CN112062682A - Novel composite double quaternary ammonium salt manganese metal halide luminescent material and preparation method and application thereof - Google Patents
Novel composite double quaternary ammonium salt manganese metal halide luminescent material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 29
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 27
- -1 trimethyl ammonium halide Chemical class 0.000 claims abstract description 61
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 150000004820 halides Chemical group 0.000 claims abstract description 5
- 125000002577 pseudohalo group Chemical group 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 24
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 16
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000012433 hydrogen halide Substances 0.000 claims description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 4
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000013256 coordination polymer Substances 0.000 claims description 2
- 125000001824 selenocyanato group Chemical group *[Se]C#N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 description 21
- 238000001704 evaporation Methods 0.000 description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 229910001512 metal fluoride Inorganic materials 0.000 description 20
- 238000002189 fluorescence spectrum Methods 0.000 description 17
- 229910001509 metal bromide Inorganic materials 0.000 description 13
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 12
- XPIIDKFHGDPTIY-UHFFFAOYSA-N F.F.F.P Chemical compound F.F.F.P XPIIDKFHGDPTIY-UHFFFAOYSA-N 0.000 description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 11
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- IXYXXQNFKSEXJM-UHFFFAOYSA-N n,n-dimethylmethanamine;hydron;fluoride Chemical compound F.CN(C)C IXYXXQNFKSEXJM-UHFFFAOYSA-N 0.000 description 8
- CURCMGVZNYCRNY-UHFFFAOYSA-N trimethylazanium;iodide Chemical compound I.CN(C)C CURCMGVZNYCRNY-UHFFFAOYSA-N 0.000 description 7
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 description 6
- 229910001510 metal chloride Inorganic materials 0.000 description 6
- NTKVWOTYTNWGRK-UHFFFAOYSA-N P.Br.Br.Br Chemical compound P.Br.Br.Br NTKVWOTYTNWGRK-UHFFFAOYSA-N 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- UNYLDXKHMGGTKT-UHFFFAOYSA-N [I-].[Mn].C[NH+](C)C Chemical compound [I-].[Mn].C[NH+](C)C UNYLDXKHMGGTKT-UHFFFAOYSA-N 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 2
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 2
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005090 crystal field Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 2
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910001511 metal iodide Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- VZJFGSRCJCXDSG-UHFFFAOYSA-N Hexamethonium Chemical compound C[N+](C)(C)CCCCCC[N+](C)(C)C VZJFGSRCJCXDSG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229950002932 hexamethonium Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- ILVUABTVETXVMV-UHFFFAOYSA-N hydron;bromide;iodide Chemical compound Br.I ILVUABTVETXVMV-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- VVIKPHGZDMHYRV-UHFFFAOYSA-J tetrabromomanganese Chemical compound Br[Mn](Br)(Br)Br VVIKPHGZDMHYRV-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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- 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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract
The invention discloses a novel composite double quaternary ammonium salt manganese metal halide luminescent material, and a preparation method and application thereof. The method comprises the following steps: adding n-methylene-1, 6-bis (trimethyl ammonium halide) into halogen acid, and dissolving to obtain a solution 1; adding manganese halide into halogen acid, and dissolving to obtain a solution 2; and uniformly mixing the solution 1 and the solution 2, filtering and crystallizing to obtain the novel composite bis-quaternary ammonium salt manganese metal halide luminescent material. The chemical formula of the material is [ C ]6+nH2n+18N2]2+[MnX4]2‑And X is selected from halide or pseudohalide. It shows good green or yellow fluorescence effect under the irradiation of ultraviolet or blue light, especially has extremely strong 460nm fluorescence effect, is an optical material with excellent performance, and uses the luminescent material andthe red luminescent material is combined with the blue LED chip to generate white light, and the luminous efficiency is not obviously changed when the white light is continuously measured for 1200min under the condition of electrifying.
Description
Technical Field
The invention belongs to the field of novel functional materials, and particularly relates to a novel composite bis-quaternary ammonium salt manganese metal halide luminescent material, and a preparation method and application thereof.
Background
Luminescent materials refer to materials of matter that are capable of absorbing energy in some way, converting it into light radiation (non-equilibrium radiation). Photoluminescence is the most common light-emitting mode in light-emitting materials, and can be applied to the fields of energy, sensing, display and the like. One of the main fields of application of photoluminescent materials is in lighting sources, such as fluorescent lamps, tricolor lamps, etc., and ultraviolet lamps, etc., and the powder thereof is an ideal material for producing luminescent coatings, anti-counterfeiting coatings, luminescent plastics, etc.
