CN109694050A - A kind of preparation method of nanometer of phosphoric acid titanyl ammonium crystal - Google Patents
A kind of preparation method of nanometer of phosphoric acid titanyl ammonium crystal Download PDFInfo
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- CN109694050A CN109694050A CN201910068733.1A CN201910068733A CN109694050A CN 109694050 A CN109694050 A CN 109694050A CN 201910068733 A CN201910068733 A CN 201910068733A CN 109694050 A CN109694050 A CN 109694050A
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- phosphoric acid
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- acid titanyl
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The present invention provides the preparation methods of a kind of nanometer of phosphoric acid titanyl ammonium crystal, are related to field of crystals.The preparation method of nanometer phosphoric acid titanyl ammonium crystal provided by the invention, comprising the following steps: after mixing titanium salt and ammonium hydroxide in water, then mix with phosphoric acid, obtain mixed liquor；The molar ratio of Ti, P and N element is 1:0.8~1:6~10 in the mixed liquor；It is cooled down after mixed liquor to be carried out to hydro-thermal reaction in confined conditions, obtains a nanometer phosphoric acid titanyl ammonium crystal.The phosphoric acid titanyl ammonium crystal of nano-scale can be prepared in method provided by the invention, and the phosphoric acid titanyl ammonium crystal dispersion effect that the present invention is prepared is preferable, does not reunite.The nanoscale phosphoric acid titanyl ammonium crystal being prepared using the present invention is conducive to growth and obtains the big crystal of phosphoric acid titanyl ammonium of high quality as raw material.
Description
Technical field
The present invention relates to field of crystals more particularly to the preparation methods of a kind of nanometer of phosphoric acid titanyl ammonium crystal.
Background technique
MTiOXO4(M=Li, Na, K, Rb, NH4, Cs, X=P or As) type crystal is famous nonlinear optical crystal body
System, such as KTiOPO4(being abbreviated as KTP) crystal is one of non-linear optical crystal material of excellent combination property.In same type
In crystal, NH4TiOPO4(being abbreviated as ATP) crystal has unique nonlinear optical effect controllably closing property, so that ATP is non-
Linear optics field possesses larger potentiality.But before ATP crystal growth, first have to obtain high-quality feedstocks, to reduce ATP crystalline substance
The defects of body growth course improves the quality of ATP crystal.
The prior art (J.Mater.Chem.A2016,4 (19), 7141-7147) discloses a kind of hydro-thermal method synthesis phosphoric acid
The report of titanyl ammonium (ATP) solid powder, but the ATP crystal that the document is finally prepared is micron-stage sheet-like rhombohedral crystal
Body, and it is unable to get nanoscale ATP crystal.Therefore, the phosphoric acid titanyl ammonium for how providing a kind of nano-scale and soilless sticking is former
Material is of great significance.
Summary of the invention
The present invention provides the preparation method of a kind of nanometer of phosphoric acid titanyl ammonium crystal, method provided by the invention is prepared
Phosphoric acid titanyl ammonium crystalline size be nanoscale, and dispersion effect is preferable, does not reunite, and is received with what the present invention was prepared
Rice phosphoric acid titanyl ammonium crystal is raw material, is conducive to the big crystal of ATP that high quality is prepared.
The present invention provides the preparation methods of a kind of nanometer of phosphoric acid titanyl ammonium crystal, comprising the following steps:
(1) it after mixing titanium salt, ammonium hydroxide and water, then mixes with phosphoric acid, obtains mixed liquor；
The molar ratio of Ti, P and N element is 1:0.8~1:6~10 in the mixed liquor；
(2) it is cooled down after the mixed liquor that the step (1) obtains being carried out hydro-thermal reaction in confined conditions, obtains nanometer
Phosphoric acid titanyl ammonium crystal.
Preferably, the quality of step (1) titanium salt and the volume ratio of water are 0.5~1.0g:2~4mL.
Preferably, titanium salt includes TiOSO in the step (1)4、TiCl4With Ti (SO4)2One of or it is a variety of.
