CN104926885A - Preparation method and testing method of metal-organic self-luminous material - Google Patents
Preparation method and testing method of metal-organic self-luminous material Download PDFInfo
- Publication number
- CN104926885A CN104926885A CN201510215400.9A CN201510215400A CN104926885A CN 104926885 A CN104926885 A CN 104926885A CN 201510215400 A CN201510215400 A CN 201510215400A CN 104926885 A CN104926885 A CN 104926885A
- Authority
- CN
- China
- Prior art keywords
- metal
- mol
- organic self
- luminescent material
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a preparation method and a testing method of a metal-organic self-luminous material. The metal-organic self-luminous material is prepared through a solvothermal method with a functional ligand 9,10-anthracene diacrylate and metal ions (Cd<2+>, Mn<2+>, or Zn<2+>). The material can absorb chemical energy released by a peroxy oxalate system, and can emit light by itself. According to tests, with an optimal chemiluminescent effect, a relative luminous intensity reaches 66.73, and a light emitting time reaches 241 min. The material can be recycled and reused with a simple filtering process. The luminous efficiency is not reduced after repeated recycling.
Description
Technical field
The present invention relates to chemiluminescent material field, be specifically related to preparation and the detection method of a kind of metal-organic self-luminescent material.
Background technology
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) be the novel hybrid inorganic-organic functional materials of a class, there is topological framework complicated and changeable and rich and varied physico-chemical property, be widely used in the fields such as catalysis, sensing and luminescence.Research at present for luminous MOFs material mainly concentrates on photoluminescence field, and then develops numerous sensing material based on photoluminescence, optical memory material and photocatalyst material etc. thus.For other luminescent properties of MOFs material, such as chemoluminescence, still lacks relevant research at present.
Oxalate ester peroxide chemical luminous system (PeroxyOxalateChemiLuminescence, POCL) be the individual system that chemoluminescence field is most widely used, there is the advantage that luminous efficiency is high, intensity is large, its commercial applications is very extensive at present, and wherein glo-stick is the most successful example of its application.
Research at present about POCL fluorescent agent is confined to homogeneous phase field more, but not the report of homogeneous fluorescent agent is then considerably less, is generally simple loading type.If by MOFs materials application in POCL, prepare metal-organic self-luminescent material, chemoluminescence can be realized in heterogeneous field, promote its economic performance by recycle, there is important actual application value.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of metal-organic self-luminescent material preparation and detection method are provided.
The preparation method that the present invention adopts is: the preparation method of metal-organic self-luminescent material, comprise the steps: that (1) is by 1 mol 9,10-dibromoanthracene, 2-5 mol methyl acrylate, 3-6 mol salt of wormwood, 0.1 mol palladium, 0.1 mol triphenylphosphine, adds in the DMF (DMF) of 1000 mL, backflow is spent the night under nitrogen protection, carries out linked reaction;
(2) treat that linked reaction terminates, by DMF evaporate to dryness, with after dichloromethane extraction again by extraction liquid evaporate to dryness, then sample is carried out separation and purification by silica gel column chromatography, purification condition is normal hexane: methylene dichloride=1:1-5:1;
(3) sample separation and purification obtained and 2-5 mol sodium hydroxide are dissolved in water/tetrahydrofuran (THF)/alcohol mixed solvent, 50-70
oc reaction is spent the night, and steams except after organic solvent, filters, and then regulates pH to 2-5 with concentrated hydrochloric acid, separates out pale yellow precipitate, suction filtration, with pure water washing, and then 50
oc is dried can obtain 9,10-diacrylate anthracene part;
(4) 9,10-diacrylate anthracene part and metal ion being dissolved in volume ratio according to the mol ratio of 1:2-1:10 is DMF: in the mixed solvent of water=1:1-10:1, add the acid-basicity that 0-5 drips the nitric acid regulator solution of pH=1,65-95
oc reacts 3-5 days, can obtain metal-organic self-luminescent material.
In order to solve the problems of the technologies described above better, the further technical scheme that the present invention adopts is: described
Metal ion is cadmium ion (Cd
2+), mn ion (Mn
2+) or zine ion (Zn
2+).
The detection method that the present invention adopts is: by two (2, 4, 5-tri-chloro-salicylic acid n-pentyl ester) barkite (CPPO) is dissolved in dibutyl phthalate the solution A being mixed with 100 mg/mL, the hydrogen peroxide of the trimethyl carbinol of 100 μ L and 9 μ L is dissolved in 1.9-2.2 mL dibutyl phthalate and is mixed with solution B, get 0.2-0.5 mL solution A and to add in solution B mixing for mixing solutions, again mixing solutions is joined in the quartz colorimetric utensil having added metal-organic self-luminescent material and catalysis rank sodium-acetate in advance, Hitachi F-4600 luminoscope is chosen luminescence pattern 35
oits chemoluminescence performance is detected, the optimum chemistry illumination effect of test: relative luminous intensity is up to 66.73, and fluorescent lifetime reaches 241 minutes under C.
