CN109694050B - Preparation method of nano ammonium titanyl phosphate crystal - Google Patents
Preparation method of nano ammonium titanyl phosphate crystal Download PDFInfo
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- CN109694050B CN109694050B CN201910068733.1A CN201910068733A CN109694050B CN 109694050 B CN109694050 B CN 109694050B CN 201910068733 A CN201910068733 A CN 201910068733A CN 109694050 B CN109694050 B CN 109694050B
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- titanyl phosphate
- ammonium 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
Abstract
The invention provides a preparation method of a nano ammonium titanyl phosphate crystal, and relates to the field of crystals. The preparation method of the nanometer ammonium titanyl phosphate crystal provided by the invention comprises the following steps: mixing titanium salt and ammonia water in water, and then mixing with phosphoric acid to obtain mixed feed liquid; the molar ratio of Ti, P and N elements in the mixed feed liquid is 1: 0.8-1: 6-10; and carrying out hydrothermal reaction on the mixed material liquid under a closed condition, and cooling to obtain the nano ammonium titanyl phosphate crystal. The method provided by the invention can be used for preparing the nanometer-sized ammonium titanyl phosphate crystal, and the prepared ammonium titanyl phosphate crystal has a good dispersion effect and is free from agglomeration. The nanometer level ammonium titanyl phosphate crystal prepared by the method is used as a raw material, and is beneficial to growth to obtain high-quality ammonium titanyl phosphate large crystals.
Description
Technical Field
The invention relates to the field of crystals, in particular to a preparation method of a nanometer ammonium titanyl phosphate crystal.
Background
MTiOXO4(M＝Li、Na、K、Rb、NH4Cs, X ═ P or As) type crystals are well known nonlinear optical crystal systems, e.g. KTiOPO4The (abbreviated as KTP) crystal is one of nonlinear optical crystal materials with excellent comprehensive performance. In the same type of crystal, NH4TiOPO4The (ATP) crystal has unique controllable turn-off property of the nonlinear optical effect, so that ATP has great potential in the field of nonlinear optics. Before the ATP crystal grows, firstly, high-quality raw materials are obtained to reduce defects in the ATP crystal growing process and improve the ATP crystal quality.
The prior art (J.Mater.chem.A2016,4(19),7141-7147) discloses a report of synthesizing Ammonium Titanyl Phosphate (ATP) solid powder by a hydrothermal method, but ATP crystals finally prepared by the document are micron-scale sheet diamond crystals, and nanoscale ATP crystals cannot be obtained. Therefore, how to provide a nano-sized and agglomeration-free titanyl ammonium phosphate raw material is of great significance.
Disclosure of Invention
The invention provides a preparation method of a nanometer ammonium titanyl phosphate crystal, the size of the ammonium titanyl phosphate crystal prepared by the method provided by the invention is nanometer, the dispersion effect is good, and agglomeration does not occur.
The invention provides a preparation method of a nano ammonium titanyl phosphate crystal, which comprises the following steps:
(1) mixing titanium salt, ammonia water and water, and then mixing with phosphoric acid to obtain a mixed feed liquid;
the molar ratio of Ti, P and N elements in the mixed feed liquid is 1: 0.8-1: 6-10;
(2) and (2) carrying out hydrothermal reaction on the mixed feed liquid obtained in the step (1) under a closed condition, and then cooling to obtain the nano-titanium ammonium phosphate crystal.
Preferably, the ratio of the mass of the titanium salt in the step (1) to the volume of water is 0.5-1.0 g: 2-4 mL.
Preferably, the titanium salt in step (1) comprises TiOSO4、TiCl4And Ti (SO)4)2One or more of (a).
Preferably, the temperature of the hydrothermal reaction in the step (2) is 180-220 ℃; the hydrothermal reaction time is 3-7 days.
Preferably, the heating rate of the temperature rising to the hydrothermal reaction temperature in the step (2) is 0.5-1.5 ℃/min.
Preferably, the temperature after cooling in the step (2) is 20-30 ℃, and the cooling rate is 2.5-3.5 ℃/h.
The invention provides a preparation method of a nano ammonium titanyl phosphate crystal, which comprises the following steps: mixing titanium salt, ammonia water and water, and then mixing with phosphoric acid to obtain a mixed feed liquid; the molar ratio of Ti, P and N elements in the mixed feed liquid is 1: 0.8-1: 6-10; and carrying out hydrothermal reaction on the mixed material liquid under a closed condition, and cooling to obtain the nano ammonium titanyl phosphate crystal. The method provided by the invention can be used for preparing the ammonium titanyl phosphate crystal which is small in size, high in purity and uniform in dispersion, and the test result of the embodiment shows that the size of the ammonium titanyl phosphate crystal prepared by the method is 20-100 nm; the titanium ammonium phosphate crystal prepared by the method has good dispersion effect and is free from agglomeration. The nano-scale ammonium titanyl phosphate crystal which is prepared by the method and has small size, high purity and uniform dispersion is taken as a raw material, and the growth of the nano-scale ammonium titanyl phosphate crystal is facilitated to obtain the ATP large crystal with high quality.
