CN107955181B - High-stability two-dimensional cationic lead halide material and preparation and application thereof - Google Patents
High-stability two-dimensional cationic lead halide material and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a high-stability two-dimensional cationic lead halide material, and preparation and application thereof, wherein the chemical molecular formula of the material is [ PbX ]+]n(H2O)m[‑O2C(CH2)4CO2 ‑]0.5nThe material is used as a single-component phosphor and is used in the field of white light L ED.
Description
Technical Field
The invention belongs to the technical field of fluorescent materials, and relates to a high-stability two-dimensional cationic lead halide material, and preparation and application thereof.
Background
Most inorganic extended topological materials existing in nature and synthesized artificially, such as zeolite molecular sieves, metal oxides, metal phosphates and the like, have an anionic or neutral main framework structure. The main reason is that these porous pure inorganic frameworks are composed of a positively charged metal center and a negatively charged bridging ligand (usually an oxygen atom), and the normal ratio and number of charges coordinated between them determine that the host framework can only be rendered neutral or anionic, while neutral guest molecules or positively charged guest ions are non-covalently within the pore diameter. Compared with a porous anionic inorganic framework, a cationic inorganic lattice framework has a coordination unsaturated metal center, and lattice distortion can be adjusted by changing a group combined with the metal center between layers, so that the porous anionic inorganic lattice framework is expected to show excellent performance in the photoelectric field. However, compared to the porous anionic inorganic framework structure, the design and preparation of the cationic inorganic lattice framework are difficult, and have limitations and challenges.
First, white light is formed by mixing L ED light sources of three or more different colors (usually three primary colors), the mixing of the single color light sources causes energy loss, the conversion efficiency of L ED quanta is extremely high, each primary color L has different driving voltage, service life and temperature characteristics, second, the blue light L ED excites a yellow phosphor to form white light, the method still has the main problems of low color rendering index, large demand of rare earth materials, aperture effect and the like, third, the ultraviolet L ED light source excites three (or more) phosphors to achieve the effect of white light, the characteristic of the ultraviolet light source in a non-visible light region, the problem of the low color rendering index, the requirement of a large amount of rare earth materials, the problem of the aperture effect and the like, the problem of the combination of the three or more color light emission of the three phosphors is solved by the combination of the three kinds of white light emitting phosphors, the stability of the combined emission of the three kinds of white light emitting phosphors is improved compared with the prior art.
At present, a single-component phosphor with inherent broadband white light emission property can respond to ultraviolet L ED light by doping rare earth metals, a small amount of two-dimensional perovskite with a 110 crystal face shows the inherent broadband white light emission property, and mechanism researches show that the broadband emission is derived from self-trapping excitons generated by material lattice distortion, but the perovskite has the problem of instability to moisture, air and heating, so that the application of the perovskite is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-stability two-dimensional cationic lead halide material for solid-state white light illumination, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a high-stability two-dimensional cationic lead halide material has a chemical molecular formula of [ PbX+]n(H2O)m[-O2C(CH2)4CO2 -]0.5nWherein X is F, Cl or Br, n is a positive integer, and m is a natural number.
When X is F, the crystal structure of the material is a tetragonal system; when X is Cl or Br, the crystal structure of the material is monoclinic.
When X is F, the space group of the material is I4/m; when X is Cl, the space group of the material is P2 (1)/n; when X is Br, the space group of the material is C2/C.
When X is F, the material is colorless crystals, white crystals or white powder; when X is Cl, the material is colorless crystals, light yellow crystals or white crystals; when X is Br, the material is colorless crystals, white crystals or white powder.
A preparation method of a high-stability two-dimensional cationic lead halide material specifically comprises the following steps:
1) respectively adding lead halide and disodium adipate into water, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, uniformly mixing, and carrying out hydrothermal reaction;
3) and after the reaction is finished, sequentially cooling, filtering, washing and drying to obtain the high-stability two-dimensional cationic lead halide material.
In the step 1), the lead halide is lead fluoride, lead chloride or lead bromide. Different lead halides are adopted to prepare cationic two-dimensional materials with different lead halide frameworks.
In the step 2), in the hydrothermal reaction process: the reaction temperature is 140 ℃ to 200 ℃, and the reaction time is 40-100 hours.
The mixing method comprises the following steps: stirring or ultrasonic vibrating for 5-30 min.
