CN113980060A - Cadmium and manganese-based solid solution luminescent material and preparation method and application thereof - Google Patents
Cadmium and manganese-based solid solution luminescent material and preparation method and application thereof Download PDFInfo
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- CN113980060A CN113980060A CN202111173844.2A CN202111173844A CN113980060A CN 113980060 A CN113980060 A CN 113980060A CN 202111173844 A CN202111173844 A CN 202111173844A CN 113980060 A CN113980060 A CN 113980060A
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000011572 manganese Substances 0.000 title claims abstract description 19
- 239000006104 solid solution Substances 0.000 title claims abstract description 17
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 7
- 229910052748 manganese Inorganic materials 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- GTYGZIMSYVALIE-UHFFFAOYSA-M [Cl-].CC=1C(=C(C=CC=1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)CC1=CC=CC=C1)C Chemical compound [Cl-].CC=1C(=C(C=CC=1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)CC1=CC=CC=C1)C GTYGZIMSYVALIE-UHFFFAOYSA-M 0.000 claims description 6
- -1 dimethylbenzyl triphenylphosphine chloride Chemical compound 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 description 5
- 150000001875 compounds Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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Abstract
The invention relates to the technical field of luminescent materials, in particular to a solid solution luminescent material based on cadmium and manganese, a preparation method and application thereof, wherein the solid solution luminescent material comprises a chemical formula (C)26H24P)2Cd1‑xMnxCl4，X∈[0，1]Belonging to the orthorhombic system, the space group is Pbca, and the unit cell parameters are as follows:
α ═ β ═ γ ═ 90 °, z ═ 8, and unit cell volume
Invention greenThe color is environment-friendly, and the adjustable light color from blue light emission to green light emission can be realized.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a solid solution luminescent material based on cadmium and manganese, and a preparation method and application thereof.
Background
Due to its excellent photoelectric properties and simple preparation process, metal halide perovskites have become promising functional materials in many fields including photovoltaic cells, light emitting diodes, photodetectors, and the like. Among them, organic-inorganic hybrid halide luminescent materials attract researchers' attention due to excellent photoelectric properties and abundant structural features. In recent years, researchers have focused on the study of halide luminescent materials, mainly on lead perovskite chloride.
In the prior art, lead halide luminescent materials (C) can be synthesized by adopting slow solvent volatilization3H8N6)PbCl4However, the drastic toxicity of lead violates the green chemistry and sustainable development concept. The solid solution luminescent material (C) can be synthesized by using a coprecipitation method10H16N)2Zn1-xMnxBr4However, (C)10H16N)2Zn1-xMnxBr4Only one metal ion Mn in solid solution2+In the presence of luminescence and Zn2+The non-luminescence, that is, only one luminescence center, cannot realize the adjustability of the emission color, and is limited in practical application.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a solid solution luminescent material based on cadmium and manganese, which has a chemical formula of (C)26H24P)2Cd1-xMnxCl4，X∈[0，1]Belonging to the orthorhombic system, the space group is Pbca, and the unit cell parameters are as follows:
α ═ β ═ γ ═ 90 °, z ═ 8, and unit cell volume
The preparation method of the solid solution luminescent material based on cadmium and manganese comprises the following steps:
s1, mixing CdCl2·2/5H2O and dimethylbenzyl triphenylphosphine chloride (C)26H24PCl) is mixed and dissolved in acetonitrile at a molar ratio of 1:2 to form a clear precursor solution, acetone is diffused into the precursor solution at room temperature, and the clear precursor solution is placed for a plurality of days to obtain colorless blocky crystals;
s2, mixing MnCl2·4H2Mixing O and dimethylbenzyl triphenyl phosphonium chloride in a molar ratio of 1:2, dissolving the mixture in acetonitrile to form a clear precursor solution, diffusing diethyl ether into the precursor solution at room temperature, and standing for several days to obtain light green blocky crystals;
s3, mixing MnCl2·4H2O，CdCl2·2/5H2O and dimethylbenzyl triphenyl phosphonium chloride are mixed according to a certain molar ratio, mechanically ground for 10 minutes, and the obtained mixture is filled into a polytetrafluoroethylene tube and calcined for 24 hours at the temperature of 200 ℃ to obtain powdery fluorescent powder.
The solid solution luminescent material based on cadmium and manganese is applied to the aspect of adjustable light color.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention successfully synthesizes the lead-free solid solution luminescent material (C) by combining solvent volatilization and a low-temperature solid phase method26H24P)2Cd1-xMnxCl4，X∈[0，1]Successfully solves the problem of severe toxicity of lead in the traditional lead halide luminescent material. In addition, the compound forms a zero-dimensional structure at the molecular level, in which MnCl is present4 2-Tetrahedron and CdCl4 2-The tetrahedra are distributed in isolated form in the unit cell, so that the luminescence center Cd2+In Mn2+Energy transfer does not exist between the materials, and the luminous efficiency of the material is improved to the maximum extent. The compound can realize adjustable light color from blue light emission to green light emission along with the change of the excitation wavelength and the X value.
Drawings
FIG. 1 is (C)26H24P)2Cd1-xMnxCl4A schematic of the crystal structure of (a);
FIG. 2 is (C)26H24P)2Cd1-xMnxCl4Diffraction patterns of the powders;
FIG. 3 is (C)26H24P)2Cd1-xMnxCl4The spectrum of (a).