Advantage of the present invention and effect are:
1, metal of the present invention-organic self-luminescent material plasticity-is strong, target design can synthesize 9,10 anthracene class derived ligands with different substituents, select many kinds of metal ions to prepare multiple metal-organic self-luminescent material with different chemical luminous efficiency, thus realize chemiluminescent desired control.
2, metal of the present invention-organic self-luminescent material crystallization degree is high, and structure and composition clearly, can illustrate its chemiluminescent mechanism at atomic scale.
3, metal of the present invention-organic self-luminescent material chemoluminescence is effective, and relative luminous intensity is up to 66.73, and fluorescent lifetime reaches 241 minutes.And this material can be recycled by simple filtration, repeatedly recycling and do not reduce luminous efficiency, is a kind of chemiluminescent material with potential commercial value.
Accompanying drawing explanation
Fig. 1 is the chemoluminescence schematic diagram (left figure is the material under illumination condition, and right figure is the material under dark condition) of metal-organic self-luminescent material.
Fig. 2 is the luminous collection of illustrative plates of metal-organic self-luminescent material.
Fig. 3 is the luminous intensity graph of a relation over time of metal in embodiment 1-organic self-luminescent material.
Fig. 4 is the luminous intensity graph of a relation over time of metal in embodiment 2-organic self-luminescent material.
Fig. 5 is the luminous intensity graph of a relation over time of metal in embodiment 3-organic self-luminescent material.
Embodiment
Particular content of the present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
The preparation method of metal-organic self-luminescent material, comprise the steps: that (1) is by 1 mol 9,10-dibromoanthracene, 2 mol methyl acrylates, 3 mol salt of wormwood, 0.1 mol palladium, 0.1 mol triphenylphosphine, adds in the DMF (DMF) of 1000 mL, backflow is spent the night under nitrogen protection, carries out linked reaction;
(2) treat that linked reaction terminates, by DMF evaporate to dryness, with after dichloromethane extraction again by extraction liquid evaporate to dryness,
Then sample is carried out separation and purification by silica gel column chromatography, purification condition is normal hexane: methylene dichloride=1:1;
(3) sample separation and purification obtained and 5 mol sodium hydroxide are dissolved in water/tetrahydrofuran (THF)/alcohol mixed solvent, and 50
oc reaction is spent the night, and steams except after organic solvent, filters, and then regulates pH to 2 with concentrated hydrochloric acid, separates out pale yellow precipitate, suction filtration, with pure water washing, and then 50
oc is dried can obtain 9,10-diacrylate anthracene part;
(4) by 9,10-diacrylate anthracene part and cadmium ion (Cd
2+) to be dissolved in volume ratio according to the mol ratio of 1:10 be DMF: in the mixed solvent of water=5:1,65
oc reacts 3 days, can obtain metal-organic self-luminescent material (Fig. 1, Fig. 2).
The detection method of metal-organic self-luminescent material, comprise the steps: CPPO to be dissolved in dibutyl phthalate the solution A being mixed with 100 mg/mL, the hydrogen peroxide of the trimethyl carbinol of 100 μ L and 9 μ L is dissolved in 1.9 mL dibutyl phthalates and is mixed with solution B, get 0.5 mL solution A and to add in solution B mixing for mixing solutions, again mixing solutions is joined in the quartz colorimetric utensil having added metal-organic self-luminescent material and catalysis rank sodium-acetate in advance, 35
otest its chemoluminescence performance under C condition, result shows that its maximum emission intensity is 66.73, luminescent lifetime about 180 min(Fig. 3).