Among illumination light sources, white LEDs have been widely used in real life due to their high efficiency, long life, low power consumption, and environmental friendliness. Commercially available white LEDs are typically composed of a single blue gallium nitride (GaN) chip combined with a yellow Yttrium Aluminum Garnet (YAG) phosphor, but have a low color rendering index (CRI < 75).
In recent years, organic-inorganic hybrid metal halides have gained wide attention in the field of LED applications. Numerous studies have shown that certain cu (i) and pb (ii) complexes exhibit excellent luminescence properties, however the cu (i) complexes have poor photo-thermal stability (t.jun, k.sim, s.iimura, m.sasase, h.kamioka, j.kim and h.hosno, Adv Mater,2018,30, e1804547.), and the pb (ii) complexes have high toxicity (l.n.quan, b.p.rand, r.h.friend, s.g.mhaiskar, t.w.lee and e.h.sargent, Chem Rev,2019,119, 7444-7477.). Therefore, the search for a substitute with low cost, high luminescence efficiency, strong stability and low toxicity is an urgent problem to be solved. Compared with luminescent materials such as Cu (I) and Pb (II), the Mn (II) compound has the obvious advantages of high-efficiency luminescence, high thermal stability, low price, low toxicity and the like, is expected to be a substitute of the traditional luminescent materials, and thus has attracted great research interest (L.Mao, P.Guo, S.Wang, A.K.Cheetham and R.Seshadri, J Am Chem Soc,2020,142,13582 and 13589.). Mn2+Having a 3d5Electronic configuration, 5 single electron resolutions occupy 5 d orbitals. From Tanabe-Sugano diagram, it can be determined that the broadband emission peak of Mn (II) complex is derived from spin-forbidden d-d transition (4T1→6A1) The luminescence characteristics of which depend mainly on the ligand and its coordination crystal field. The organic-inorganic hybrid manganese metal halide has abundant organic ligands, so that the crystal field can be regulated and controlled by changing the ligands, and great attention is paid.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a novel composite bis-quaternary ammonium salt manganese metal halide luminescent material, and a preparation method and application thereof.
The invention aims to provide a zero-dimensional novel compound biquaternary ammonium salt manganese metal halide with fluorescence property, namely tetrahalogenated manganese-n methylene-1, 6-bis (trimethyl ammonium) salt, which is a compound [ C ] composed of tetrahalogenated manganese anions and n methylene-1, 6-bis (trimethyl ammonium) cations12H30N2]2+[MnX4]2-Abbreviated as [ Hexamethonium][MnX4]And X is selected from halide or pseudohalide. Preferably, X is Br. The fluorescent material shows good green or yellow fluorescent effect under the irradiation of ultraviolet or blue light, particularly has extremely strong 460nm fluorescent effect, and is an optical material with excellent performance.
The invention also discloses a method for preparing the material, which has the advantages of high yield, cost saving, easy operation and contribution to industrial production.
The invention also aims to provide a zero-dimensional novel composite biquaternary ammonium salt manganese metal halide luminescent material with fluorescence property, which is obtained by the preparation method and is applied to the fields of white light LEDs and the like.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a novel composite bis-quaternary ammonium salt manganese metal halide luminescent material (zero-dimensional manganese metal halide), which is tetrahalogenated manganese-n methylene-1, 6-bis (trimethyl ammonium) salt and is tetrahalogenated manganese anion and n methyleneCompound [ C ] composed of radical-1, 6-bis (trimethylammonium) cation6+nH2n+18N2]2+[MnX4]2-And X is selected from halide or pseudohalide.
The novel composite bis-quaternary ammonium salt manganese metal halide luminescent material (zero-dimensional manganese metal halide) provided by the invention has the following structural general formula (formula I):
wherein n represents the number of carbon atoms, and the value of n is more than or equal to 4; each X is independently selected from halogen or pseudohalogen.
Further, X is selected from F, Cl, Br, I, CN, SCN, NCS, CP, NC, OCN, OSCN, SeCN and N3One or more of them.
Preferably, the X is selected from one or more of F, Cl, Br, I, CN and SCN.
Further preferably, the X is selected from one or more of F, Cl, Br and I.
Further, the halide luminescent material is in a crystal form belonging to a monoclinic system, P21/n space group, and a is b isc isAlpha is 90 deg., beta is 93.40-93.41 deg., and gamma is 90 deg..
