatite
Stone fluorescent powder and its preparation method and application.
Background technique
Since hydroxyapatite (HA) does not have toxicity, have many advantages, such as good biocompatibility and bioactivity, thus
HA becomes ideal biological fluorescent labelling material matrix.Studies have shown that the machinery of the microscopic appearance of HA material, partial size to itself
Intensity, bioactivity, fluorescence intensity have large effect.It is more preferable that research finds that nano HA particulate material has than common HA material
Bioactivity, the advantages that tensile strength, higher fatigue resistance and bone implant torsion modulus；At the same time it can also contain one
The growth and proliferation of a little tumour cells, and normal cell negative effect is not obvious, nano HA particle easily enters cell.For
Rear-earth-doped HA fluorescent powder the study found that nano rare earth adulterates HA compared with other materials, there is higher fluorescence intensity, red
Therefore orange is than synthesizing specific morphology, the nano rare earth doping HA fluorescent powder of partial size is beneficial to mention with higher quenching concentration
It rises, extend its application in terms of biologic medical, photoelectric material, intelligence.
The method for preparing rare earth mixing with nano HA fluorescent powder at present mainly has chemical precipitation method, hydro-thermal method, sol-gal process,
HA fluorescent powder is adulterated mainly for the preparation of single.But the product prepared at present there are patterns inhomogenous, irregular, dispersed and fluorescence
The deficiencies of performance is poor causes it not strong in biological fluorescent labelling and otherwise application.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation side of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder
Method, the preparation method is simple, and preparation time is short, makes hydro-thermal reaction more complete by the way that microwave is added, the rare earth prepared
Doped one-dimensional nanometer hydroxyapatite fluorescent powder product pattern is single, is monodimension nanometer material, good dispersion.
The second object of the present invention is to provide a kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder, product shape
Looks are single, are monodimension nanometer material, good dispersion.
It is glimmering in biology that the third object of the present invention is to provide a kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder
Application in signal, fluorescence property are preferable.
The present invention is implemented as follows:
In a first aspect, the embodiment of the present invention provides a kind of preparation side of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder
Method comprising: the mixed liquor containing calcium salt, at least two rare earth metal salts, phosphate and surfactant is placed in micro-strip
Hydro-thermal reaction is carried out under part, reaction solution is separated by solid-liquid separation after reaction, and rear-earth-doped 1-dimention nano hydroxy-apatite is made in drying
Stone fluorescent powder.
In alternative embodiments, the hydro-thermal reaction is to carry out under the microwave condition of 500-1000W in power；
Preferably, the reaction temperature of the hydro-thermal reaction is 140-160 DEG C；
Preferably, the reaction time of the hydro-thermal reaction is 10-60min.
In alternative embodiments, any rare earth element at least two rare earth metal salts and the calcium salt
In calcium constituent molar ratio be 0.01-0.1:1；Preferably, the calcium constituent in the calcium salt and the phosphorus in the phosphate
The molar ratio of element is 1.6-1.7:1.
In alternative embodiments, the amount ratio of the calcium salt and the surfactant is 1mol calcium constituent: 1-50g
Surfactant.
In alternative embodiments, the surfactant is Macrogol 4000, neopelex and ten
At least one of six alkyl trimethyl ammonium bromides；Preferably, the surfactant is Macrogol 4000；
Preferably, the calcium salt is selected from any one of calcium nitrate and calcium chloride, it is preferable that the calcium salt is calcium nitrate；
Preferably, the rare earth metal salt is selected from europium nitrate, terbium nitrate, scandium nitrate, yttrium nitrate, lanthanum nitrate, cerous nitrate, nitre
Sour praseodymium, neodymium nitrate, nitric acid promethium, samaric nitrate, gadolinium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, in lutecium nitrate
Both at least；Preferably, the rare earth metal salt is europium nitrate and terbium nitrate；
Preferably, the phosphate is any one of ammonium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate；Preferably, described
Phosphate is ammonium dihydrogen phosphate；
Preferably, when the calcium salt is calcium nitrate, the rare earth metal salt is europium nitrate and terbium nitrate, the phosphate are
When ammonium dihydrogen phosphate, the surfactant are Macrogol 4000, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent
The chemical composition of powder is Ca5-x-y(PO4)3(OH): xEu3+, yTb3+, wherein 0.01≤x≤0.1,0.01≤y≤0.1；It is preferred that
Ground, x=0.02-0.08, y=0.02-0.08.