In the step 2), the hydrothermal reaction is carried out in a closed reaction vessel, and the volume of the closed reaction vessel is 1.2-2 times of the volume of the water in the step 1). The volume of the closed reaction container is controlled to be 1.2-2 times of the volume of water, so that the experimental safety can be ensured, and the yield of the product can be ensured.
In step 3), after cooling to room temperature, crystals or powder are precipitated. Filtering to obtain crystal or powder.
In the step 3), a solvent is adopted for washing, and the solvent comprises one or two of water or ethanol. The solvent used for washing should be capable of dissolving the reaction raw material without destroying the crystals themselves, and includes, but is not limited to, water, ethanol, etc.
In the step 1), the molar ratio of the lead halide to the disodium adipate is 1:1-2.5, 8-20m L of water is added to 1mmol of lead halide, and in the step 2), the dosage of perchloric acid is 2-5 equivalents of perchloric acid per equivalent of lead halide.
The application of high-stability two-dimensional cationic lead halide material as single-component phosphor in the field of white light L ED is provided.
The material consists of a cationic two-dimensional lead halide inorganic layer and adipate dianions for balancing charges among layers. In the preparation process, perchloric acid is used as a pH regulator and a structure stabilizer, and disodium adipate is used as an anion structure directing agent. The coordination unsaturation of the metal center Pb and the inert electron pair effect enable the material to present a cationic inorganic framework, and the corrugated two-dimensional lead halide layer is formed due to the coordination of the metal center Pb and carboxylate radical of the interlayer anion.
Compared with the prior art, the invention has the following characteristics:
1) the invention takes carboxylic acid ligand as an anion structure guiding agent template to synthesize a corrugated two-dimensional cationic lead halide hybrid material, solves the problem of poor stability of the traditional perovskite by utilizing covalent chemical bond of the carboxylic acid ligand and metal, has high structural stability compared with the traditional perovskite material, can keep stable for a long time in organic solvents such as ethanol and the like and hot water, can keep the appearance and the structure intact in aqueous solution with the pH range of 3-12, has higher tolerance to high-temperature environment, and can still keep stable for a long time when being burned at the high temperature of more than 200 ℃ in the air;
2) the material has a highly distorted two-dimensional lead halide inorganic layer, a large number of self-trapping excitons, inherent matrix white light emission property covering a visible light range, and great application potential in the field of white light L ED, wherein when X is F, the material has the widest half-peak width, and when X is Cl, the material has the highest fluorescence quantum yield;
3) the defects of self-absorption of light emission and unstable light emission color of the conventional white light L ED assembly mode of exciting three-component three-primary-color phosphors by ultraviolet L ED are overcome, broadband white light emission in a visible wavelength range is realized, the wide application value is realized in the fields of single-component phosphors and white light L ED, the preparation process is mild, the operation is easy, the reaction is carried out in water, and the preparation method is a green preparation technology.
Drawings
FIG. 1 shows [ PbF ] prepared in example 1+][-O2C(CH2)4CO2 -]0.5A schematic of the crystal structure of (a);
FIG. 2 shows [ PbF ] prepared in example 1+][-O2C(CH2)4CO2 -]0.5X-ray powder diffraction patterns after treatment under different conditions;
FIG. 3 shows [ PbF ] prepared in example 1+][-O2C(CH2)4CO2 -]0.5Fluorescence emission spectrum of (a);
FIG. 4 shows [ PbCl ] prepared in example 2+][-O2C(CH2)4CO2 -]0.5A schematic of the crystal structure of (a);
FIG. 5 shows [ PbCl ] prepared in example 2+][-O2C(CH2)4CO2 -]0.5X-ray powder diffraction patterns after treatment under different conditions;
FIG. 6 shows [ PbCl ] prepared in example 2+][-O2C(CH2)4CO2 -]0.5Fluorescence emission spectrum of (a);
FIG. 7 shows [ PbBr ] prepared in example 3+]3(H2O)[-O2C(CH2)4CO2 -]1.5A schematic of the crystal structure of (a);
FIG. 8 shows [ PbBr ] prepared in example 3+]3(H2O)[-O2C(CH2)4CO2 -]1.5X-ray powder diffraction patterns after treatment under different conditions;