The invention provides a method for preparing the novel composite double quaternary ammonium salt manganese metal halide luminescent material, which comprises the following steps:
(1) adding n-methylene-1, 6-bis (trimethyl ammonium halide) into halogen acid, and fully and uniformly dissolving to obtain a solution 1; adding manganese halide into halogen acid, and fully and uniformly dissolving to obtain a solution 2;
(2) and uniformly mixing the solution 1 and the solution 2 in a container, filtering to obtain filtrate, and crystallizing to obtain the novel composite bis-quaternary ammonium manganese metal halide luminescent material.
Further, the n-methylene-1, 6-bis (trimethylammonium halide) in the step (1) is hexamethylene-1, 6-bis (trimethylammonium bromide); the hydrohalic acid is hydrobromic acid; the manganese halide in the step (1) is manganese bromide, and the hydrohalic acid is hydrobromic acid.
Further, in the solution 1 in the step (1), the concentration of hexamethylene-1, 6-bis (trimethyl ammonium halide) is 0.1-1mmol/L, and the concentration of hydrogen halide is 4-13 mol/L; in the solution 2 in the step (1), the concentration of manganese halide is 0.1-4mmol/L, and the concentration of hydrogen halide is 4-13 mol/L. In solution 2, the HBr of the hydrobromic acid is greater than MnBr2Two times the molar ratio.
Further, the volume ratio of the solution 1 to the solution 2 in the step (2) is 4:1-1: 2;
further, the temperature of the crystallization treatment in the step (2) is 50 ℃, and the time of the crystallization treatment is 120 hours.
The invention provides application of a novel composite bis-quaternary ammonium manganese metal halide luminescent material in a white light LED.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the zero-dimensional novel biquaternary ammonium salt manganese metal halide with the fluorescence property shows good green or yellow fluorescence effect under the irradiation of ultraviolet light or blue light, particularly has extremely strong fluorescence effect at 460nm, and is an optical material with excellent performance; the luminescent material and the red luminescent material are combined with a blue LED chip to generate white light, and the luminous efficiency is not obviously changed when the white light is continuously measured for 1200min under the condition of electrifying, which is shown in a reference figure 6.
Drawings
FIG. 1 is a comparison of XRD versus single crystal data fitting for the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide phosphor prepared in example 1;
FIG. 2 is an infrared spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide phosphor prepared in example 1;
FIG. 3 is a Raman spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide phosphor prepared in example 1;
FIG. 4 is a graph of the excitation and emission fluorescence spectra of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide phosphor prepared in example 1;
FIG. 5 is a graph showing the fluorescence lifetime of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide phosphor prepared in example 1;
FIG. 6 is a graph of the luminous efficiency of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide luminescent material prepared in example 1 as a function of time;
FIG. 7 is an XRD of a novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor of example 2;
FIG. 8 is a fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 2;
FIG. 9 is an XRD of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal chloride phosphor prepared in example 3;
FIG. 10 is a fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal chloride phosphor prepared in example 3;
FIG. 11 is an XRD of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese iodide luminescent material prepared in example 4;
FIG. 12 is a fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese iodide luminescent material prepared in example 4;
FIG. 13 is an XRD of a novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 6;
FIG. 14 is a fluorescence spectrum of a novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 6;
FIG. 15 is an XRD of a novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal chloride luminescent material prepared in example 7;
FIG. 16 is a fluorescence spectrum of a novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal chloride luminescent material prepared in example 7;
FIG. 17 is an XRD of a novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal bromide luminescent material prepared in example 8;
FIG. 18 is a fluorescence spectrum of a novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal bromide luminescent material prepared in example 8;
FIG. 19 is an XRD of the novel composite decamethylene-1, 6-bis (trimethylammonium) manganese iodide luminescent material prepared in example 9;
FIG. 20 is a fluorescence spectrum of the novel composite decamethylene-1, 6-bis (trimethylammonium) manganese iodide luminescent material prepared in example 9.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
The preparation method of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium bromide) into a container, and adding 2ml of hydrobromic acid with the concentration of 8mol/L to fully dissolve the mixture;
(2) 1mmol of manganese halide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(3) and (2) taking the solution with the volume ratio of 1:1 in the steps (1) and (2), uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle head type filter, taking filtrate, putting the filtrate into a 50 ℃ oven for evaporation, and generating crystals (the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide luminescent material) after 120 hours.
