CN110255606B - Radial all-inorganic perovskite nano material and preparation method thereof - Google Patents
Radial all-inorganic perovskite nano material and preparation method thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 50
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 47
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 47
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 47
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000005642 Oleic acid Substances 0.000 claims abstract description 47
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 47
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 29
- 239000002070 nanowire Substances 0.000 claims abstract description 24
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 150000004820 halides Chemical class 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 65
- 239000000047 product Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 21
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 15
- 239000002243 precursor Substances 0.000 description 13
- 229910052792 caesium Inorganic materials 0.000 description 10
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- UVTGXFAWNQTDBG-UHFFFAOYSA-N [Fe].[Pb] Chemical compound [Fe].[Pb] UVTGXFAWNQTDBG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 octadecylene Chemical group 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a radial all-inorganic perovskite nano material, which comprises a center and nanowires radially growing from the center along a two-dimensional direction; the center is composed of a plurality of perovskite nano particles with the particle size of 30-80 nm, and the particle size of the center is 100-200 nm; the diameter of the nanowire is 30-80 nm, and the length of the nanowire is 2-20 mu m; the structural formula is CsPbX3And X is selected from Cl, Br or I. The preparation method comprises the following steps: (1) mixing cesium carbonate, oleic acid and octadecene to obtain a solution I; (2) mixing lead halide, oleic acid and oleylamine to obtain a solution II; the volume ratio of the oleic acid to the oleylamine is less than or equal to 1: 10; (3) and mixing the solution I and the solution II, and fully reacting to obtain the radial all-inorganic perovskite material. The invention discloses an all-inorganic perovskite nano material with an all-new shape, which is radial, regular and unique in shape and is expected to be used in the fields of solar cells, photocatalysis and the like.
Description
Technical Field
The invention relates to the field of perovskite materials and preparation thereof, in particular to a radial all-inorganic perovskite nano material and a preparation method thereof.
Background
The Lead halide perovskite nanomaterials (Lead halide perovskite nanomaterials) show attractive application prospects in the aspects of light-emitting and display devices, solar photovoltaic cells, photodetectors and the like due to the fact that the Lead halide perovskite nanomaterials have physical characteristics of wide spectral range, high absorption coefficient, high carrier mobility, shallow defect energy level and the like.
The zero-dimensional perovskite material is unstable, has a plurality of surface defects, is easy to compound electrons and holes on the surface, and is not beneficial to the effective separation of the electrons and the holes. How to improve the stability of perovskite materials and control the effective separation of electrons and holes has become a direction of great interest, with one-dimensional and multi-dimensional perovskite materials becoming a viable approach.
The one-dimensional and multi-dimensional perovskite materials have the advantages of long carrier diffusion distance, good structural stability and the like. The one-dimensional material is more beneficial to generation, separation and transmission of charges, effective separation of photo-generated electrons and holes, and can be widely applied to the photoelectric fields of solar cells, LEDs and the like.
At present, the shapes of common one-dimensional and multi-dimensional perovskite materials are mostly in a nanometer linear shape or a nanometer sheet shape. For example, chinese patent publication No. CN 108502918A discloses a method for synthesizing inorganic perovskite nanowires, which comprises: step 1, adding cesium carbonate into the mixed solution A, stirring for 15-35min at 110-160 ℃, and then naturally cooling to room temperature to form a cesium precursor solution; the mixed solution A is composed of oleic acid and octadecene, wherein the volume ratio of oleic acid: octadecene 1: 8; in the precursor solution of cesium, the molar concentration of cesium is 0.12-0.25M; step 2, adding lead bromide into the mixed solution B, stirring for 15-35min at 90-130 ℃, and then cooling to room temperature under the condition of water bath to form a lead bromide precursor solution; the mixed solution B consists of oleylamine, oleic acid and octadecene, wherein the volume ratio of oleylamine: oleic acid: octadecene is 1:1:8, and the molar concentration of lead bromide in a lead bromide precursor solution is 0.09-0.15M; step 3, heating the precursor solution of cesium to 60-100 ℃, transferring the cesium to a reaction kettle, naturally cooling the cesium to room temperature, adding the precursor solution of lead bromide, and carrying out ultrasonic treatment for 15-35min at room temperature to obtain a mixed solution D; precursor solution of lead bromide in volume ratio: a precursor solution of cesium is 7: 1-16: 1; step 4, reacting the mixed solution D at 80-150 ℃ for 30-90 h, and naturally cooling to obtain a reactant solution E; and centrifuging the reactant solution E, and washing to obtain a final product.