In alternative embodiments, the preparation method of the mixed liquor includes:
A after) adding water to mix the calcium salt and at least two rare earth metal salts, the first mixed liquor is obtained；
B after) adding water to mix the phosphate and the surfactant, the second mixed liquor is obtained；
C) first mixed liquor is added into second mixed liquor, obtains mixed liquor；
Preferably, step A) in, the dosage of the calcium salt is calculated as 0.005-0.035mol, the rare earth metal with calcium constituent
The dosage of salt is calculated as the 1-10% of calcium constituent mole dosage with rare earth element, and the dosage of the water is 20-40mL；
Preferably, step B) in, the phosphatic dosage is calculated as 0.003-0.02mol with P elements, and the surface is living
Property agent dosage be 0.05-0.25g, the dosage of the water is 10-30mL.
In alternative embodiments, the pH value for controlling the mixed liquor is 8-10；Preferably, described in being adjusted using ammonium hydroxide
The pH value of mixed liquor；
Preferably, further include step D): the mixed liquor is stirred into 20-60min.
It in alternative embodiments, further include utilizing water and anhydrous after carrying out hydro-thermal reaction to the reaction solution
Ethyl alcohol successively washs, and repeats 2-4 times, is then dried；
Preferably, the dry 4-24h at 70-90 DEG C.
Second aspect, the embodiment of the present invention provide a kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder, are to adopt
With the preparation method preparation of the described in any item rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder of such as aforementioned embodiments
；
Preferably, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is in cone-shaped, and length is 200nm-1 μ
M, diameter is 50nm-100nm；
Preferably, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder in the form of sheets, and length be 500nm-1 μm,
With a thickness of 10nm-50nm, width 50-100nm；
Preferably, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is in rodlike, and length is 100-500nm,
Diameter is 50nm-100nm.
The third aspect, the embodiment of the present invention provide such as the described in any item rear-earth-doped 1-dimention nano hydroxyls of aforementioned embodiments
The rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder of the preparation method preparation of base apatite fluorescent powder or such as aforementioned embodiment party
Application of the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder in biological fluorescent labelling described in formula.
The invention has the following advantages: the application made using surfactant in mixed liquor reactant (calcium salt,
At least two rare earth metal salts and phosphate) dispersion is more evenly.Hydro-thermal reaction is placed under microwave condition simultaneously and is carried out, it can
Quickly heating, and homogeneous heating is realized, so that final product pattern is single, uniform in size.Through preparation provided by the present application
Method obtain rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder product pattern is single, good dispersion.It can be answered extensively
For in biological fluorescent labelling.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the XRD (A) and EDS (B) figure that the embodiment of the present invention 1 prepares product；
Fig. 2 is the XRD that 2-8 of the embodiment of the present invention prepares product；
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 1 prepares product；
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 2 prepares product；
Fig. 5 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 3 prepares product；
Fig. 6 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 4 prepares product；
Fig. 7 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 5 prepares product；
Fig. 8 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 6 prepares product；
Fig. 9 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 7 prepares product；
Figure 10 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 8 prepares product；
Figure 11 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 9 prepares product；
Figure 12 is the scanning electron microscope (SEM) photograph (SEM) that comparative example 1 of the present invention prepares product；
Figure 13 is the scanning electron microscope (SEM) photograph (SEM) that comparative example 2 of the present invention prepares product；
Figure 14 is the scanning electron microscope (SEM) photograph (SEM) that comparative example 3 of the present invention prepares product；
Figure 15 is the XRD that comparative example 4 of the present invention prepares product；
Figure 16 is the scanning electron microscope (SEM) photograph (SEM) that comparative example 5 of the present invention prepares product；
Figure 17 is fluorescence emission spectrogram of compound (λ the ex=395nm) (a: implementation that the embodiment of the present invention and comparative example prepare product
Example 6, b: comparative example 1, c: embodiment 1, d: comparative example 5, e: embodiment 3；F: embodiment 9, g: comparative example 2).
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
On the one hand, the present invention provides a kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder, preparation method packets
Include following steps:
S1, mixed liquor is prepared.
The mixed liquor be containing calcium salt, at least two rare earth metal salts, phosphate and surfactant mixed liquor, system
Preparation Method includes: after adding water to mix calcium salt and at least two rare earth metal salts, to obtain the first mixed liquor；By phosphate and surface
After activating agent adds water to mix, the second mixed liquor is obtained；First mixed liquor is added into the second mixed liquor, mixed liquor is obtained；Benefit
The pH value of the mixed liquor is adjusted with ammonium hydroxide, so that the pH value of mixed liquor is 8-10, it is preferable that the pH value of mixed liquor is 9-10.