And carrying out related detection on the obtained green transparent crystal, wherein the specific data are as follows:
crystal structure: at 150K, Cu Ka radiation monochromatized by a graphite monochromator is used as a light source on a Bruker X-ray single crystal diffractometerDiffraction data were collected over a range of angles (0-90) in a beta-omega scan at room temperature. All data reduction is carried out by using CrysAlisPro software and analysis is carried out by using Olex2 software, coordinates and anisotropic thermal parameters of all non-hydrogen atoms are refined by a full matrix least square method, and all hydrogen atoms are theoretically hydrogenated. The tetrabromo manganese-hexamethylene-1, 6-bis (trimethyl ammonium) salt belongs to monoclinic system, P21/n space group, and one asymmetric unit contains 8 hexamethylene-1, 6-bis (trimethyl ammonium) cations [ C12H30N2]2+And 8 tetrabromomanganese [ MnX ]4]2-. The crystal structure is shown in figure 1, and the crystallographic data are shown in table 1.
Powder X-ray diffraction: powder X-ray diffraction of tetrabromomanganese-hexamethylene-1, 6-bis (trimethylammonium) salt (novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal bromide luminescent material)The spectra were tested at room temperature using a model PANalytical produced by Pasnacaceae, the Netherlands.
The measurement conditions were tube pressure: 40kV, pipe flow: 20mA, Cu k alpha radiation scanning speed of 1 degree/min-1Step interval: 0.02 °, scan range (2 θ): 5-90 deg. and the scanning mode is continuous scanning, see figure 1. As can be seen from FIG. 1, the XRD peaks observed in the experiment are well matched with the XRD pattern with the close data of the crystal structure, which shows that the tetrabromomanganic-hexamethylene-1, 6-bis (trimethylammonium) salt has better crystallinity and purity.
Infrared: v (methylene C-H): 2939, 2887; v (methyl C-H): 2836, 1345; v (C-N): 1024. see figure 2 for details.
Raman: at 158cm-1Is a characteristic peak of Mn-Br bond, and is detailed in figure 3.
Fluorescence spectrum analysis: the fluorescence spectrum of tetrabromomanganese-hexamethylene-1, 6-bis (trimethylammonium) salt was measured with an F-4600 spectrophotometer manufactured by Hitachi corporation. When excited at the maximum excitation wavelength of 460nm, the manganese tetrabromide-hexamethylene-1, 6-bis (trimethylammonium) salt has a sharp strong peak at 534nm, as shown in FIG. 4.
And (3) fluorescence lifetime test: fluorescence lifetime test of tetrabromomanganese-hexamethylene-1, 6-bis (trimethylammonium) salt was tested using FLS-920, manufactured by Edinburgh corporation. When the excitation was carried out at a maximum excitation wavelength of 460nm, the lifetime was found to be 0.317. mu.m when the excitation was carried out at 534 nm. See figure 5 for details.
The green luminescent material and K prepared by the implementation2SiF6:Mn4+The red fluorescent powder is packaged into a white light LED, and the light saturation performance of the white light LED chip is researched by changing the current. As can be seen from the graph of fig. 6, the light effect versus current variation shows that no significant light saturation is observed as the current increases. This shows that the prepared green luminescent material can be used in white light LED, as shown in FIG. 6.
TABLE 1 Crystal data of tetrabromomanganese-hexamethylene-1, 6-bis (trimethylammonium) salt
Example 2
The preparation method of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium fluoride) into a container, and adding 2ml of 49 wt% hydrofluoric acid to fully dissolve;
(2) 1mmol of manganese fluoride is put into a container, and 2ml of 49 wt% hydrofluoric acid is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours. The XRD pattern of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material prepared in example 2 is shown in figure 7. The fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 2 is shown in FIG. 8.
Example 3
The preparation method of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal chloride luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium chloride) into a container, and adding 2ml of hydrochloric acid with the concentration of 12mol/L to fully dissolve;
(2) 1mmol of manganese chloride is put into a container, and 2ml of hydrochloric acid with the concentration of 12mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours. The XRD pattern of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material prepared in example 3 is shown in figure 9. The fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 3 is shown in FIG. 10.
Example 4
The preparation method of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal iodide luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium iodide) into a container, and adding 2ml of 45 wt% hydriodic acid to fully dissolve;
(2) 1mmol of manganese iodide is put into a container, and 2ml of 45 wt% hydriodic acid is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours. The XRD pattern of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material prepared in example 4 is shown in figure 11. The fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 4 is shown in FIG. 12.