FIG. 9 shows [ PbBr ] prepared in example 3+]3(H2O)[-O2C(CH2)4CO2 -]1.5Fluorescence emission spectrum of (a).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
material [ PbF ]+][-O2C(CH2)4CO2 -]0.5Preparation and performance investigation of (1):
material [ PbF ]+][-O2C(CH2)4CO2 -]0.5The preparation of (1):
0.272g of PbF was weighed20.528g of disodium adipate is dissolved in 8m L water, 230m of L g of perchloric acid is weighed and added into the solution, the obtained suspension is stirred for 30 minutes to be uniformly mixed, the uniform suspension is transferred into a high-pressure reaction kettle with the volume of 12m L and is sealed completely, the high-pressure reaction kettle is placed in a drying oven with the constant temperature of 150 ℃ for reaction for 48 hours, after the reaction is finished, the high-pressure reaction kettle is taken out and opened, the obtained solid is statically transferred into a beaker, the high-pressure reaction kettle is washed by 20m of L water and 20m of L ethanol in sequence and is dried in the air to obtain the material [ PbF ]+][-O2C(CH2)4CO2 -]0.5。
The material obtained in this example was white crystals. The framework connection structure of the material is shown in figure 1, which is confirmed by X-ray single crystal diffraction characterization, and the material is provided with a highly distorted two-dimensional lead fluoride inorganic layer.
Material [ PbF ]+][-O2C(CH2)4CO2 -]0.5Stability investigation of (1):
weighing 0.1g of the sample prepared in this example, soaking in hydrochloric acid having pH 3, an aqueous solution of sodium hydroxide having pH 12, boiling water, or calcining in air at 250 ℃; after 24 hours the material was filtered off, washed clean with ethanol and dried. The crystallinity of the sample is characterized by X-ray powder diffraction (PXRD) and compared with a PXRD image of an untreated sample to examine the stability of the sample, and a comparison graph is shown in figure 2, so that the prepared material has high acid-base stability and high-temperature stability.
Material [ PbF ]+][-O2C(CH2)4CO2 -]0.5Examination of light-emitting properties:
weighing a certain amount of sample, respectively measuring an ultraviolet-visible absorption spectrum of the sample by using a Shimadzu UV-2600 ultraviolet-visible diffuse reflection instrument, and measuring a fluorescence excitation spectrum, a fluorescence emission spectrum, a fluorescence attenuation curve and a fluorescence quantum yield of the sample by using an Edinburgh F L S980 steady-state/transient fluorescence spectrometer, wherein the fluorescence emission spectrum is shown in figure 3, and the material has good fluorescence emission performance.
Example 2:
material [ PbCl ]+][-O2C(CH2)4CO2 -]0.5Preparation and performance investigation of (1):
material [ PbCl ]+][-O2C(CH2)4CO2 -]0.5The preparation of (1):
0.417g of PbCl was weighed20.570g of disodium adipate, dissolving the disodium adipate in 8m L water, measuring 430m L perchloric acid, adding the solution into the suspension, stirring the obtained suspension for 30 minutes to mix the suspension uniformly, transferring the uniform suspension into a high-pressure reaction kettle with the volume of 15m L, sealing the high-pressure reaction kettle completely, placing the high-pressure reaction kettle in an oven with the constant temperature of 175 ℃ for reacting for 48 hours, taking out the high-pressure reaction kettle after the reaction is finished, transferring the obtained solid to a beaker, washing the beaker with 20m L water and 20m L ethanol in sequence, and airing to obtain a material [ PbCl ]+][-O2C(CH2)4CO2 -]0.5。
The material obtained in this example was white crystals. The framework connection structure of the material is confirmed by X-ray single crystal diffraction characterization as shown in figure 4, and the material is seen to possess a highly distorted two-dimensional lead chloride inorganic layer.
Material [ PbCl ]+][-O2C(CH2)4CO2 -]0.5Stability investigation of (1):
weighing 0.1g of the sample obtained in this example, and soaking in hydrochloric acid having a pH of 3, an aqueous solution of sodium hydroxide having a pH of 12, boiling water, or calcining at 200 ℃ in air; after 24 hours the material was filtered off, washed clean with ethanol and dried. The crystallinity of the sample is characterized by X-ray powder diffraction (PXRD) and compared with a PXRD image of an untreated sample to examine the stability of the sample, and a comparison graph is shown in figure 5, so that the prepared material has high acid-base stability and high-temperature stability.