In the application, using surfactant make in mixed liquor reactant (calcium salt, at least two rare earth metal salts with
And phosphate) dispersion is more evenly.In addition, in the application, by controlling the addition sequence of component, it is initially formed that be respectively formed first mixed
Liquid and the second mixed liquor are closed, then the first mixed liquor is slowly added into the second mixed liquor, so that the calcium in the first mixed liquor
Salt and at least two rare earth metal salts can be sufficiently uniformly scattered in the second mixed liquor, and dispersion effect is more preferably.Form mixing
Its pH value is adjusted after liquid and is constantly stirred, and is further mixed and is uniformly dispersed.
Through inventor the study found that in codope rare earth HA fluorescent powder, due to the transmitting light of different doping with rare-earth ions
Color is different, can adjust color and its intensity by adjusting doping ionic species, proportion；Furthermore it can be carried out between Doped ions
Energy transmission can optimize its fluorescence intensity, luminous efficiency.
Preferably, the calcium salt in the application is selected from any one of calcium nitrate and calcium chloride, it is further preferred that calcium salt is
Calcium nitrate.Preferably, rare earth metal salt be selected from europium nitrate, terbium nitrate, scandium nitrate, yttrium nitrate, lanthanum nitrate, cerous nitrate, praseodymium nitrate,
Neodymium nitrate, nitric acid promethium, samaric nitrate, gadolinium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, in lutecium nitrate at least
The two；It is further preferred that rare earth metal salt is europium nitrate and terbium nitrate.Preferably, phosphate is ammonium dihydrogen phosphate, phosphoric acid
Any one of sodium, dibastic sodium phosphate；It is further preferred that phosphate is ammonium dihydrogen phosphate.Preferably, surfactant is poly- second
At least one of glycol 4000, neopelex and cetyl trimethylammonium bromide；It is further preferred that surface
Activating agent is Macrogol 4000.
The molar ratio of the calcium constituent in any rare earth element and calcium salt at least two rare earth metal salts is 0.01-
0.1:1.The molar ratio of the P elements in calcium constituent and phosphate in calcium salt is 1.6-1.7:1.Calcium salt and surfactant
Amount ratio is 1mol calcium constituent: 1-50g surfactant.Specific in the application, the dosage of calcium salt in terms of calcium constituent substantially
0.005mol-0.035mol, the dosage of rare earth metal salt are calculated as the 1-10% of calcium constituent mole dosage with rare earth element, form the
The dosage of water when one mixed liquor is 20-40mL；Phosphatic dosage substantially 0.003-0.02mol, surface in terms of P elements
The dosage of activating agent substantially 0.05g-0.25g.The dosage substantially 10-30mL of water when forming the second mixed liquor.At other
In embodiment, above-mentioned dosage expand or shrink by multiple.
Preferably, when calcium salt is calcium nitrate, rare earth metal salt is europium nitrate and terbium nitrate, phosphate be ammonium dihydrogen phosphate,
When surfactant is Macrogol 4000, the chemical composition of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is Ca5-x-y
(PO4)3(OH): xEu3+, yTb3+, wherein 0.01≤x≤0.1,0.01≤y≤0.1, it is preferable that x=0.02-0.08, y=
0.02-0.08。
In the application, it is defined by the chemical composition to rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder, really
The content for having determined calcium salt therein, phosphate and at least two rare earth metal salts, through inventor the study found that working as calcium salt, phosphorus
Within the above range, the product pattern obtained is single, good dispersion for the molar ratio of hydrochlorate and at least two rare earth metal salts.
S2, hydro-thermal reaction is carried out under microwave condition to mixed liquor.
The mixed liquor that step S1 is obtained is to carry out hydro-thermal reaction under the microwave condition of 500-1000W in power, and hydro-thermal is anti-
The reaction temperature answered is 140-160 DEG C, reaction time 10-60min.Common hydro-thermal in being different from the prior art in the application
Reaction, carries out under microwave condition, by the way that mixed liquor to be transferred in hydrothermal reaction kettle, is subsequently placed in microwave reactor
It is inside reacted, the interaction of molecule can occur with the various reactants in mixed liquor for microwave, generate molecular polarization, take
It to, friction, collision, absorbs microwave energy and generates fuel factor, and then heated.Since microwave heating is after object absorbs microwave
Self-heating, heating start simultaneously at from interior of articles, outside, can accomplish inside and outside while heat.It can be realized quick heating, and add
It is hot uniform, so that final product pattern is single, uniform in size.
