CN113307303B - High-stability all-inorganic perovskite/aluminum phosphate composite nano material and preparation method and application thereof - Google Patents
High-stability all-inorganic perovskite/aluminum phosphate composite nano material and preparation method and application thereof Download PDFInfo
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 33
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 5
- 238000012984 biological imaging Methods 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims 1
- 239000012216 imaging agent Substances 0.000 claims 1
- 229940124597 therapeutic agent Drugs 0.000 claims 1
- 229910017119 AlPO Inorganic materials 0.000 abstract description 20
- 238000006862 quantum yield reaction Methods 0.000 abstract description 8
- 239000003929 acidic solution Substances 0.000 abstract description 7
- 239000002159 nanocrystal Substances 0.000 abstract description 5
- 239000012670 alkaline solution Substances 0.000 abstract description 4
- 239000011812 mixed powder Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 12
- 239000010453 quartz Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 235000019668 heartiness Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- C01B25/36—Aluminium phosphates
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention relates to a high-stability all-inorganic perovskite/aluminum phosphate composite nano material, and a preparation method and application thereof. CsPbX is prepared by mechanical grinding method 3 Fully grinding and uniformly mixing the precursor of the nanocrystals with aluminum oxide and ammonium dihydrogen phosphate solids; sintering the mixed powder at high temperature to obtain AlPO 4 Encapsulated CsPbX 3 A nanocrystalline; placing the sintered sample in an acidic solution for washing to obtain CsPbX with high stability 3 @AlPO 4 The prepared nano material can be stably dispersed in ethanol, water, acidic and alkaline solutions. The nano material can be stably placed in the air for more than 1 year, and the fluorescence quantum yield is still kept unchanged. The invention realizes the preparation of the ultra-high stable perovskite nanocrystalline, and has potential application in the aspects of light-emitting diodes, biological imaging and photothermal treatment.
Description
Technical Field
The invention relates to the technical field of inorganic nano materials, in particular to a high-stability all-inorganic perovskite/aluminum phosphate composite nano material, and a preparation method and application thereof.
Background
In recent years, as an emerging semiconductor material, all-inorganic perovskite nanocrystals have many excellent properties including low preparation cost, high fluorescence quantum yield, adjustable luminescence spectrum in the visible light range, etc., so that they have been surprisingly developed in the fields of photoelectric devices, photocatalysis, etc. However, the self-ionic property of the all-inorganic perovskite makes the all-inorganic perovskite extremely sensitive to water, oxygen, light and heat, and the structure of the all-inorganic perovskite nanocrystalline is easily damaged. In practical applications, researchers have addressed this problem by increasing the stability of perovskite nanocrystals themselves.
At present, silicon dioxide, aluminum oxide, organic matters and the like are generally selected to coat perovskite, so that contact between the perovskite and water and oxygen is blocked, and the stability of the perovskite is improved. However, the methods reported so far still have disadvantages in improving the stability of perovskite, such as the inability to achieve long-term storage, heat treatment and dispersion in acidic solutions. Therefore, it is of great importance to prepare all-inorganic perovskite nanomaterial that can be stored for a long period of time, heat treated and dispersed in an acidic solution.
Disclosure of Invention
The invention aims to provide a method for preparing high-stability all-inorganic perovskite nanocrystalline, the prepared nanocrystalline can be stably dispersed in ethanol, water, acidic and alkaline solutions, the nanocrystalline can be stably placed in the air for more than 1 year, and the initial fluorescence quantum yield is maintained.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a high-stability all-inorganic perovskite/aluminum phosphate composite nano material comprises perovskite and aluminum phosphate; the aluminum phosphate encapsulates the perovskite.
Preferably, the high-stability all-inorganic perovskite/aluminum phosphate composite nano material consists of perovskite and aluminum phosphate wrapping the perovskite.
The invention discloses a preparation method of the high-stability all-inorganic perovskite/aluminum phosphate composite nano material, which comprises the following steps of mixing and grinding a perovskite precursor, aluminum oxide and ammonium dihydrogen phosphate, and then sintering at a high temperature to obtain a sintered product; and washing and drying the sinter to obtain the high-stability all-inorganic perovskite/aluminum phosphate composite nano material.
Preferably, the perovskite is CsPbX 3 The perovskite precursor is Cs 2 CO 3 、PbX 2 And NaX; x is halogen, and is one or more of Cl, br and I.
Preferably, al 2 O 3 (aluminum oxide), NH 4 H 2 PO 4 (monoammonium phosphate), cs 2 CO 3 、PbX 2 The mass ratio of NaX is (0.5-10) to (5-20) to 1 to (1-1.5) to (0.5-2).