Material [ PbCl ]+][-O2C(CH2)4CO2 -]0.5Examination of light-emitting properties:
weighing a certain amount of sample, respectively measuring an ultraviolet-visible absorption spectrum of the sample by using a Shimadzu UV-2600 ultraviolet-visible diffuse reflection instrument, and measuring a fluorescence excitation spectrum, a fluorescence emission spectrum, a fluorescence attenuation curve and a fluorescence quantum yield of the sample by using an Edinburgh F L S980 steady-state/transient fluorescence spectrometer, wherein the fluorescence emission spectrum is shown in figure 6, and the material has good fluorescence emission performance.
Example 3:
material [ PbBr ]+]3(H2O)[-O2C(CH2)4CO2 -]1.5Preparation and performance investigation of (1):
material [ PbBr ]+]3(H2O)[-O2C(CH2)4CO2 -]1.5The preparation of (1):
0.551g of PbBr was weighed20.570g of disodium adipate is dissolved in 8m L of water, 430m of L of perchloric acid is weighed and added into the solution, the obtained suspension is stirred for 30 minutes to be uniformly mixed, the uniform suspension is transferred into a high-pressure reaction kettle with the volume of 20m L and is sealed completely, the high-pressure reaction kettle is placed in an oven with the constant temperature of 175 ℃ for reaction for 48 hours, after the reaction is finished, the high-pressure reaction kettle is taken out and opened, the obtained solid is statically transferred into a beaker, and the high-pressure reaction kettle is washed by 20m of L of water and 20m of L of ethanol in sequence and then dried to obtain the material.
The material obtained in this example was white crystals. The framework connection structure of the material is confirmed by X-ray single crystal diffraction characterization as shown in FIG. 7, and the material is seen to possess a highly distorted two-dimensional lead bromide inorganic layer.
Material [ PbBr ]+]3(H2O)[-O2C(CH2)4CO2 -]1.5Stability investigation of (1):
weighing 0.1g of the sample obtained in this example, and soaking in hydrochloric acid having a pH of 3, an aqueous solution of sodium hydroxide having a pH of 12, boiling water, or calcining at 200 ℃ in air; after 24 hours the material was filtered off, washed clean with ethanol and dried. The crystallinity of the sample is characterized by X-ray powder diffraction (PXRD) and compared with a PXRD image of an untreated sample to examine the stability of the sample, and a comparison graph is shown in figure 8, so that the prepared material has high acid-base stability and high-temperature stability.
Material [ PbBr ]+]3(H2O)[-O2C(CH2)4CO2 -]1.5Examination of light-emitting properties:
weighing a certain amount of sample, respectively measuring an ultraviolet-visible absorption spectrum of the sample by using a Shimadzu UV-2600 ultraviolet-visible diffuse reflection instrument, and measuring a fluorescence excitation spectrum, a fluorescence emission spectrum, a fluorescence attenuation curve and a fluorescence quantum yield of the sample by using an Edinburgh F L S980 steady-state/transient fluorescence spectrometer, wherein the fluorescence emission spectrum is shown in figure 9, and the material has good fluorescence emission performance.
Example 4:
material [ PbF ]+][-O2C(CH2)4CO2 -]0.5The synthesis of (2):
the chemical formula of the cationic lead fluoride material in this embodiment is [ PbF+][-O2C(CH2)4CO2 -]0.5The material was white powder.
The preparation method of the high-stability two-dimensional cationic lead fluoride material specifically comprises the following steps:
1) adding lead fluoride and disodium adipate into water, and fully mixing to obtain a uniform suspension;
2) adding perchloric acid into the suspension obtained in the step 1), and fully mixing;
3) transferring the uniform suspension obtained in the step 2) into a closed reaction container for hydrothermal reaction;
4) after the hydrothermal reaction is finished, cooling the system to room temperature, and precipitating crystals or powder;
5) taking out the crystal or powder obtained in the step 4), washing the crystal or powder to be pure by using a solvent, and drying to obtain the high-stability two-dimensional cationic lead fluoride material.
In the step 1), the molar ratio of the lead fluoride to the disodium adipate is 1: 1.5.
In the step 1), the amount of water is 8m L per 1mmol of lead fluoride.