S3, washing.
After hydro-thermal reaction, hydrothermal reaction kettle is taken out and is cooled to room temperature, is then separated by solid-liquid separation.It is separated by solid-liquid separation
There are many modes, utilizes filter paper filtering, centrifuge separation or vacuum filtration.After isolation, further include using water and dehydrated alcohol according to
It is secondary that solid is washed, specifically, solid is washed first with water, is then washed again with dehydrated alcohol, then
It repeats 2-4 times, in repetitive process, also using being washed first with water to solid, is then washed again with dehydrated alcohol
Mode carries out.
S4, drying.
After the completion of washing, 4-24h is dried to solid at 70-90 DEG C, obtains products C a5-x-y(PO4)3(OH): xEu3 +,yTb3+, wherein 0.01≤x≤0.1,0.01≤y≤0.1, it is preferable that x=0.02-0.08, y=0.02-0.08；
Preferably, rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is in cone-shaped, and length is 200nm-1 μm, directly
Diameter is 50nm-100nm；
Preferably, rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder in the form of sheets, and length be 500nm-1 μm, thickness
For 10nm-50nm, width 50-100nm；
Preferably, rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is in rodlike, and length is 100-500nm, diameter
For 50nm-100nm.
Rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder provided by the present application, pattern is single, good dispersion, shines
Intensity is high, can be widely applied to answering for biologic medical, photoelectric material, biological fluorescent labelling involved in intelligent sensitive material etc.
With.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is present embodiments provided, preparation method includes as follows
Step:
By 0.02mol Ca (NO3)2·4H2O and according to Eu3+With Ca2+Molar ratio be 0.06:1, Tb3+With Ca2+Mole
Europium nitrate, the terbium nitrate that corresponding amount is added than the ratio for 0.06:1 add 30mL water to mix, and obtain the first solution；
It is that 1.67:1 weighs 0.012mol (NH by the molar ratio of calcium and phosphorus4)H2PO4Add with the mixing of 0.1g Macrogol 4000
30mL distilled water is configured to the second solution；
First solution is slowly added into the second solution, is 10 with the pH value that ammonium hydroxide adjusts solution, continues to stir 30min
Afterwards by mixed liquor be transferred to hydrothermal reaction kettle in microwave reactor in power be 800W microwave condition and 150 DEG C at a temperature of
40min is reacted, taking-up is cooled to room temperature.
Reaction solution is filtered by vacuum, solid is washed three times with 50 DEG C of warm water, dehydrated alcohol respectively, in 80 DEG C of dry 12h
Obtain products C a4.88(PO4)3(OH): 0.06Eu3+,0.06Tb3+。
Fig. 1 is the XRD spectra that embodiment 1 prepares product.It may be seen that the peak shape of product and peak position and Ca5(PO4)3
(OH) (the associated diffraction peak position of (JCPDS 86-0740) standard spectrogram is almost the same, without Eu3+And Tb3+Compound spread out
Penetrate peak appearance.This shows do not have new object mutually to be formed in sample, sample substrate Ca5(PO4)3(OH).It can be seen that from EDS figure
Contain 5 kinds of elements of Ca, P, O, Eu and Tb in product, shows that Eu, Tb are successfully adulterated in conjunction with its XRD spectra and enter matrix, on a small quantity
Eu3+、Tb3+Doping the bulk crystal structure of matrix is influenced it is smaller.
Fig. 3 is the low power and high power SEM figure that embodiment 1 prepares product, be can be seen that from low power figure, and product pattern is single,
For cone-shaped, good dispersion；Can be seen that from high power figure, cone-shaped size is inhomogenous, length is about 200nm-1 μm, diameter about
It is monodimension nanometer material for 50nm-100nm.