Drawings
FIG. 1 is an XRD spectrum of the product prepared in example 1;
FIG. 2 is a transmission electron micrograph of the product prepared in example 1;
FIG. 3 is an XRD spectrum of the product prepared in example 2;
FIG. 4 is a transmission electron micrograph of the product prepared in example 2;
FIG. 5 is an XRD spectrum of the product prepared in comparative example 1;
fig. 6 is an XRD spectrum of the product prepared in comparative example 2.
Detailed Description
The invention provides a preparation method of a nano ammonium titanyl phosphate crystal, which comprises the following steps:
(1) mixing titanium salt, ammonia water and water, and then mixing with phosphoric acid to obtain a mixed feed liquid;
(2) and (2) carrying out hydrothermal reaction on the mixed feed liquid obtained in the step (1) under a closed condition, and then cooling to obtain the nano-titanium ammonium phosphate crystal.
In the present invention, all the raw materials are commercially available.
The invention mixes titanium salt, ammonia water and water, and then mixes with phosphoric acid to obtain mixed feed liquid.
In the present invention, the titanium salt preferably comprises TiOSO4、TiCl4And Ti (SO)4)2One or more of; the mass concentration of the ammonia water is preferably 25%; the phosphoric acid is preferably present at a concentration of 85% by mass. In the present invention, the ratio of the mass of the titanium salt to the volume of water is preferably 0.5 to 1.0 g/2 to 4mL, and more preferably 0.6 to 0.9 g/2 to 4 mL. In the invention, the molar ratio of Ti, P and N elements in the mixed feed liquid is 1: 0.8-1: 6-10, preferably 1:0.9: 7-9.
After the invention is mixed with phosphoric acid, the mixture system is preferably stirred to obtain mixed feed liquid. In the invention, the stirring time is preferably 3-4 h, so that the titanium salt, the ammonia water and the phosphoric acid can be fully mixed.
The invention firstly mixes the titanium salt and the ammonia water, then mixes the titanium salt and the phosphoric acid, and follows the feeding sequence of firstly adding alkali and then adding acid, so that the whole reaction is carried out under the alkaline condition, thereby efficiently producing a large amount of target products.
The invention controls the molar ratio of Ti, P and N elements in the mixed feed liquid in the range, and can ensure that the prepared product is ATP crystal.
After the mixed material liquid is obtained, the mixed material liquid is subjected to hydrothermal reaction under a closed condition and then is cooled to obtain the nano-titanium ammonium phosphate crystals.
In the invention, the temperature of the hydrothermal reaction is preferably 180-220 ℃, more preferably 190-220 ℃, and the heating rate of heating to the hydrothermal reaction temperature is preferably 0.5-1.5 ℃/min, more preferably 0.8-1.2 ℃/min. In the present invention, the hydrothermal reaction time is preferably 3 to 7 days, and more preferably 4 to 6 days.
After the hydrothermal reaction is finished, the reaction system is cooled to obtain the nano ammonium titanyl phosphate crystal. In the invention, the temperature after cooling is preferably 20-30 ℃, and more preferably 25 ℃; the cooling rate is preferably 2.5-3.5 ℃/h, and more preferably 3 ℃/h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Weighing TiOSO with the molar ratio of raw material elements Ti, P, N being 1:1:64、H3PO4And NH3·H2And O. 0.955g of TiOSO with a purity of 93 wt%4Dissolving the mixture in 3mL of deionized water, and then dropwise adding 2.49mL of NH with the mass concentration of 25 wt% into the solution3·H2O stirring for 30s, then adding 0.38mL of H with the mass concentration of 85 wt%3PO4After stirring for 4h, the resulting white emulsion was transferred to a 25mL liner and placed in an autoclave, which was then sealed and placed in an oven. The oven was raised to 220 ℃ for 3h, incubated for 4 days, and then allowed to cool to room temperature at a rate of 3 ℃/h. White ATP powder was collected by filtration, washed thoroughly with deionized water, and dried at 50 ℃ to give 0.91g ATP in 92.6% yield.
The white powder obtained in example 1 was subjected to X-ray diffraction analysis and transmission electron microscopy analysis, and the results are shown in fig. 1 and 2, in which fig. 1 is an XRD spectrum and fig. 2 is a transmission electron microscopy spectrum. As can be seen from FIG. 1, the white powder prepared by the invention is ATP crystal and has higher purity; as can be seen from FIG. 2, the ATP crystal prepared by the invention has an elliptical shape, a nano-scale size, a diameter of 20-60 nm, uniform quality and a complete structure.