Detailed Description
As shown in figures 1-3, the invention provides a solid solution luminescent material based on cadmium and manganese, which has a chemical formula of (C)26H24P)2Cd1-xMnxCl4，X∈[0，1]Belonging to the orthorhombic system, the space group is Pbca, and the unit cell parameters are as follows:
α ═ β ═ γ ═ 90 °, z ═ 8, and unit cell volume
The preparation method of the solid solution luminescent material based on cadmium and manganese comprises the following steps:
s1, mixing CdCl2·2/5H2O and dimethylbenzyl triphenylphosphine chloride (C)26H24PCl) is mixed and dissolved in acetonitrile at a molar ratio of 1:2 to form a clear precursor solution, acetone is diffused into the precursor solution at room temperature, and the clear precursor solution is placed for a plurality of days to obtain colorless blocky crystals;
s2, mixing MnCl2·4H2Mixing O and dimethylbenzyl triphenyl phosphonium chloride in a molar ratio of 1:2, dissolving the mixture in acetonitrile to form a clear precursor solution, diffusing diethyl ether into the precursor solution at room temperature, and standing for several days to obtain light green blocky crystals;
s3, mixing MnCl2·4H2O，CdCl2·2/5H2O and dimethylbenzyl triphenyl phosphonium chloride are mixed according to a certain molar ratio, mechanically ground for 10 minutes, and the obtained mixture is filled into a polytetrafluoroethylene tube and calcined for 24 hours at the temperature of 200 ℃ to obtain powdery fluorescent powder.
The invention successfully synthesizes the lead-free solid solution luminescent material (C) by combining solvent volatilization and a low-temperature solid phase method26H24P)2Cd1-xMnxCl4，X∈[0，1]Successfully solves the problem of severe toxicity of lead in the traditional lead halide luminescent material. Furthermore, the compounds form a zero-dimensional structure at the molecular level, in whichMnCl4 2-Tetrahedron and CdCl4 2-The tetrahedra are distributed in isolated form in the unit cell, so that the luminescence center Cd2+In Mn2+Energy transfer does not exist between the materials, and the luminous efficiency of the material is improved to the maximum extent. The compound can realize adjustable light color from blue light emission to green light emission along with the change of the excitation wavelength and the X value.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited thereto, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (3)
1. A solid solution luminescent material based on cadmium and manganese, characterized in that:
has a chemical formula of (C)26H24P)2Cd1-xMnxCl4，X∈[0，1]Belonging to the orthorhombic system, the space group is Pbca, and the unit cell parameters are as follows:
α ═ β ═ γ ═ 90 °, z ═ 8, and unit cell volume
2. The method for preparing a solid solution luminescent material based on cadmium and manganese according to claim 1, comprising the steps of:
s1, mixing CdCl2·2/5H2O and dimethylbenzyl triphenylphosphine chloride (C)26H24PCl) is mixed and dissolved in acetonitrile at a molar ratio of 1:2 to form a clear precursor solution, acetone is diffused into the precursor solution at room temperature, and the clear precursor solution is placed for a plurality of days to obtain colorless blocky crystals;
s2, mixing MnCl2·4H2O and dimethyl benzyl triphenyl phosphonium chloride are mixed in a molar ratio of 1:2 and dissolved in acetonitrile to form a clear precursor solutionDispersing diethyl ether into the precursor solution at room temperature, and standing for several days to obtain light green blocky crystals;
s3, mixing MnCl2·4H2O，CdCl2·2/5H2O and dimethylbenzyl triphenyl phosphonium chloride are mixed according to a certain molar ratio, mechanically ground for 10 minutes, and the obtained mixture is filled into a polytetrafluoroethylene tube and calcined for 24 hours at the temperature of 200 ℃ to obtain powdery fluorescent powder.
3. Use of a cadmium and manganese based solid solution luminescent material according to claim 1 for light color tunability.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105936668A (en) * | 2016-01-26 | 2016-09-14 | 安庆师范大学 | Cd coordination compound based on flexible amido pyridine ligand and preparation method thereof |
| CN109810139A (en) * | 2019-01-29 | 2019-05-28 | 华南农业大学 | NEW TYPE OF COMPOSITE quaternary alkylphosphonium salt and preparation method thereof and fluorescent applications |
| CN111171074A (en) * | 2020-02-23 | 2020-05-19 | 江西理工大学 | Benzyl triphenyl phosphine tetranuclear manganese (II) complex |
| CN112852413A (en) * | 2021-01-08 | 2021-05-28 | 广西大学 | Manganese-containing perovskite tunable luminescent material and preparation method and application thereof |
| CN113265064A (en) * | 2021-05-28 | 2021-08-17 | 重庆师范大学 | Cadmium-based supramolecular polymer and preparation method and application thereof |
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- 2021-10-09 CN CN202111173844.2A patent/CN113980060A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105936668A (en) * | 2016-01-26 | 2016-09-14 | 安庆师范大学 | Cd coordination compound based on flexible amido pyridine ligand and preparation method thereof |
| CN109810139A (en) * | 2019-01-29 | 2019-05-28 | 华南农业大学 | NEW TYPE OF COMPOSITE quaternary alkylphosphonium salt and preparation method thereof and fluorescent applications |
| CN111171074A (en) * | 2020-02-23 | 2020-05-19 | 江西理工大学 | Benzyl triphenyl phosphine tetranuclear manganese (II) complex |
| CN112852413A (en) * | 2021-01-08 | 2021-05-28 | 广西大学 | Manganese-containing perovskite tunable luminescent material and preparation method and application thereof |
| CN113265064A (en) * | 2021-05-28 | 2021-08-17 | 重庆师范大学 | Cadmium-based supramolecular polymer and preparation method and application thereof |
Non-Patent Citations (6)
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