Also, for example, chinese patent document with application publication No. CN 109810704 a discloses a perovskite nanosheet material, and a preparation method and an application thereof, wherein the preparation method of the perovskite nanosheet material includes: (1) mixing cesium carbonate powder with octadecene and oleic acid, heating to 100-130 ℃ under the protection of inert gas, keeping the temperature for a period of time until the cesium carbonate powder is dissolved, and then heating the system to 140-160 ℃ to react for 10-60 min to obtain a cesium oleate precursor; mixing ferric bromide powder with octadecylene, oleic acid and oleylamine, stirring at normal temperature until the powder is dissolved, then adding lead bromide powder into the mixed solution, heating to 100-120 ℃ under the protection of inert gas, and maintaining for a period of time until the lead bromide powder is dissolved to obtain an iron-lead mixed solution; (2) heating the iron-lead mixed solution to 120-140 ℃, heating the cesium oleate precursor to 80-100 ℃, then mixing the cesium oleate precursor with the iron-lead mixed solution uniformly, carrying out heat preservation reaction at 120-140 ℃ for 5 s-5 min, cooling, and carrying out centrifugal separation to obtain a precipitate, namely the perovskite nanosheet material.
The perovskite nano materials with different morphologies have different characteristics and are expected to be applied to different application fields, so that the development of perovskite nano materials with new morphologies is necessary.
Disclosure of Invention
The invention discloses an all-inorganic perovskite nano material with an all-new shape and a preparation method thereof.
The specific technical scheme is as follows:
a radial all-inorganic perovskite nano material comprises a center and nanowires radially growing from the center along a two-dimensional direction;
the center is composed of a plurality of perovskite nano particles, the particle size of the center is 100-200 nm, and the particle size of a single perovskite nano particle is 30-80 nm;
the diameter of the nanowire is 30-80 nm, and the length of the nanowire is 2-20 mu m;
the number of the nanowires is 10-40;
the structural formula of the radial all-inorganic perovskite nano material is CsPbX3And X is selected from Cl, Br or I.
The all-inorganic perovskite nano material prepared by the invention has a radial nanowire structure and a larger specific surface area, and is beneficial to the transmission of current carriers; in addition, in the all-inorganic perovskite nano material, each nanowire is not in the same direction, the contact point is only at the center, electrons and holes can be transferred to all directions through the center, and the electrons and the holes are not easy to meet and are compounded, so that the photoelectric property of the material is improved.
The invention also discloses a preparation method of the radial all-inorganic perovskite nano material, which comprises the following steps:
(1) mixing cesium carbonate, oleic acid and octadecene, and heating until the cesium carbonate, the oleic acid and the octadecene are completely dissolved to obtain a solution I;
(2) mixing lead halide, oleic acid and oleylamine, and heating until the lead halide, the oleic acid and the oleylamine are completely dissolved to obtain a solution II;
the volume ratio of the oleic acid to the oleylamine is less than or equal to 1: 10;
(3) and mixing the solution I and the solution II, heating to 150-220 ℃, and fully reacting to obtain the radial all-inorganic perovskite material.
In the existing preparation process for preparing the all-inorganic perovskite nano material, the preparation of a lead halide precursor solution mostly uses oleic acid and oleylamine as ligands and octadecene as a solvent, and the morphology of the product is regulated and controlled by adjusting the proportion of the oleic acid and the oleylamine or selectively adding extra halogen. In the invention, the inventor unexpectedly finds out in experiments that when the lead halide precursor solution is prepared in the step (2), octadecene is not added, but oleylamine which is greatly excessive than oleic acid is added (the volume ratio of oleic acid to oleylamine is less than or equal to 1:10), the radial all-inorganic perovskite nano material with unique morphology can be prepared. In this case, oleylamine serves the dual function of ligand and solvent.