Embodiment 2
A kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is present embodiments provided, preparation method includes as follows
Step:
By 0.03mol Ca (NO3)2·4H2O and according to Eu3+With Ca2+Molar ratio be 0.02:1, Tb3+With Ca2+Mole
Europium nitrate, the terbium nitrate that corresponding amount is added than the ratio for 0.02:1 add 30mL water to mix, and obtain the first solution；
It is that 1.60:1 weighs 0.019mol (NH by the molar ratio of calcium and phosphorus4)H2PO4Add with the mixing of 0.2g Macrogol 4000
30mL distilled water is configured to the second solution；
First solution is slowly added into the second solution, is 9 with the pH value that ammonium hydroxide adjusts solution, continues to stir 30min
Afterwards by mixed liquor be transferred to hydrothermal reaction kettle in microwave reactor in power be 500W microwave condition and 140 DEG C at a temperature of
60min is reacted, taking-up is cooled to room temperature.
Reaction solution is filtered by vacuum, solid is washed four times with 60 DEG C of warm water, dehydrated alcohol respectively, in 70 DEG C of dry 16h
Obtain products C a4.96(PO4)3(OH): 0.02Eu3+,0.02Tb3+。
(a) is the XRD spectra that embodiment 2 prepares product in Fig. 2.It may be seen that the peak shape of product and peak position and Ca5
(PO4)3(OH) (the associated diffraction peak position of (JCPDS 86-0740) standard spectrogram is almost the same to show that the product matrix is Ca5
(PO4)3(OH)。
Fig. 4 is the low power and high power SEM figure that embodiment 2 prepares product, be can be seen that from low power figure, and product pattern is single,
For sheet；It can be seen that from high power figure, sheet size is more uniform, and length is about 200nm, width is about 50nm, thickness is about
20nm is monodimension nanometer material.
Embodiment 3
A kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is present embodiments provided, preparation method includes as follows
Step:
By 0.005mol Ca (NO3)2·4H2O and according to Eu3+With Ca2+Molar ratio be 0.08:1, Tb3+With Ca2+Rub
You add 20mL water to mix than europium nitrate, the terbium nitrate of the ratio addition corresponding amount for being 0.08:1, obtain the first solution；
It is that 1.7:1 weighs a certain amount of (0.003mol) (NH by the molar ratio of calcium and phosphorus4)H2PO4With 0.05g polyethylene glycol
4000 mixing plus 20mL distilled water are configured to the second solution；
First solution is slowly added into the second solution, is 8 with the pH value that ammonium hydroxide adjusts solution, continues to stir 30min
Mixed liquor is transferred to hydrothermal reaction kettle in microwave reactor in microwave condition and 160 DEG C of temperature that power is 1000W afterwards
Lower reaction 20min, taking-up are cooled to room temperature.
Reaction solution is filtered by vacuum, solid is washed twice with 60 DEG C of warm water, dehydrated alcohols respectively, in 90 DEG C of dry 10h
Obtain products C a4.84(PO4)3(OH): 0.08Eu3+,0.08Tb3+。
(b) is the XRD spectra that embodiment 3 prepares product in Fig. 2.It may be seen that the peak shape of product and peak position and Ca5
(PO4)3(OH) (the associated diffraction peak position of (JCPDS 86-0740) standard spectrogram is almost the same to show that the product matrix is Ca5
(PO4)3(OH)。
Fig. 5 is the low power and high power SEM figure that embodiment 3 prepares product, be can be seen that from low power figure, and product pattern is single,
For sheet；It can be seen that from high power figure, sheet size is more uniform, and length is about 300nm, width is about 50nm, thickness is about
40nm is monodimension nanometer material.
Embodiment 4
Preparation method provided in this embodiment is substantially the same manner as Example 1, the difference is that only addition polyethylene glycol
4000 amounts are adjusted to 0.25g, obtain products C a4.88(PO4)3(OH): 0.06Eu3+,0.06Tb3+。
(c) is the XRD spectra that embodiment 4 prepares product in Fig. 2.It may be seen that the peak shape of product and peak position and Ca5
(PO4)3(OH) (the associated diffraction peak position of (JCPDS 86-0740) standard spectrogram is almost the same to show that the product matrix is Ca5
(PO4)3(OH)。
Fig. 6 is the low power and high power SEM figure that embodiment 4 prepares product.It can be seen that from low power figure (a), product pattern list
One, it is corynebacterium, is uniformly dispersed, size is more uniform.It can be seen that from high power figure (b), stub length is about 100-300nm, directly
Diameter is about 50nm-100nm, is monodimension nanometer material.