Example 2
Weighing Ti (SO) at a molar ratio of Ti to P to N of 1:1:64)2、H3PO4And NH3·H2And O. Weigh 0.654gTi (SO)4)2Dissolving the mixture in 3mL of deionized water, and then dropwise adding 1.22mL of NH with the mass concentration of 25 wt% into the solution3·H2O stirring for 30s, then adding 0.19mL of H with the mass concentration of 85 wt%3PO4After stirring for 4h, the resulting white emulsion was transferred to a 25mL liner and placed in an autoclave, which was then sealed and placed in an oven. The oven was ramped up to 220 ℃ for 3h, held for 3 days, and then ramped down to room temperature at a rate of 3 ℃/h. White ATP powder was collected by filtration, washed thoroughly with deionized water, and dried at 50 ℃ to give 0.46g of ATP in 95.3% yield.
The white powder obtained in example 2 was subjected to X-ray diffraction analysis and transmission electron microscopy analysis, and the results are shown in fig. 3 and 4, where fig. 3 is an XRD spectrum and fig. 4 is a transmission electron microscopy spectrum. FIG. 3 shows the XRD curve of the product of example 2 in the upper layer, and the standard spectrum of ATP crystal in the lower layer, as can be seen from FIG. 3, the white powder prepared by the present invention is ATP crystal with high purity; as can be seen from FIG. 4, the ATP crystal prepared by the invention has an elliptical shape, a nano-scale size, a diameter of 20-70 nm, uniform quality and a complete structure.
Comparative example 1
Example 2 was repeated except that: raw material elements molar ratio of Ti to P to NH4＝1:1:4。
The product obtained in comparative example 1 was not ATP but NH after the reaction under the same conditions as in example 24H(PO3)2、TiO2And the like of ammonium phosphate. XRD test was carried out on the product obtained in comparative example 1, and the test results are shown in FIG. 5, the upper curve of FIG. 5The XRD profile of the product of comparative example 1, the lower curve of FIG. 5 is the ATP crystal standard spectrum. As can be seen from FIG. 5, the ratio of the raw materials is important for the preparation of ATP crystals.
Comparative example 2
Example 2 was repeated except that: to Ti4+Solution, adding H first3PO4Stirring for 30s, then adding NH3·H2O stirring for 4 h.
The product obtained in comparative example 2 was not ATP but TiO, which was subjected to the same reaction conditions as in example 22And the like of ammonium phosphate. The XRD test was performed on the product obtained in comparative example 2, and the results are shown in fig. 6, in which the upper curve of fig. 6 is the XRD curve of the product of comparative example 2, and the lower curve of fig. 6 is the ATP crystal simulation standard spectrum. As can be seen from FIG. 6, the order of addition of the raw materials plays an important role in the production of ATP crystals.
Example 3
Weighing the molar ratio of the raw material elements Ti to P to NH41:0.8:6 Ti (SO)4)2、H3PO4And NH3·H2And O. Weigh 0.685g of Ti (SO)4)2Dissolving the mixture in 4mL of deionized water, and then dropwise adding 1.28mL of NH with the mass concentration of 25 wt% into the solution3·H2O stirring for 40s, then adding 0.16mL of H with the mass concentration of 85 wt%3PO4After stirring for 4h, the resulting white emulsion was transferred to a 25mL liner and placed in an autoclave, which was then sealed and placed in an oven. The oven was raised to 180 ℃ for 3h, incubated for 7 days, and then allowed to cool to room temperature at a rate of 3 ℃/h. Filtering and collecting white ATP powder, fully washing with deionized water, and drying at 50 ℃ to obtain 0.47g of ATP, wherein the yield is 93.1%; the obtained white powder is an elliptical nanoscale ATP crystal through X-ray diffraction analysis and transmission electron microscope analysis, the diameter of the ATP crystal is 20-90 nm, the quality is uniform, and the structure is complete.
Example 4
Weighing the molar ratio of the raw material elements Ti to P to NH41:1:10 Ti (SO)4)2、H3PO4And NH3·H2And O. Weighed 0.566g of Ti (S)O4)2Dissolving the mixture in 3mL of deionized water, and then dropwise adding 1.77mL of NH with the mass concentration of 25 wt% into the solution3·H2O stirring for 30s, then adding 0.16mL of H with the mass concentration of 85 wt%3PO4After stirring for 5h, the resulting white emulsion was transferred to a 25mL liner and placed in an autoclave, which was then sealed and placed in an oven. The oven was raised to 220 ℃ for 3h, incubated for 4 days, and then allowed to cool to room temperature at a rate of 3 ℃/h. Filtering and collecting white ATP powder, fully washing with deionized water, and drying at 50 ℃ to obtain 0.38g of ATP with the yield of 90.9%; the obtained white powder is an elliptical nanoscale ATP crystal through X-ray diffraction analysis and transmission electron microscope analysis, the diameter of the ATP crystal is 20-80 nm, the quality is uniform, and the structure is complete.