Preferably, milling is ball milling; further preferably, the rotational speed of the ball mill is 300 to 600rpm for a time of 1 to 5 h.
Preferably, the high-temperature sintering is carried out at a heating rate of 2-10 ℃/min from room temperature to 400 ℃, and the temperature is kept for 5-30 min; further preferably, the high temperature sintering is performed in air; and after the high-temperature sintering is finished, naturally cooling in air.
Preferably, the washing is acid washing, water washing and alcohol washing; further preferably, the concentration of the acid is 1 to 6. 6M.
The invention discloses application of the high-stability all-inorganic perovskite/aluminum phosphate composite nano material in the fields of light emitting diodes, biological imaging and photothermal treatment.
Advantageous effects
The all-inorganic perovskite/aluminum phosphate composite nano material has extremely high stability: 1) The material is placed in moist air for one year, and the fluorescence quantum yield can still keep the initial value; 2) The material can exist in an acidic solution and an alkaline solution stably, and the fluorescence intensity is not changed obviously after the material is placed for half a year; 3) After the material is heated to 24 h at the high temperature of 300 ℃, the initial fluorescence intensity is still maintained; 4) The material still maintained 88% of the original intensity after 1000 a h a uv exposure.
Drawings
FIG. 1 is a photograph of a sample prepared in example 1 under a fluorescent lamp;
FIG. 2 is a photograph of the sample prepared in example 1 under an ultraviolet lamp;
FIG. 3 is XRD of the sample prepared in example 1;
FIG. 4 is a diagram showing the elemental distribution of the sample prepared in example 1, to a scale of 500 nm;
FIG. 5 shows the change in fluorescence intensity of the sample prepared in example 1 when placed in solutions of different pH values for half a year;
FIG. 6 shows the sample prepared in example 1 and CsPbBr 3 /AlPO 4 (from PbBr) 2 、Cs 2 CO 3 、AlPO 4 Direct milling preparation) and CsPbBr prepared by conventional methods 3 Fluorescence intensity contrast after nanocrystal heating.
Detailed Description
The method for preparing the high-stability all-inorganic perovskite/aluminum phosphate composite nano material comprises the following steps of:
step one: weighing a certain mass of reaction precursor, putting the reaction precursor into a ball milling tank, and performing mechanical ball milling;
step two: treating the mixed powder at high temperature;
step three: washing the sintered sample, and drying to obtain CsPbX with high stability 3 @AlPO 4 And (3) nanocrystalline.
The raw materials related to the invention are all commercial products, and the specific ball milling, sintering and washing operations are conventional methods; the technical scheme of the invention is carried out under the conventional environment unless specified otherwise.
Example 1 preparation of high stability all inorganic perovskite/aluminum phosphate composite nanomaterial
Step 1: 0.5 g of Al is weighed 2 O 3 、4.6 g NH 4 H 2 PO 4 、1.63 g Cs 2 CO 3 、2.75 g PbBr 2 And 0.5 g NaBr are put into a quartz ball milling tank, ball milling balls are added into the quartz ball milling tank, the quartz ball milling tank is sealed, and mechanical ball milling is carried out, wherein the ball milling speed is 400 rpm, and the time is 2 h;
step 2: transferring the ball-milled powder into a ceramic crucible, and putting into a muffle furnace to obtain a powder with a particle size of 8 o C/min from room temperature to 400 o C, immediately taking out after heat treatment for 15 min, and naturally cooling in the air;
step 3: placing the heat-treated sample in 2M nitric acid aqueous solution, performing conventional ultrasonic treatment for 20 min, centrifuging at 6000 rpm for 5 min, taking the lower precipitate, washing with nitric acid by the same method once, adding 60 mL deionized water into the lower precipitate, performing conventional ultrasonic treatment for 20 min, centrifuging at 6000 rpm for 5 min, taking the lower precipitate deionized water, washing with 50mL ethanol by the same method once, taking the precipitate, and performing washing with 70 o C, drying to obtain a powder sample CsPbBr 3 @AlPO 4 The powder obtained in fig. 1 is light green under fluorescent lamps, and exhibits a very bright green under ultraviolet lamps as shown in fig. 2. As shown in FIG. 3, csPbBr with cubic phase is simultaneously present in the prepared powder 3 Crystal and AlPO 4 . The elemental distribution shown in fig. 4 can be found with Cs, pb, br, al and P elements uniformly distributed within the nanoparticle. Proof CsPbBr 3 The nanocrystalline is successfully coated on AlPO 4 Is a kind of medium.