Embodiment 5
Preparation method provided in this embodiment is substantially the same manner as Example 1, the difference is that only used herein
Rare earth metal salt is yttrium nitrate and europium nitrate, and products C a is prepared4.88(PO4)3(OH): 0.06Y3+,0.06Eu3+。
(d) is the XRD spectra that embodiment 5 prepares product in Fig. 2.It may be seen that the peak shape of product and peak position and Ca5
(PO4)3(OH) (the associated diffraction peak position of (JCPDS 86-0740) standard spectrogram is almost the same to show that the product matrix is Ca5
(PO4)3(OH)。
Fig. 7 is the low power and high power SEM figure that embodiment 5 prepares product, be can be seen that from low power figure, and product pattern is single,
It is plate-like；It can be seen that from high power figure, plate-like size is more uniform, and length is about 200-300nm, width is about 50nm, thickness
Degree is about 30-50nm, is monodimension nanometer material.
Embodiment 6
Preparation method provided in this embodiment is substantially the same manner as Example 1, the difference is that only in microwave reactor
The reaction time is adjusted to 50min at 150 DEG C, obtains products C a4.88(PO4)3(OH): 0.06Eu3+,0.06Tb3+。
(e) is the XRD spectra that embodiment 6 prepares product in Fig. 2.It may be seen that the peak shape of product and peak position and Ca5
(PO4)3(OH) (the associated diffraction peak position of (JCPDS 86-0740) standard spectrogram is almost the same to show that the product matrix is Ca5
(PO4)3(OH)。
Fig. 8 is the low power and high power SEM figure that embodiment 6 prepares product.It can be seen that from low power figure (a), product pattern list
One, it is rodlike, good dispersion；It can be seen that from high power figure (b), rodlike length is about 500nm, and thickness is about 50nm-100nm, is
Monodimension nanometer material.
Embodiment 7
Preparation method provided in this embodiment is substantially the same manner as Example 1, the difference is that only used herein
Calcium salt is calcium chloride.
(f) is the XRD spectra that embodiment 7 prepares product in Fig. 2.It may be seen that the peak shape of product and peak position and Ca5
(PO4)3(OH) (the associated diffraction peak position of (JCPDS 86-0740) standard spectrogram is almost the same to show that the product matrix is Ca5
(PO4)3(OH)。
Fig. 9 is the low power and high power SEM figure that embodiment 7 prepares product.It can be seen that from low power figure (a), product pattern list
One, it is rodlike, good dispersion；It can be seen that from high power figure (b), rodlike length is about 500nm, and diameter is about 50nm, is a wiener
Rice material.
Embodiment 8
Preparation method provided in this embodiment is substantially the same manner as Example 1, the difference is that only used herein
Phosphate is disodium hydrogen phosphate.
(g) is the XRD spectra that embodiment 8 prepares product in Fig. 2.It may be seen that the peak shape of product and peak position and Ca5
(PO4)3(OH) (the associated diffraction peak position of (JCPDS 86-0740) standard spectrogram is almost the same to show that the product matrix is Ca5
(PO4)3(OH)。
Figure 10 is the low power and high power SEM figure that embodiment 8 prepares product.It can be seen that from low power figure (a), product pattern list
One, it is sheet, good dispersion；It can be seen that from high power figure (b), sheet length is about 300nm, and thickness is about 30nm, and width is about
50nm is monodimension nanometer material.
Embodiment 9
Preparation method provided in this embodiment is substantially the same manner as Example 1, the difference is that only used herein
Surfactant is cetyl trimethylammonium bromide.
Figure 11 is the low power and high power SEM figure that embodiment 9 prepares product.It can be seen that from low power figure (a), product pattern list
One, it is sheet, good dispersion；It can be seen that from high power figure (b), sheet length is about 300nm, and thickness is about 30nm, and width is about
50nm is monodimension nanometer material.
Comparative example 1
The preparation method that comparative example 1 provides is substantially the same manner as Example 1, the difference is that only reaction time 2h, prepares
Obtain products C a4.88(PO4)3(OH): 0.06Eu3+,0.06Tb3+。
Figure 12 is the low power and high power SEM figure that comparative example 1 prepares product.It can be seen that from low power figure (a), product pattern is not
Single, different morphologies are simultaneously deposited.There are mainly two types of pattern, for one kind to be a small amount of existing irregular rodlike, one is a large amount of existing
It is irregular granular.It can be seen that from high power figure (b), granular appearance and size is in 50nm-200nm range；Rodlike size is inhomogenous, long
500nm-3 μm of degree, shape is relatively regular.