In the invention, besides the volume ratio of oleic acid to oleylamine, the control of the reaction temperature in step (3) plays a crucial role in the morphology of the product.
Experiments show that when the reaction temperature is controlled to be 150-160 ℃, the prepared product mainly adopts a unilateral radial perovskite structure, namely, nanowires radially grow from the center along a two-dimensional direction (along a plane) and a single direction.
When the reaction temperature is controlled to be 160-200 ℃, the prepared product is mainly of a bilateral radial perovskite structure, namely, the nanowires grow radially and symmetrically from the center along the two-dimensional direction.
In the step (1):
preferably, in the solution I, the concentration of cesium carbonate is 0.05-0.1 mol/L;
preferably, the molar ratio of cesium carbonate to oleic acid is 1: 2 to 6.
In the step (1), the temperature is heated to be more than or equal to 100 ℃, and preferably to be 110-130 ℃.
In the step (2):
in the solution II, the concentration of the lead halide is 0.015-0.05 mol/L.
In the step (2), the temperature is heated to be more than or equal to 100 ℃, and preferably to be 110-130 ℃.
Preferably, the volume ratio of oleic acid to oleylamine is 1:10 to 20.
In the step (3):
preferably, the volume ratio of the solution I to the solution II is 1:10 to 30.
Preferably, the reaction time is 12-24 h.
Compared with the prior art, the invention has the following advantages:
the invention adopts an organic phase synthesis method, and obtains a radial all-inorganic perovskite nano material with unique appearance by optimizing the volume ratio of oleic acid to oleylamine and the reaction temperature in the preparation process.
Drawings
FIG. 1 is an XRD pattern of the product of example 1;
FIG. 2 is an SEM photograph of a product prepared in example 1;
FIG. 3 is a TEM photograph of a product prepared in example 1;
FIG. 4 is an SEM photograph of a product prepared in comparative example 1;
FIG. 5 is an SEM photograph of a product prepared in comparative example 2;
FIG. 6 is an SEM photograph of a product prepared in example 2;
FIG. 7 is an SEM photograph of a product prepared in example 5.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Fully reacting and dissolving 0.1g of cesium carbonate (0.3mmol), 0.3mL (1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) mixing 69mg (0.188mmol) of lead bromide, 0.5mL (1.5mmol) of oleic acid and 10mL (0.03mol) of oleylamine, and fully dissolving at 120 ℃ in an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 160 ℃, injecting 0.4mL of the solution I into the solution II (10.5mL), and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 12h to obtain reaction liquid, and finally centrifuging, separating and washing to obtain a final product.
FIG. 1 is an XRD pattern of the product prepared in this example, which was confirmed by observation of the XRD pattern, and the product composition was CsPbBr3The main growth crystal planes are (100) and (200) as judged from the diffraction peak intensity in XRD.
Fig. 2 is an SEM image of the product prepared in this example, and it can be seen from the figure that the obtained radial all-inorganic perovskite nano material includes a center and about 20 nanowires radially and symmetrically grown from the center along two-dimensional direction, the center particle size is about 150nm, and the material is composed of a plurality of perovskite nano particles, the particle size of a single perovskite nano particle is about 50nm, the diameter of a single nanowire is about 50nm, and the length of a single side is about 20 μm. The perovskite nano-particles and the nano-wires are CsPbBr3。
FIG. 3 is a TEM image of the product prepared in this example, and it can be seen that the main interplanar spacing is 0.75nm, which is in accordance with CsPbBr3The crystal plane spacing of the perovskite material (100) also indicates that the main growth crystal plane of the prepared radial perovskite structure material is (100).