In the step 2), the dosage of perchloric acid is as follows: each equivalent of lead fluoride corresponds to 2 equivalents of perchloric acid.
In the step 3), the hydrothermal reaction conditions are as follows: the reaction temperature was 140 ℃ and the reaction time was 100 hours.
In step 3), the volume of the closed reaction vessel was 1.2 times the volume of the water used in step 1).
The high-stability cationic two-dimensional lead fluoride material can be used as a single-component white phosphor in the field of white light L ED.
Example 5:
a high-stability two-dimensional cationic lead halide material has a chemical molecular formula of [ PbF+][-O2C(CH2)4CO2 -]0.5The crystal structure of the material is tetragonal system, and the space group of the material is I4/m.
The preparation method of the material specifically comprises the following steps:
1) respectively adding lead fluoride and disodium adipate into water according to the molar ratio of 1:1, adding water of 20m L into each 1mmol of lead fluoride, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead fluoride to correspond to 2 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction for 40 hours at 200 ℃, wherein the volume of the closed reaction container is 2 times of that of water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with ethanol, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
Example 6:
a high-stability two-dimensional cationic lead halide material has a chemical molecular formula of [ PbF+][-O2C(CH2)4CO2 -]0.5The crystal structure of the material is tetragonal system, and the space group of the material is I4/m.
The preparation method of the material specifically comprises the following steps:
1) respectively adding lead fluoride and disodium adipate into water according to the mol ratio of 1:2.5, adding 8m L water into each 1mmol of lead fluoride, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead fluoride to correspond to 5 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction for 100 hours at 140 ℃, wherein the volume of the closed reaction container is 1.2 times of the volume of the water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with water, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
Example 7:
a high-stability two-dimensional cationic lead halide material has a chemical molecular formula of [ PbF+][-O2C(CH2)4CO2 -]0.5The crystal structure of the material is tetragonal system, and the space group of the material is I4/m.
The preparation method of the material specifically comprises the following steps:
1) respectively adding lead fluoride and disodium adipate into water according to the mol ratio of 1:1.8, adding 14m L water into each 1mmol of lead fluoride, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead fluoride to correspond to 3 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction at 170 ℃ for 70 hours, wherein the volume of the closed reaction container is 1.6 times of that of water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with water and ethanol, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
Example 8:
a high-stability two-dimensional cationic lead halide material has a chemical formula of [ PbCl+][-O2C(CH2)4CO2 -]0.5The crystal structure of the material is monoclinic, and the space group of the material is P2 (1)/n.
The preparation method of the material specifically comprises the following steps:
1) respectively adding lead chloride and disodium adipate into water according to the molar ratio of 1:1, adding water of 20m L into each 1mmol of lead chloride, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead chloride to correspond to 2 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction for 40 hours at 200 ℃, wherein the volume of the closed reaction container is 2 times of that of water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with water, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
Example 9:
a high-stability two-dimensional cationic lead halide material has a chemical formula of [ PbCl+][-O2C(CH2)4CO2 -]0.5The crystal structure of the material is monoclinic, and the space group of the material is P2 (1)/n.
The preparation method of the material specifically comprises the following steps:
1) adding lead chloride and disodium adipate into water according to a molar ratio of 1:2.5 respectively, adding 8m L water into each 1mmol of lead chloride, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead chloride to correspond to 5 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction for 100 hours at 140 ℃, wherein the volume of the closed reaction container is 1.2 times of the volume of the water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with ethanol, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
Example 10:
a high-stability two-dimensional cationic lead halide material has a chemical formula of [ PbCl+][-O2C(CH2)4CO2 -]0.5The crystal structure of the material is monoclinic, and the space group of the material is P2 (1)/n.
The preparation method of the material specifically comprises the following steps:
1) respectively adding lead chloride and disodium adipate into water according to the mol ratio of 1:1.6, adding 15m L water into each 1mmol of lead chloride, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead chloride to correspond to 4 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction for 60 hours at 160 ℃, wherein the volume of the closed reaction container is 1.5 times of the volume of the water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with water and ethanol, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
Example 11:
a high-stability two-dimensional cationic lead halide material has a chemical molecular formula of [ PbBr ]+]3(H2O)[-O2C(CH2)4CO2 -]1.5The crystal structure of the material is monoclinic, and the space group of the material is C2/C.