Preferably, the temperature of hydro-thermal reaction is 180~220 DEG C in the step (2)；The time of hydro-thermal reaction is 3~7
It.
Preferably, the heating rate that hydrothermal temperature is warming up in the step (2) is 0.5~1.5 DEG C/min.
Preferably, the step (2) temperature after cooling is 20~30 DEG C, the rate of the cooling is 2.5~3.5 DEG C/
h。
The present invention provides the preparation methods of a kind of nanometer of phosphoric acid titanyl ammonium crystal, comprising the following steps: by titanium salt, ammonium hydroxide
It is mixed after water mixing, then with phosphoric acid, obtains mixed liquor；The molar ratio of Ti, P and N element is 1:0.8 in the mixed liquor
~1:6~10；It is cooled down after mixed liquor to be carried out to hydro-thermal reaction in confined conditions, obtains a nanometer phosphoric acid titanyl ammonium crystal.This
The method that invention provides can be prepared that size is small, with high purity and finely dispersed phosphoric acid titanyl ammonium crystal, be surveyed by embodiment
Test result is it is found that the phosphoric acid titanyl ammonium crystalline size that the present invention is prepared is 20~100nm；And the present invention is prepared
Phosphoric acid titanyl ammonium crystal dispersion effect is preferable, does not reunite.With the size that the present invention is prepared, small, with high purity and dispersion is equal
Even nanoscale phosphoric acid titanyl ammonium crystal is raw material, is conducive to growth and obtains the big crystal of ATP of high quality.
Detailed description of the invention
Fig. 1 is the XRD spectra for the product that embodiment 1 is prepared；
Fig. 2 is the transmission electron microscope picture for the product that embodiment 1 is prepared；
Fig. 3 is the XRD spectra for the product that embodiment 2 is prepared；
Fig. 4 is the transmission electron microscope picture for the product that embodiment 2 is prepared；
Fig. 5 is the XRD spectra for the product that comparative example 1 is prepared；
Fig. 6 is the XRD spectra for the product that comparative example 2 is prepared.
Specific embodiment
The present invention provides the preparation methods of a kind of nanometer of phosphoric acid titanyl ammonium crystal, comprising the following steps:
(1) it after mixing titanium salt, ammonium hydroxide and water, then mixes with phosphoric acid, obtains mixed liquor；
(2) it is cooled down after the mixed liquor that the step (1) obtains being carried out hydro-thermal reaction in confined conditions, obtains nanometer
Phosphoric acid titanyl ammonium crystal.
In the present invention, all raw materials are commercial goods.
It after the present invention mixes titanium salt, ammonium hydroxide and water, then mixes with phosphoric acid, obtains mixed liquor.
In the present invention, the titanium salt preferably includes TiOSO4、TiCl4With Ti (SO4)2One of or it is a variety of；The ammonia
The mass concentration of water is preferably 25%；The mass concentration of the phosphoric acid is preferably 85%.In the present invention, the quality of the titanium salt
Volume ratio with water is preferably 0.5~1.0g:2~4mL, further preferably 0.6~0.9g:2~4mL.In the present invention, institute
Stating the molar ratio of Ti, P and N element in mixed liquor is 1:0.8~1:6~10, preferably 1:0.9:7~9.
After the present invention is mixed with phosphoric acid, preferably mixture system is stirred, obtains mixed liquor.In the present invention,
The time of the stirring is preferably 3~4h, so that titanium salt, ammonium hydroxide and phosphoric acid can be sufficiently mixed.
The present invention first mixes titanium salt and ammonium hydroxide, then mixes again with phosphoric acid, it then follows sour feeding sequence is put after first putting alkali,
So that W-response carries out under alkaline condition, thus efficiently a large amount of productive target product.
The present invention controls the molar ratio of Ti, P in mixed liquor and N element in above range, can guarantee to be prepared
Product be ATP crystal.