Comparative example 1
(1) Fully reacting and dissolving 0.1g of cesium carbonate (0.3mmol), 0.3mL (1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) dissolving 69mg (0.188mmol) of lead bromide, 0.5mL (1.5mmol) of oleic acid and 0.5mL (1.5mmol) of oleylamine in 5mL of octadecene, and fully dissolving at 120 ℃ under an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 160 ℃, injecting 0.4mL of the solution I into the solution II, and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 12h to obtain reaction liquid, and finally centrifuging, separating and washing to obtain a product.
FIG. 4 is an SEM image of the product prepared in this comparative example, and it can be seen that the prepared product has large particle size of 10-30 μm and no linear structure exists.
Comparative example 2
(1) Fully reacting and dissolving 0.1g of cesium carbonate (0.3mmol), 0.3mL (1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) dissolving 69mg (0.188mmol) of lead bromide, 0.5mL (1.5mmol) of oleic acid and 10mL (0.03mol) of oleylamine fully at 120 ℃ in an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 160 ℃, injecting 0.4mL of the solution I into the solution II, and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 3h to obtain reaction liquid, and finally centrifuging, separating and washing to obtain a product.
FIG. 5 is an SEM image of the product prepared in this comparative example, and it can be seen from the SEM image that the product has some small particle perovskite structures with particle size of 0.2-1 μm and a small amount of perovskite nanowire structures with length of about 10 μm.
Example 2
(1) Fully reacting and dissolving 0.1g (0.3mmol) of cesium carbonate, 0.35mL (1.1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) dissolving 69mg (0.188mmol) of lead bromide and 0.5mL (1.5mmol) of oleic acid in 10mL (0.03mol) of oleylamine sufficiently at 120 ℃ under an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 150 ℃, injecting 0.4mL of the solution I into the solution II, and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 12h to obtain reaction liquid, and finally centrifuging, separating and washing to obtain a product.
FIG. 6 is an SEM photograph of the product prepared in this example, from which it can be seen that CsPbBr was prepared at 150 deg.C3The perovskite structure has a single-side radial perovskite structure and is formed by about 10 perovskite nano wires, the diameter of a single nano wire is about 80nm, and the length of the single nano wire is about 10 mu m.
Example 3
(1) Fully reacting and dissolving 0.1g (0.3mmol) of cesium carbonate, 0.35mL (1.1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) dissolving 69mg (0.188mmol) of lead bromide and 0.5mL (1.5mmol) of oleic acid in 5mL (0.015mol) of oleylamine fully at 120 ℃ under an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 180 ℃, injecting 0.4mL of the solution I into the solution II, and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 12h to obtain reaction liquid, and finally centrifuging, separating and washing to obtain a product.
The morphology of the product prepared in this example was tested to be substantially consistent with that of example 1.
Example 4
(1) Fully reacting and dissolving 0.1g (0.3mmol) of cesium carbonate, 0.3mL (1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) dissolving 69(0.188mmol) mg of lead bromide and 0.5mL (1.5mmol) of oleic acid in 10mL (0.03mol) of oleylamine sufficiently at 120 ℃ under an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 220 ℃, injecting 0.4mL of the solution I into the solution II, and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 12h to obtain reaction liquid, and finally centrifuging, separating and washing to obtain a product.
The morphology of the product prepared in this example was tested to be substantially consistent with that of example 1.
Example 5
(1) Fully reacting and dissolving 0.1g (0.3mmol) of cesium carbonate, 0.35mL (1.1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) dissolving 87mg (0.188mmol) of lead iodide and 0.5mL (1.5mmol) of oleic acid in 10mL (0.03mol) of oleylamine sufficiently at 120 ℃ under an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 160 ℃, injecting 0.4mL of the solution I into the solution II, and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 12h to obtain reaction liquid, and finally centrifuging, separating and washing to obtain a product.
FIG. 7 shows the diluted CsPbI prepared in this example3SEM image of the radial perovskite structure material, from which the radial perovskite structure was obtained, was consistent in morphology with the structure prepared in example 1.