Comparative example 2
The preparation method that comparative example 2 provides is substantially the same manner as Example 1, the difference is that only and is added without polyethylene glycol
4000, Ca5-x-y(PO4)3(OH): 0.06Eu3+,0.06Tb3+。
Figure 13 is the low power and high power SEM figure that comparative example 2 prepares product.It can be seen that from low power figure, product pattern is not single
One, different morphologies are simultaneously deposited, there are mainly two types of pattern: one is irregular rodlike, one is irregular granular.It can from high power figure
To find out, rodlike size is inhomogenous, and it is 500nm-3 μm of length, diameter 100-400nm, in irregular shape, it is micron order material；It is granular
Appearance and size is in 50nm-200nm range.
Comparative example 3
Preparation method provided in this embodiment is substantially the same manner as Example 1, the difference is that only mixed liquor with ammonium hydroxide
PH value be adjusted to 7, obtain products C a4.88(PO4)3(OH): 0.06Eu3+,0.06Tb3+。
Figure 14 is the low power and high power SEM figure that comparative example 3 prepares product.It can be seen that from low power figure (a), product pattern list
One, it is sheet.It can be seen that from high power figure (b), sheet size is inhomogenous, and length is about 500nm-1 μm, thickness is about 50nm-
100nm, wide about 100-200nm are two-dimension nano materials, are not monodimension nanometer materials.
Comparative example 4
Preparation method provided in this embodiment is substantially the same manner as Example 1, the difference is that only will be adjusted with ammonium hydroxide it is molten
The pH value of liquid is 5, and product is prepared.
Figure 15 is that comparative example 4 prepares X-ray diffraction (XRD) figure of product, as shown, by with CaHPO4Standard spectrum
Scheme (JCPDS:71-1759) control discovery, prepares all diffraction maximums of XRD and CaHPO of product4Standard spectrogram (JCPDS:71-
1759) unanimously, show that this matrix is CaHPO4, it is not Ca5(PO4)3(OH)。
Comparative example 5
The preparation method that comparative example 5 provides is substantially the same manner as Example 1, the difference is that only solution being transferred to hydro-thermal
Reaction kettle reacts 6h at 150 DEG C in a conventional oven, using common hydro-thermal method.
Figure 16 is the low power and high power SEM figure that comparative example 5 prepares product.It can be seen that from low power figure (a), product pattern is not
It is single, there are mainly two types of pattern, it is most of be it is irregular microgranular, separately have a small amount of irregular sheet.It can from high power figure (b)
Out, flake shape is irregular, and size is inhomogenous, about 1 μm -5 μm long, thickness about 100-200nm；Granular appearance and size exists
50nm-200nm range.
Comparative example 6
The embodiment of the present application 1,3,6,9 and comparative example 1,2,5 are prepared into product and carry out fluorescent emission analysis, obtains fluorescence hair
Spectrogram (λ ex=395nm) is penetrated, Figure 17 (a: embodiment 6, b: comparative example 1, c: embodiment 1, d: comparative example 5, e: real is please referred to
Apply example 3；F: embodiment 9, g: comparative example 2).It can be seen that the emission peak positions for preparing product are almost the same in figure, wherein
The emission peak occurred at 592nm, 617nm, 652nm, 697nm is respectively belonging to Eu3+'s5D0-7F1、5D0-7F2、5D0-7F3、5D0-7F4Energy level transition, wherein highest peak is located at 617nm, be emitting red light, show Eu3+Mainly occupy no centre of inversion case.
It is found in figure, embodiment, which prepares product emission peak intensity at wavelength 592nm, 617nm and is integrally higher than comparative example, prepares product, table
Bright the method for the present invention prepares product with better luminescent properties.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder, characterized in that it comprises: will contain
Calcium salt, at least two rare earth metal salts, phosphate and surfactant mixed liquor be placed under microwave condition and carry out hydro-thermal reaction,
Reaction solution is separated by solid-liquid separation after reaction, rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is made in drying.
2. the preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder according to claim 1, feature exist
In the hydro-thermal reaction is to carry out under the microwave condition of 500-1000W in power；
Preferably, the reaction temperature of the hydro-thermal reaction is 140-160 DEG C；
Preferably, the reaction time of the hydro-thermal reaction is 10-60min.
3. the preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder according to claim 1, feature exist
In the molar ratio of any rare earth element and the calcium constituent in the calcium salt at least two rare earth metal salts is
0.01-0.1:1；
Preferably, the molar ratio of the calcium constituent in the calcium salt and the P elements in the phosphate is 1.6-1.7:1.