The preparation method of the material specifically comprises the following steps:
1) respectively adding lead bromide and disodium adipate into water according to the molar ratio of 1:1, adding 20m L water into every 1mmol of lead bromide, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead bromide to correspond to 2 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction for 40 hours at 200 ℃, wherein the volume of the closed reaction container is 2 times of that of water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with water, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
Example 12:
a high-stability two-dimensional cationic lead halide material has a chemical molecular formula of [ PbBr ]+]3(H2O)[-O2C(CH2)4CO2 -]1.5The crystal structure of the material is monoclinic, and the space group of the material is C2/C.
The preparation method of the material specifically comprises the following steps:
1) respectively adding lead bromide and disodium adipate into water according to the mol ratio of 1:2.5, adding 8m L water into each 1mmol of lead bromide, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead bromide to correspond to 5 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction for 100 hours at 140 ℃, wherein the volume of the closed reaction container is 1.2 times of the volume of the water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with ethanol, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
Example 13:
a high-stability two-dimensional cationic lead halide material has a chemical molecular formula of [ PbBr ]+]3(H2O)[-O2C(CH2)4CO2 -]1.5The crystal structure of the material is monoclinic, and the space group of the material is C2/C.
The preparation method of the material specifically comprises the following steps:
1) respectively adding lead bromide and disodium adipate into water according to the molar ratio of 1:2, adding 17m L water into each 1mmol of lead bromide, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, enabling each equivalent of lead bromide to correspond to 4 equivalents of perchloric acid, uniformly mixing, transferring into a closed reaction container, and carrying out hydrothermal reaction for 70 hours at 180 ℃, wherein the volume of the closed reaction container is 1.8 times of the volume of the water in the step 1);
3) and after the reaction is finished, cooling and filtering to obtain a solid, washing the solid with water and ethanol, and drying to obtain the high-stability two-dimensional cationic lead halide material.
The material is used as a single-component phosphor in the field of white light L ED.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A high-stability two-dimensional cationic lead halide material is characterized in that the chemical molecular formula of the material is [ PbX ]+]n(H2O)m[-O2C(CH2)4CO2 -]0.5nWherein X is F, Cl or Br, n is a positive integer, and m is a natural number.
2. The high-stability two-dimensional cationic lead halide material as claimed in claim 1, wherein when X is F, the crystal structure of the material is tetragonal; when X is Cl or Br, the crystal structure of the material is monoclinic.
3. The high-stability two-dimensional cationic lead halide material as claimed in claim 1, wherein when X is F, the space group of the material is I4/m; when X is Cl, the space group of the material is P2 (1)/n; when X is Br, the space group of the material is C2/C.
4. A method for preparing the high-stability two-dimensional cationic lead halide material according to any one of claims 1 to 3, which comprises the following steps:
1) respectively adding lead halide and disodium adipate into water, and uniformly mixing to obtain a suspension;
2) adding perchloric acid into the suspension, uniformly mixing, and carrying out hydrothermal reaction;
3) after the reaction is finished, sequentially cooling, filtering, washing and drying to obtain the high-stability two-dimensional cationic lead halide material;
in the step 1), the molar ratio of the lead halide to the disodium adipate is 1:1-2.5, 8-20m L of water is added to 1mmol of lead halide, and in the step 2), the dosage of perchloric acid is 2-5 equivalents of perchloric acid per equivalent of lead halide.
5. The method for preparing the high-stability two-dimensional cationic lead halide material according to claim 4, wherein in the step 1), the lead halide is lead fluoride, lead chloride or lead bromide.
6. The method for preparing the high-stability two-dimensional cationic lead halide material according to claim 4, wherein in the step 2), the hydrothermal reaction process comprises: the reaction temperature is 140 ℃ to 200 ℃, and the reaction time is 40-100 hours.
7. The method according to claim 4, wherein the hydrothermal reaction is performed in a closed reaction vessel in step 2), and the volume of the closed reaction vessel is 1.2-2 times of the volume of the water in step 1).
8. The method for preparing the high-stability two-dimensional cationic lead halide material according to claim 4, wherein the washing step 3) is performed with a solvent, and the solvent comprises one or both of water and ethanol.
9. Use of the high stability two-dimensional cationic lead halide material according to any one of claims 1 to 3 as a single component phosphor in the field of white light L ED.
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