Example 6
(1) Fully reacting and dissolving 0.1g (0.3mmol) of cesium carbonate, 0.35mL (1.1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) dissolving 52mg (0.188mmol) of lead chloride, 1mL of n-trioctylphosphine oxide and 0.5mL (1.5mmol) of oleic acid in 10mL (0.03mol) of oleylamine sufficiently at 120 ℃ under an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 160 ℃, injecting 0.4mL of the solution I into the solution II, and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 12h to obtain reaction liquid, and finally centrifuging, separating and washing to obtain a product.
The product prepared in this example was tested to be CsPbCl3The morphology substantially corresponds to that of example 1.
Example 7
(1) Fully reacting and dissolving 0.1g (0.3mmol) of cesium carbonate, 0.35mL (1.1mmol) of oleic acid and 3.75mL of octadecene at 120 ℃ in an inert atmosphere to obtain a solution I;
(2) dissolving 69mg (0.188mmol) of lead bromide and 0.5mL (1.5mmol) of oleic acid in 10mL (0.03mol) of oleylamine sufficiently at 120 ℃ under an inert atmosphere to obtain a solution II;
(3) raising the temperature of the solution II to 160 ℃, injecting 0.4mL of the solution I into the solution II, and continuing to react and stir;
(4) keeping the same temperature, continuously stirring and reacting for 24h to obtain reaction liquid, and then centrifuging, separating and washing to obtain a final product.
The morphology of the product prepared in this example was tested to be substantially consistent with that of example 1.
Claims (10)
1. A radial all-inorganic perovskite nano material is characterized by comprising a center and nanowires radially growing from the center along a two-dimensional direction;
the center is composed of a plurality of perovskite nano particles, the particle size of the center is 100-200 nm, and the particle size of a single perovskite nano particle is 30-80 nm;
the diameter of the nanowire is 30-80 nm, and the length of the nanowire is 2-20 mu m;
the structural formula of the radial all-inorganic perovskite nano material is CsPbX3And X is selected from Cl, Br or I.
2. The radial all-inorganic perovskite nanomaterial as claimed in claim 1, wherein the nanowires are grown radially symmetrically from the center in two dimensions;
the number of the nanowires is 10-40.
3. A method for preparing a radial all-inorganic perovskite nano-material according to claim 1, which comprises the following steps:
(1) mixing cesium carbonate, oleic acid and octadecene, and heating until the cesium carbonate, the oleic acid and the octadecene are completely dissolved to obtain a solution I;
(2) mixing lead halide, oleic acid and oleylamine, and heating until the lead halide, the oleic acid and the oleylamine are completely dissolved to obtain a solution II;
the volume ratio of the oleic acid to the oleylamine is less than or equal to 1: 10;
(3) and mixing the solution I and the solution II, heating to 150-220 ℃, and fully reacting to obtain the radial all-inorganic perovskite material.
4. The method for preparing a radially all-inorganic perovskite nano-material as claimed in claim 3, wherein in the step (1):
in the solution I, the concentration of cesium carbonate is 0.05-0.1 mol/L;
the molar ratio of cesium carbonate to oleic acid is 1: 2 to 6.
5. The method for preparing a radial all-inorganic perovskite nano material as claimed in claim 3, wherein in the step (1), the heating is carried out to a temperature of 100 ℃ or higher.
6. The method for preparing a radial all-inorganic perovskite nano material as claimed in claim 3, wherein in the step (2), the concentration of the lead halide in the solution II is 0.015-0.05 mol/L.
7. The method for preparing radial all-inorganic perovskite nano material as claimed in claim 3, wherein in the step (2), the heating is carried out to a temperature of 100 ℃ or higher.
8. The method for preparing radial all-inorganic perovskite nano material as claimed in claim 3, wherein in the step (2), the volume ratio of oleic acid to oleylamine is 1:10 to 20.
9. The method for preparing a radially all-inorganic perovskite nano-material as claimed in claim 3, wherein in the step (3):
the volume ratio of the solution I to the solution II is 1:10 to 30.
10. The method for preparing radial all-inorganic perovskite nano material as claimed in claim 3, wherein in the step (3), the reaction temperature is 160-200 ℃ and the reaction time is 12-24 h.
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