4. the preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder according to claim 1, feature exist
In the amount ratio of the calcium salt and the surfactant is 1mol calcium constituent: 1-50g surfactant.
5. the preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder according to claim 1, feature exist
In, the surfactant be in Macrogol 4000, neopelex and cetyl trimethylammonium bromide extremely
Few one kind；
Preferably, the calcium salt is selected from any one of calcium nitrate and calcium chloride, it is preferable that the calcium salt is calcium nitrate；
Preferably, the rare earth metal salt is selected from europium nitrate, terbium nitrate, scandium nitrate, yttrium nitrate, lanthanum nitrate, cerous nitrate, nitric acid
Praseodymium, neodymium nitrate, nitric acid promethium, samaric nitrate, gadolinium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, in lutecium nitrate
Both at least；Preferably, the rare earth metal salt is europium nitrate and terbium nitrate；
Preferably, the phosphate is any one of ammonium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate；Preferably, the phosphoric acid
Salt is ammonium dihydrogen phosphate；
Preferably, when the calcium salt is calcium nitrate, the rare earth metal salt is europium nitrate and terbium nitrate, the phosphate are phosphoric acid
When ammonium dihydrogen, the surfactant are Macrogol 4000, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder
Chemical composition is Ca5-x-y(PO4)3(OH): xEu3+, yTb3+, wherein 0.01≤x≤0.1,0.01≤y≤0.1；Preferably, x=
0.02-0.08, y=0.02-0.08.
6. the preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder according to claim 1, feature exist
In the preparation method of the mixed liquor includes:
A after) adding water to mix the calcium salt and at least two rare earth metal salts, the first mixed liquor is obtained；
B after) adding water to mix the phosphate and the surfactant, the second mixed liquor is obtained；
C) first mixed liquor is added into second mixed liquor, obtains mixed liquor；
Preferably, step A) in, the dosage of the calcium salt is calculated as 0.005-0.035mol with calcium constituent, the rare earth metal salt
Dosage is calculated as the 1-10% of calcium constituent mole dosage with rare earth element, and the dosage of the water is 20-40mL；
Preferably, step B) in, the phosphatic dosage is calculated as 0.003-0.02mol, the surfactant with P elements
Dosage be 0.05-0.25g, the dosage of the water is 10-30mL.
7. the preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder according to claim 1, feature exist
In the pH value for controlling the mixed liquor is 8-10；Preferably, the pH value of the mixed liquor is adjusted using ammonium hydroxide；
Preferably, further include step D): the mixed liquor is stirred into 20-60min.
8. the preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder according to claim 1, feature exist
In, after carrying out hydro-thermal reaction to the reaction solution, further includes successively being washed using water and dehydrated alcohol, repeat 2-4 times, with
After be dried；
Preferably, the dry 4-24h at 70-90 DEG C.
9. a kind of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder, which is characterized in that it is appointed using such as claim 1-8
The preparation method of rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder described in one is prepared；
Preferably, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is in cone-shaped, and length is 200nm-1 μm, directly
Diameter is 50nm-100nm；
Preferably, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder in the form of sheets, and length be 500nm-1 μm, thickness
For 50nm-100nm, width 100-200nm；
Preferably, the rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder is in rodlike, and length is 100-500nm, diameter
For 50nm-100nm.
10. such as the preparation method system of the described in any item rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder of claim 1-8
Standby rear-earth-doped 1-dimention nano hydroxyl apatite fluorescent powder or rear-earth-doped 1-dimention nano hydroxyl phosphorus as claimed in claim 9
Application of the lime stone fluorescent powder in biological fluorescent labelling.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107487765A (en) * | 2017-07-06 | 2017-12-19 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire base fluorescence incombustible paper and its application |
-
2019
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107487765A (en) * | 2017-07-06 | 2017-12-19 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire base fluorescence incombustible paper and its application |
Non-Patent Citations (2)
| Title |
|---|
| CAI ZHENGWEI: "Large-scale and fast synthesis of nano-hydroxyapatite powder by a microwave hydrothermal method", 《RSC ADVANCES》 * |
| 吴占敖: "反应温度和有机修饰剂对医用纳米羟基磷灰石尺寸的影响", 《中国组织工程研究与临床康复》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748337A (en) * | 2020-07-27 | 2020-10-09 | 吉林大学 | Preparation method of fluorescent marker applied to osteoporosis |
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