Example 5
Weighing the molar ratio of the raw material elements Ti to P to NH41:1:8 TiCl4、H3PO4And NH3·H2And O. Weighed 0.537g TiCl4Dissolving the mixture in 3mL of deionized water under the ice bath condition, and then dropwise adding 1.69mL of NH with the mass concentration of 25 wt% into the solution3·H2O stirring for 30s, then adding 0.19mL of H with the mass concentration of 85 wt%3PO4After stirring for 5h, the resulting white emulsion was transferred to a 25mL liner and placed in an autoclave, which was then sealed and placed in an oven. The oven was raised to 200 ℃ for 3h, incubated for 4 days, and then allowed to cool to room temperature at a rate of 3 ℃/h. Filtering and collecting white ATP powder, fully washing with deionized water, and drying at 50 ℃ to obtain 0.47g of ATP with the yield of 93.8%; the obtained white powder is an elliptical nanoscale ATP crystal through X-ray diffraction analysis and transmission electron microscope analysis, the diameter of the ATP crystal is 20-90 nm, the quality is uniform, and the structure is complete.
Example 6
Weighing the molar ratio of the raw material elements Ti to P to NH41:1:8 Ti (SO)4)2、H3PO4And urea. Weigh 0.84g Ti (SO)4)2Dissolving in 5mL of deionized water, then dropwise adding 0.83g of urea into the solution, stirring for 90s, and then adding 0.24mL of H with the mass concentration of 85 wt%3PO4Stirring for 5h to obtain whiteThe color emulsion was transferred to a 25mL liner and placed in an autoclave, which was then sealed and placed in an oven. The oven was raised to 220 ℃ for 3h, incubated for 4 days, and then allowed to cool to room temperature at a rate of 3 ℃/h. Filtering and collecting white ATP powder, fully washing with deionized water, and drying at 50 ℃ to obtain 0.56g of ATP with the yield of 91.5%; the obtained white powder is an elliptical nanoscale ATP crystal through X-ray diffraction analysis and transmission electron microscope analysis, the diameter of the ATP crystal is 40-100 nm, the quality is uniform, and the structure is complete.
In conclusion, the method provided by the invention can prepare the titanium ammonium phosphate crystal which is small in size, high in purity, free from agglomeration and uniform in dispersion, and in the preparation process, the raw material proportion and the raw material feeding sequence have important influence on whether the nano-sized titanium ammonium phosphate crystal can be finally prepared. The size of the ammonium titanyl phosphate crystal prepared by the method is 20-100 nm. In addition, the yield of the nano ATP crystal prepared by the method provided by the invention is high and can reach more than 90%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A preparation method of nano ammonium titanyl phosphate crystals comprises the following steps:
(1) mixing titanium salt, ammonia water and water, and then mixing with phosphoric acid to obtain a mixed feed liquid;
the molar ratio of Ti, P and N elements in the mixed feed liquid is 1: 0.8-1: 6-10;
(2) carrying out hydrothermal reaction on the mixed feed liquid obtained in the step (1) under a closed condition, and cooling to obtain a nano ammonium titanyl phosphate crystal;
the temperature after cooling in the step (2) is 20-30 ℃, and the cooling rate is 2.5-3.5 ℃/h;
the size of the nanometer ammonium titanyl phosphate crystal is 20-100 nm;
the shape of the nanometer ammonium titanyl phosphate crystal is oval.
2. The preparation method according to claim 1, wherein the volume ratio of the titanium salt to the water in the step (1) is 0.5-1.0 g: 2-4 mL.
3. The method according to claim 1 or 2, wherein the titanium salt in the step (1) comprises TiOSO4、TiCl4And Ti (SO)4)2One or more of (a).
4. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction in the step (2) is 180-220 ℃; the hydrothermal reaction time is 3-7 days.
5. The method according to claim 1 or 4, wherein the rate of temperature increase to the hydrothermal reaction temperature in the step (2) is 0.5 to 1.5 ℃/min.
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| Novel 1.5 V anode materials, ATiOPO4(A=NH4, K, Na), for room-temperature sodium-ion batteries;Linqin Mu et al.;《J. Mater. Chem. A》;20160427;第4卷;第2节、图2 * |
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