After obtaining mixed liquor, mixed liquor is carried out cooling after hydro-thermal reaction by the present invention in confined conditions, is received
Rice phosphoric acid titanyl ammonium crystal.
In the present invention, the temperature of the hydro-thermal reaction is preferably 180~220 DEG C, and further preferably 190~220 DEG C,
The heating rate for being warming up to the hydrothermal temperature is preferably 0.5~1.5 DEG C/min, further preferably 0.8~1.2 DEG C/
min.In the present invention, the time of the hydro-thermal reaction is preferably 3~7 days, and further preferably 4~6 days.
After the completion of hydro-thermal reaction, the present invention cools down reaction system, obtains a nanometer phosphoric acid titanyl ammonium crystal.In this hair
In bright, the temperature after cooling is preferably 20~30 DEG C, and further preferably 25 DEG C；The rate of the cooling is preferably 2.5
~3.5 DEG C/h, further preferably 3 DEG C/h.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1
Weigh the TiOSO of starting material element molar ratio Ti:P:N=1:1:64、H3PO4And NH3·H2O.It is by 0.955g purity
The TiOSO of 93wt%4It is dissolved in 3mL deionized water, it is 25wt%'s that 2.49mL mass concentration is then first added dropwise into solution
NH3·H2O stirs 30s, and the H that 0.38mL mass concentration is 85wt% is then added3PO4, 4h is stirred, obtained white emulsion turns
It moves on in 25mL liner and is put into autoclave, be then sealed against being placed in baking oven.Baking oven is raised to 220 DEG C with 3h, keeps the temperature 4 days, so
Room temperature is dropped to the speed of 3 DEG C/h afterwards.It is collected by filtration to obtain white ATP powder, sufficiently be washed with deionized water, 50 DEG C dry
To the ATP of 0.91g, yield 92.6%.
X-ray diffraction analysis and transmission electron microscope analysis are carried out to the white powder that embodiment 1 obtains, as a result such as Fig. 1 and figure
Shown in 2, Fig. 1 is XRD spectra, and Fig. 2 is transmission electron microscope spectrogram.As shown in Figure 1, the white powder that the present invention is prepared is ATP
Crystal, and purity is higher；As shown in Figure 2, the ATP crystal morphology that the present invention is prepared is ellipse, having a size of nanoscale, directly
Diameter is 20~60nm, greater homogeneity, structural integrity.
Embodiment 2
Weigh the Ti (SO of starting material element molar ratio Ti:P:N=1:1:64)2、H3PO4And NH3·H2O.It will be load weighted
0.654gTi(SO4)2It is dissolved in 3mL deionized water, it is 25wt%'s that 1.22mL mass concentration is then first added dropwise into solution
NH3·H2O stirs 30s, and the H that 0.19mL mass concentration is 85wt% is then added3PO4, 4h is stirred, obtained white emulsion turns
It moves on in 25mL liner and is put into autoclave, be then sealed against being placed in baking oven.Baking oven is raised to 220 DEG C with 3h, keeps the temperature 3 days, so
Room temperature is dropped to the speed of 3 DEG C/h afterwards.It is collected by filtration to obtain white ATP powder, sufficiently be washed with deionized water, 50 DEG C dry
To the ATP of 0.46g, yield 95.3%.
X-ray diffraction analysis and transmission electron microscope analysis are carried out to the white powder that embodiment 2 obtains, as a result such as Fig. 3 and figure
Shown in 4, Fig. 3 is XRD spectra, and Fig. 4 is transmission electron microscope spectrogram.The curve on the upper layer Fig. 3 is the XRD curve of 2 product of embodiment, Fig. 3
The curve of lower layer is ATP crystal standard spectrogram, from the figure 3, it may be seen that the white powder that the present invention is prepared is ATP crystal, and pure
It spends higher；As shown in Figure 4, the ATP crystal morphology that the present invention is prepared is ellipse, having a size of nanoscale, diameter is 20~
70nm, greater homogeneity, structural integrity.