Comparative example
Step 1: weigh 8 g AlPO 4 、1.63 g Cs 2 CO 3 、2.75 g PbBr 2 And 0.5 g NaBr are put into a quartz ball milling tank, ball milling balls are added into the quartz ball milling tank, the quartz ball milling tank is sealed, and mechanical ball milling is carried out, wherein the ball milling speed is 400 rpm, and the time is 2 h;
step 2: transferring the ball-milled powder into a ceramic crucible, and putting into a muffle furnace to obtain a powder with a particle size of 8 o C/min from room temperature to 400 o C, immediately taking out after heat treatment for 15 min, and naturally cooling in the air;
step 3: placing the heat-treated sample in 2M nitric acid water solution, performing conventional ultrasonic treatment for 20 min, centrifuging at 6000 rpm for 5 min, collecting the lower precipitate, washing with nitric acid by the same method, collecting the lower precipitate, and adding 60 mLIonized water, conventional ultrasonic treatment for 20 min, centrifuging at 6000 rpm for 5 min, collecting the precipitate, washing with deionized water, washing with 50mL ethanol, collecting precipitate, and washing with 70 o C, drying to obtain a powder sample CsPbBr 3 /AlPO 4 。
CsPbBr prepared by traditional method 3 Nanocrystalline reference [ (]Nano Lett. 2015, 15(6), 3692-3696.）。
Example 2: preparation of high-stability all-inorganic perovskite/aluminum phosphate composite nano material
Step 1: 0.5 g of Al is weighed 2 O 3 、4.6 g NH 4 H 2 PO 4 、1.63 g Cs 2 CO 3 、2.75 g PbBr 2 And 0.25 g of NaCl are put into a quartz ball milling tank, ball milling balls are added into the quartz ball milling tank, the quartz ball milling tank is sealed, and mechanical ball milling is carried out, wherein the ball milling rotating speed is 400 rpm, and the time is 2 h;
step 2: transferring the ball-milled powder into a ceramic crucible, and putting into a muffle furnace to obtain powder with a particle diameter of 7 o C/min from room temperature to 400 o Taking out the product immediately after heat treatment for 15 min, and naturally cooling in air;
step 3: placing the heat-treated sample in 2M nitric acid aqueous solution for conventional ultrasonic treatment for 20 min, washing off excessive reactant, centrifuging at 6000 rpm for 5 min, collecting lower precipitate, washing with nitric acid by the same method, washing with deionized water twice, washing with ethanol once, collecting precipitate, and collecting precipitate 70 o C drying to obtain powder sample CsPb (Cl/Br) 3 @AlPO 4 。
Example 3: preparation of high-stability all-inorganic perovskite/aluminum phosphate composite nano material
Step 1: 0.25 g of Al is weighed 2 O 3 、4.6 g NH 4 H 2 PO 4 、1.63 g Cs 2 CO 3 、2.75 g PbBr 2 And 1.5 g NaI are put into a quartz ball milling tank, ball milling balls are added into the quartz ball milling tank, the ball milling tank is sealed, and mechanical ball milling is carried out, wherein the ball milling rotating speed is 400 rpm, and the time is 2 h.
Step 2: transferring the ball-milled powder into a ceramic crucible, putting the ceramic crucible into a muffle furnace,400 o taking out immediately after heat treatment for 10 min, wherein the temperature rising rate is 5 o C/min。
Step 3: placing the heat-treated sample in 2M nitric acid solution, ultrasonic treating for 20 min, washing off excessive reactant, centrifuging at 6000 rpm for 5 min, collecting lower precipitate, washing with nitric acid by the same method, washing with deionized water twice, washing with ethanol once, collecting precipitate, and collecting precipitate 70 o C drying to obtain powder sample CsPb (Br/I) 3 @AlPO 4 。
Application Performance
Fluorescence intensity was measured using a fluorescence spectrometer (FLUOROMAX-4). Fluorescence quantum yield was tested using an absolute quantum yield measurement system (kokumi pine).
Powder sample CsPbBr of example 1, 0.1. 0.1 g 3 @AlPO 4 Respectively adding the solution into the existing buffer solution with the pH value of 2, the existing buffer solution with the pH value of 13 and the aqueous solution with the pH value of 7 (the solutions are all 3 mL), placing the solution into a cuvette, and periodically testing the fluorescence intensity; after half a year of standing, the fluorescence intensity is not obviously changed, as shown in figure 5, and the powder in the solution is uniformly dispersed, so that the phenomena of sedimentation, agglomeration and the like are avoided. Further, the powder sample CsPbBr of example 1 3 @AlPO 4 The water-free ethanol dispersion has no sedimentation, agglomeration and other phenomena in half a year.