Example 5
The preparation method of the novel composite hexamethylene-1, 6-bis (trimethyl ammonium) manganese metal bromide iodide luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium iodide) into a container, and adding 2ml of 45 wt% hydriodic acid to fully dissolve;
(2) putting 1mmol of manganese bromide into a container, and adding 2ml of hydrobromic acid with the concentration of 8mol/L to fully dissolve the manganese bromide;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 6
The preparation method of the novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium fluoride) is put into a container, and 2ml of 49 wt% hydrofluoric acid is added to be fully dissolved;
(2) putting 1mmol of manganese fluoride into a container, and adding 2ml of 49 wt% hydrofluoric acid for fully dissolving;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
The XRD pattern of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material prepared in example 6 is shown in figure 13. The fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 6 is shown in FIG. 14.
Example 7
The preparation method of the novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal chloride luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium chloride) is put into a container, and 2ml of hydrochloric acid with the concentration of 12mol/L is added to fully dissolve the decamethylene-1, 6-bis (trimethyl ammonium chloride);
(2) 1mmol of manganese chloride is put into a container, and 2ml of hydrochloric acid with the concentration of 12mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
The XRD pattern of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material prepared in example 7 is shown in figure 15. The fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 7 is shown in FIG. 16.
Example 8
The preparation method of the novel composite decamethylene-1, 6-bis (trimethylammonium) manganese metal bromide luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium bromide) is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
The XRD pattern of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material prepared in example 8 is shown in figure 17. The fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 8 is shown in FIG. 18.
Example 9
The preparation method of the novel composite decamethylene-1, 6-bis (trimethyl ammonium) manganese metal iodide luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium iodide) is put into a container, and 2ml of 45 wt% hydriodic acid is added to fully dissolve the decamethylene-1, 6-bis (trimethyl ammonium iodide);
(2) 1mmol of manganese iodide is put into a container, and 2ml of 45 wt% hydriodic acid is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
The XRD pattern of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride luminescent material prepared in example 9 is shown in figure 19. The fluorescence spectrum of the novel composite hexamethylene-1, 6-bis (trimethylammonium) manganese metal fluoride phosphor prepared in example 9 is shown in FIG. 20.
Example 10
The preparation method of the novel composite double quaternary ammonium salt manganese metal iodobromide luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium iodide) is put into a container, and 2ml of 45 wt% hydriodic acid is added to fully dissolve the decamethylene-1, 6-bis (trimethyl ammonium iodide);
(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 11
The preparation method of the novel composite bis-quaternary ammonium manganese metal chlorobromide luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium chloride) is put into a container, and 2ml of hydrochloric acid with the concentration of 12mol/L is added to fully dissolve the decamethylene-1, 6-bis (trimethyl ammonium chloride);
(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 12
The preparation method of the novel composite double quaternary ammonium salt manganese metal fluorobromide luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium fluoride) is put into a container, and 2ml of 49 wt% hydrofluoric acid is added to be fully dissolved;
(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 13
The preparation method of the novel composite double quaternary ammonium salt manganese metal fluorine chloride luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium fluoride) is put into a container, and 2ml of 49 wt% hydrofluoric acid is added to be fully dissolved;
(2) 1mmol of manganese chloride is put into a container, and 2ml of hydrochloric acid with the concentration of 12mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 14
The preparation method of the novel composite bis-quaternary ammonium salt manganese metal oxyfluoride luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethyl ammonium fluoride) is put into a container, and 2ml of 49 wt% hydrofluoric acid is added to be fully dissolved;
(2) 1mmol of manganese iodide is put into a container, and 2ml of 45 wt% hydriodic acid is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 15
The preparation method of the novel composite bis-quaternary ammonium salt manganese metal chlorine iodide luminescent material comprises the following steps:
(1) 1mmol of decamethylene-1, 6-bis (trimethylammonium chloride) was placed in a container, and 2ml of 49 wt% hydrochloric acid was added to dissolve it sufficiently;
(2) 1mmol of manganese iodide is put into a container, and 2ml of 45 wt% hydriodic acid is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 16
The preparation method of the novel composite double quaternary ammonium salt manganese metal iodobromide luminescent material comprises the following steps:
(1) 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium iodide) is put into a container, and 2ml of 45 wt% hydriodic acid is added to be fully dissolved;
(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 17
The preparation method of the novel composite bis-quaternary ammonium manganese metal chlorobromide luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium chloride) into a container, and adding 2ml of hydrochloric acid with the concentration of 12mol/L to fully dissolve;
(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 18
The preparation method of the novel composite double quaternary ammonium salt manganese metal fluorobromide luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium fluoride) into a container, and adding 2ml of 49 wt% hydrofluoric acid for fully dissolving;
(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 19
The preparation method of the novel composite double quaternary ammonium salt manganese metal fluorine chloride luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium fluoride) into a container, and adding 2ml of 49 wt% hydrofluoric acid for fully dissolving;
(2) 1mmol of manganese chloride is put into a container, and 2ml of hydrochloric acid with the concentration of 12mol/L is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 20
The preparation method of the novel composite bis-quaternary ammonium salt manganese metal oxyfluoride luminescent material comprises the following steps:
(1) putting 1mmol of hexamethylene-1, 6-bis (trimethyl ammonium fluoride) into a container, and adding 2ml of 49 wt% hydrofluoric acid for fully dissolving;
(2) 1mmol of manganese iodide is put into a container, and 2ml of 45 wt% hydriodic acid is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
Example 21
The preparation method of the novel composite bis-quaternary ammonium salt manganese metal chlorine iodide luminescent material comprises the following steps:
(1) 1mmol of hexamethylene-1, 6-bis (trimethylammonium chloride) was put into a container, and 2ml of 49 wt% hydrochloric acid was added to dissolve it sufficiently;
(2) 1mmol of manganese iodide is put into a container, and 2ml of 45 wt% hydriodic acid is added to be fully dissolved;
(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A novel composite double quaternary ammonium salt manganese metal halide luminescent material is characterized in that the structural general formula is as follows:
wherein n represents the number of carbon atoms, and the value of n is more than or equal to 4; each X is independently selected from halogen or pseudohalogen.
2. The novel composite bis-quaternary ammonium salt manganese metal halide luminescent material as claimed in claim 1, wherein X is selected from F, Cl, Br, I, CN, SCN, NCS, CP, NC, OCN, OSCN, SeCN and N3One or more of them.
3. The novel composite bis-quaternary ammonium salt manganese metal halide luminescent material as claimed in claim 2, wherein X is selected from one or more of F, Cl, Br, I, CN and SCN.
4. The novel composite bis-quaternary ammonium manganese metal halide luminescent material as claimed in claim 1, wherein the halide luminescent material is in a crystal form belonging to monoclinic system, P21/n space group, and a isb isc isAlpha is 90 deg., beta is 93.40-93.41 deg., and gamma is 90 deg..
5. A method for preparing the novel composite bis-quaternary ammonium salt manganese metal halide luminescent material as claimed in any one of claims 1 to 4, which comprises the following steps:
(1) adding n-methylene-1, 6-bis (trimethyl ammonium halide) into halogen acid, and dissolving uniformly to obtain a solution 1; adding manganese halide into halogen acid, and dissolving uniformly to obtain a solution 2;
(2) and uniformly mixing the solution 1 and the solution 2, filtering to obtain filtrate, and crystallizing to obtain the novel composite bis-quaternary ammonium salt manganese metal halide luminescent material.
6. The method for preparing a novel composite bis-quaternary ammonium salt manganese metal halide luminescent material according to claim 5, wherein the n-methylene-1, 6-bis (trimethylammonium halide) in step (1) is hexamethylene-1, 6-bis (trimethylammonium bromide); the hydrohalic acid is hydrobromic acid; the manganese halide in the step (1) is manganese bromide, and the hydrohalic acid is hydrobromic acid.
7. The method for preparing a novel composite bis-quaternary ammonium salt manganese metal halide luminescent material according to claim 5, wherein in the solution 1 in the step (1), the concentration of hexamethylene-1, 6-bis (trimethyl ammonium halide) is 0.1-1mmol/L, and the concentration of hydrogen halide is 4-13 mol/L; in the solution 2 in the step (1), the concentration of manganese halide is 0.1-4mmol/L, and the concentration of hydrogen halide is 4-13 mol/L.
8. The method for preparing a novel composite bis-quaternary ammonium salt manganese metal halide luminescent material as claimed in claim 5, wherein the volume ratio of the solution 1 to the solution 2 in the step (2) is 4:1-1: 2.
9. The method for preparing a novel composite bis-quaternary ammonium salt manganese metal halide luminescent material as claimed in claim 5, wherein the temperature of the crystallization treatment in the step (2) is 50 ℃ and the time of the crystallization treatment is 120 hours.
10. The use of the novel composite bis-quaternary ammonium manganese metal halide luminescent material of any one of claims 1 to 4 in white light LEDs.
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