Comparative example 1
Embodiment 2 is repeated, unlike: starting material element molar ratio Ti:P:NH4=1:1:4.
By the reaction of condition same as Example 2, the product that comparative example 1 obtains is not ATP but NH4H(PO3)2、
TiO2With the analog of ammonium phosphate.XRD test is carried out to the product that comparative example 1 obtains, test results are shown in figure 5, the upper layer Fig. 5
Curve be 1 product of comparative example XRD curve, the curve of Fig. 5 lower layer is ATP crystal standard spectrogram.As shown in Figure 5, raw material is matched
Than playing a significant role for ATP crystal can be prepared.
Comparative example 2
Embodiment 2 is repeated, unlike: toward Ti4+H is first added in solution3PO4Then plus NH 30s is stirred,3·H2O stirring
4h。
By the reaction of condition same as Example 2, the product that comparative example 2 obtains not instead of ATP, TiO2And ammonium phosphate
Analog.XRD test is carried out to the product that comparative example 2 obtains, test results are shown in figure 6, and the curve on the upper layer Fig. 6 is comparison
The XRD curve of 2 product of example, the curve of Fig. 6 lower layer are ATP crystal mock standard spectrogram.It will be appreciated from fig. 6 that the charging sequence of raw material
For ATP crystal can be prepared, play a significant role.
Embodiment 3
Weigh starting material element molar ratio Ti:P:NH4Ti (the SO of=1:0.8:64)2、H3PO4And NH3·H2O.It will weigh
0.685g Ti (SO4)2It is dissolved in 4mL deionized water, it is 25wt%'s that 1.28mL mass concentration is then first added dropwise into solution
NH3·H2O stirs 40s, and the H that 0.16mL mass concentration is 85wt% is then added3PO4, 4h is stirred, obtained white emulsion turns
It moves on in 25mL liner and is put into autoclave, be then sealed against being placed in baking oven.Baking oven is raised to 180 DEG C with 3h, keeps the temperature 7 days, so
Room temperature is dropped to the speed of 3 DEG C/h afterwards.It is collected by filtration to obtain white ATP powder, sufficiently be washed with deionized water, 50 DEG C dry
To the ATP of 0.47g, yield 93.1%；Obtained white powder is analyzed through X-ray diffraction and transmission electron microscope analysis, is ellipse
Round nanoscale ATP crystal, 20~90nm of diameter, greater homogeneity, structural integrity.
Embodiment 4
Weigh starting material element molar ratio Ti:P:NH4Ti (the SO of=1:1:104)2、H3PO4And NH3·H2O.It will be load weighted
0.566g Ti(SO4)2It is dissolved in 3mL deionized water, it is 25wt%'s that 1.77mL mass concentration is then first added dropwise into solution
NH3·H2O stirs 30s, and the H that 0.16mL mass concentration is 85wt% is then added3PO4, 5h is stirred, obtained white emulsion turns
It moves on in 25mL liner and is put into autoclave, be then sealed against being placed in baking oven.Baking oven is raised to 220 DEG C with 3h, keeps the temperature 4 days, so
Room temperature is dropped to the speed of 3 DEG C/h afterwards.It is collected by filtration to obtain white ATP powder, sufficiently be washed with deionized water, 50 DEG C dry
To the ATP of 0.38g, yield 90.9%；Obtained white powder is analyzed through X-ray diffraction and transmission electron microscope analysis, is ellipse
Round nanoscale ATP crystal, 20~80nm of diameter, greater homogeneity, structural integrity.