The powder sample CsPbBr of example 1 3 @AlPO 4 The fluorescent quantum yield is tested after one year in room temperature air with the humidity of 65%, and the initial value can be still maintained.
The powder sample CsPbBr of example 1 3 @AlPO 4 Powder sample CsPbBr of comparative example 3 /AlPO 4 Powder sample CsPbBr 3 The fluorescent light intensity was measured at regular time by placing in 300℃environment (air) and continuously heating, see FIG. 6. The samples of example 2 and example 3 also maintained 95% or more of the original fluorescence intensity after 24 hours at 300 ℃.
The powder sample CsPbBr of example 1 3 @AlPO 4 The exposure to ultraviolet light (wavelength 365, nm) was continued, with a 1000-h retention of 88% of the initial intensity.
The invention is thatCsPbX is prepared by mechanical grinding method 3 Precursor of nanocrystals and Al 2 O 3 And NH 4 H 2 PO 4 Grinding and mixing the solid; sintering the mixed powder at high temperature to obtain AlPO 4 Encapsulated CsPbX 3 A nanomaterial; washing and drying the sintered sample to obtain CsPbX with high stability 3 @AlPO 4 The composite nano material is the high-stability all-inorganic perovskite/aluminum phosphate composite nano material. According to the invention, other raw materials and preparation steps are not needed, and the obtained product high-stability all-inorganic perovskite/aluminum phosphate composite nano material is placed in moist air for one year, so that the fluorescence quantum yield can still keep an initial value; the fluorescent light can exist in an acidic solution and an alkaline solution stably, and the fluorescent light intensity is not changed obviously after the fluorescent light is placed for half a year; after heating 24 h at 300 ℃ high temperature, the initial fluorescence intensity is still maintained; 88% of the initial intensity is maintained after 1000 a h a of the uv light exposure.
Claims (6)
1. The high-stability all-inorganic perovskite/aluminum phosphate composite nano material is characterized by comprising perovskite and aluminum phosphate; the aluminum phosphate encapsulates the perovskite; perovskite CsPbX 3 X is one or more of Cl, br and I; the preparation method of the high-stability all-inorganic perovskite/aluminum phosphate composite nano material comprises the following steps of mixing and grinding a perovskite precursor with aluminum oxide and ammonium dihydrogen phosphate, and then sintering at a high temperature to obtain a sintered product; washing and drying the sinter to obtain a high-stability all-inorganic perovskite/aluminum phosphate composite nano material; the perovskite precursor is Cs 2 CO 3 、PbX 2 And NaX, X is one or more of Cl, br and I; the high-temperature sintering is carried out at a heating rate of 2-10 ℃/min from room temperature to 400 ℃, and the temperature is kept for 5-30 min.
2. The preparation method of the high-stability all-inorganic perovskite/aluminum phosphate composite nano material is characterized by comprising the following steps of mixing and grinding a perovskite precursor, aluminum oxide and ammonium dihydrogen phosphate, and then sintering at a high temperature to obtain a sintered product; the sinter is washed and driedObtaining the high-stability all-inorganic perovskite/aluminum phosphate composite nano material; the perovskite precursor is Cs 2 CO 3 、PbX 2 And NaX, X is one or more of Cl, br and I; high-temperature sintering is carried out at a heating rate of 2-10 ℃/min from room temperature to 400 ℃, and the temperature is kept for 5-30 min; the high-stability all-inorganic perovskite/aluminum phosphate composite nano material comprises perovskite and aluminum phosphate; the aluminum phosphate encapsulates the perovskite; perovskite CsPbX 3 X is one or more of Cl, br and I.
3. The method for preparing the high-stability all-inorganic perovskite/aluminum phosphate composite nano material according to claim 2, wherein the method is characterized in that Al 2 O 3 、NH 4 H 2 PO 4 、Cs 2 CO 3 、PbX 2 The mass ratio of NaX is (0.5-10) to (5-20) to 1 to (1-1.5) to (0.5-2).
4. The method for preparing a high-stability all-inorganic perovskite/aluminum phosphate composite nanomaterial according to claim 2, wherein the grinding is ball milling; the rotation speed of ball milling is 300-600 rpm, and the time is 1-5 h.
5. The method for preparing the high-stability all-inorganic perovskite/aluminum phosphate composite nano material according to claim 2, wherein the washing is acid washing, water washing and alcohol washing.
6. The use of the high-stability all-inorganic perovskite/aluminum phosphate composite nanomaterial of claim 1 in the preparation of light emitting diodes, biological imaging agents and photothermal therapeutic agents.
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