Embodiment 5
Weigh starting material element molar ratio Ti:P:NH4The TiCl of=1:1:84、H3PO4And NH3·H2O.It will be load weighted
0.537g TiCl4It is dissolved under condition of ice bath in 3mL deionized water, 1.69mL mass concentration is first then added dropwise into solution is
The NH of 25wt%3·H2O stirs 30s, and the H that 0.19mL mass concentration is 85wt% is then added3PO4, 5h is stirred, what is obtained is white
Color lotion is transferred in 25mL liner and is put into autoclave, is then sealed against being placed in baking oven.Baking oven is raised to 200 DEG C with 3h, protects
Temperature 4 days, then drops to room temperature with the speed of 3 DEG C/h.It is collected by filtration to obtain white ATP powder, sufficiently be washed with deionized water, 50
DEG C drying obtains the ATP of 0.47g, yield 93.8%；Obtained white powder is analyzed through X-ray diffraction and transmission electron microscope
Analysis, for oval nanoscale ATP crystal, 20~90nm of diameter, greater homogeneity, structural integrity.
Embodiment 6
Weigh starting material element molar ratio Ti:P:NH4Ti (the SO of=1:1:84)2、H3PO4And urea.By load weighted 0.84g
Ti(SO4)2It is dissolved in 5mL deionized water, 0.83g urea is then first added dropwise into solution, stir 90s, 0.24mL matter is then added
Measure the H that concentration is 85wt%3PO4, 5h is stirred, obtained white emulsion, which is transferred in 25mL liner, is put into autoclave, then by it
It is sealed and placed in baking oven.Baking oven is raised to 220 DEG C with 3h, keeps the temperature 4 days, then drops to room temperature with the speed of 3 DEG C/h.It is collected by filtration
It to white ATP powder, is sufficiently washed with deionized water, 50 DEG C of drying obtain the ATP of 0.56g, yield 91.5%；It is obtained
White powder is analyzed through X-ray diffraction and transmission electron microscope analysis, for oval nanoscale ATP crystal, 40~100nm of diameter, product
Matter is uniform, structural integrity.
To sum up, method provided by the invention can be prepared size it is small, it is with high purity and do not occur reunite, it is finely dispersed
Phosphoric acid titanyl ammonium crystal, in this preparation process, can the charging sequence of raw material proportioning and raw material be received for finally be prepared
The phosphoric acid titanyl ammonium crystal of meter ruler cun has great influence.The size for the phosphoric acid titanyl ammonium crystal that the present invention is prepared be 20~
100nm.In addition, the nanometer ATP crystal yield that method provided by the invention is prepared is higher, up to 90% or more.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. the preparation method of a kind of nanometer of phosphoric acid titanyl ammonium crystal, comprising the following steps:
(1) it after mixing titanium salt, ammonium hydroxide and water, then mixes with phosphoric acid, obtains mixed liquor；
The molar ratio of Ti, P and N element is 1:0.8~1:6~10 in the mixed liquor；
(2) it is cooled down after the mixed liquor that the step (1) obtains being carried out hydro-thermal reaction in confined conditions, obtains a nanometer phosphoric acid
Titanyl ammonium crystal.
2. preparation method according to claim 1, which is characterized in that the quality of step (1) titanium salt and the volume of water
Than for 0.5~1.0g:2~4mL.
3. preparation method according to claim 1 or 2, which is characterized in that titanium salt includes TiOSO in the step (1)4、
TiCl4With Ti (SO4)2One of or it is a variety of.
4. preparation method according to claim 1, which is characterized in that the temperature of hydro-thermal reaction is 180 in the step (2)
~220 DEG C；The time of hydro-thermal reaction is 3~7 days.
5. preparation method according to claim 1 or 4, which is characterized in that be warming up to hydro-thermal reaction temperature in the step (2)
The heating rate of degree is 0.5~1.5 DEG C/min.
6. preparation method according to claim 1, which is characterized in that the step (2) temperature after cooling is 20~30
DEG C, the rate of the cooling is 2.5~3.5 DEG C/h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114620700A (en) * | 2020-12-09 | 2022-06-14 | 山东大学 | RbTiOPO4Method for preparing nano crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114620700A (en) * | 2020-12-09 | 2022-06-14 | 山东大学 | RbTiOPO4Method for preparing nano crystal |
| CN114620700B (en) * | 2020-12-09 | 2023-03-31 | 山东大学 | RbTiOPO 4 Method for preparing nanocrystals |
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