Embodiment 2
The preparation method of metal-organic self-luminescent material, comprises the steps: that (1) is by 1 mol 9,10-dibromoanthracene, 3 mol methyl acrylates, 4 mol salt of wormwood, 0.1 mol palladium, 0.1 mol triphenylphosphine,
Add in the DMF (DMF) of 1000 mL, backflow is spent the night under nitrogen protection, carries out linked reaction;
(2) treat that linked reaction terminates, by DMF evaporate to dryness, with after dichloromethane extraction again by extraction liquid evaporate to dryness, then sample is carried out separation and purification by silica gel column chromatography, purification condition is normal hexane: methylene dichloride=3:1;
(3) sample separation and purification obtained and 3 mol sodium hydroxide are dissolved in water/tetrahydrofuran (THF)/alcohol mixed solvent, and 60
oc reaction is spent the night, and steams except after organic solvent, filters, and then regulates pH to 4 with concentrated hydrochloric acid, separates out pale yellow precipitate, suction filtration, with pure water washing, and then 50
oc is dried can obtain 9,10-diacrylate anthracene part;
(4) by 9,10-diacrylate anthracene part and mn ion (Mn
2+) to be dissolved in volume ratio according to the mol ratio of 1:5 be DMF: in the mixed solvent of water=1:1, add the acid-basicity of the nitric acid regulator solution of 3 pH=1,95
oc reacts 4 days, can obtain metal-organic self-luminescent material.
The detection method of metal-organic self-luminescent material, comprise the steps: CPPO to be dissolved in dibutyl phthalate the solution A being mixed with 100 mg/mL, the hydrogen peroxide of the trimethyl carbinol of 100 μ L and 9 μ L is dissolved in 2.05 mL dibutyl phthalates and is mixed with solution B, get 0.35 mL solution A and to add in solution B mixing for mixing solutions, again mixing solutions is joined in the quartz colorimetric utensil having added metal-organic self-luminescent material and catalysis rank sodium-acetate in advance, 35
otest its chemoluminescence performance under C condition, result shows that its maximum emission intensity is 11.68, luminescent lifetime about 86 min(Fig. 4).
Embodiment 3
The preparation method of metal-organic self-luminescent material, comprise the steps: that (1) is by 1 mol 9,10-dibromoanthracene, 5 mol methyl acrylates, 6 mol salt of wormwood, 0.1 mol palladium, 0.1 mol triphenylphosphine, adds in the DMF (DMF) of 1000 mL, backflow is spent the night under nitrogen protection, carries out linked reaction;
(2) treat that linked reaction terminates, by DMF evaporate to dryness, with after dichloromethane extraction again by extraction liquid evaporate to dryness, then sample is carried out separation and purification by silica gel column chromatography, purification condition is normal hexane: methylene dichloride=5:1;
(3) sample separation and purification obtained and 2 mol sodium hydroxide are dissolved in water/tetrahydrofuran (THF)/alcohol mixed solvent, and 70
oc reaction is spent the night, and steams except after organic solvent, filters, and then regulates pH to 5 with concentrated hydrochloric acid, separates out pale yellow precipitate, suction filtration, with pure water washing, and then 50
oc is dried can obtain 9,10-diacrylate anthracene part;
(4) by 9,10-diacrylate anthracene part and zine ion (Zn
2+) to be dissolved in volume ratio according to the mol ratio of 1:2 be DMF: in the mixed solvent of water=10:1, add the acid-basicity of the nitric acid regulator solution of 5 pH=1,80
oc reacts 5 days, can obtain metal-organic self-luminescent material.
The detection method of metal-organic self-luminescent material, comprise the steps: CPPO to be dissolved in dibutyl phthalate the solution A being mixed with 100 mg/mL, the hydrogen peroxide of the trimethyl carbinol of 100 μ L and 9 μ L is dissolved in 2.2 mL dibutyl phthalates and is mixed with solution B, get 0.2 mL solution A and to add in solution B mixing for mixing solutions, again mixing solutions is joined in the quartz colorimetric utensil having added metal-organic self-luminescent material and catalysis rank sodium-acetate in advance, 35
otest its chemoluminescence performance under C condition, result shows that its maximum emission intensity is 4.461, luminescent lifetime about 70 min(Fig. 5).
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (3)
1. the preparation method of metal-organic self-luminescent material, it is characterized in that: comprise the steps: that (1) is by 1 mol 9,10-dibromoanthracene, 2-5 mol methyl acrylate, 3-6 mol salt of wormwood, 0.1 mol palladium, 0.1 mol triphenylphosphine, adds in the DMF (DMF) of 1000 mL, backflow is spent the night under nitrogen protection, carries out linked reaction;
(2) treat that linked reaction terminates, by DMF evaporate to dryness, with after dichloromethane extraction again by extraction liquid evaporate to dryness, then sample is carried out separation and purification by silica gel column chromatography, purification condition is normal hexane: methylene dichloride=1:1-5:1;
(3) sample separation and purification obtained and 2-5 mol sodium hydroxide are dissolved in water/tetrahydrofuran (THF)/alcohol mixed solvent, 50-70
oc reaction is spent the night, and steams except after organic solvent, filters, and then regulates pH to 2-5 with concentrated hydrochloric acid, separates out pale yellow precipitate, suction filtration, with pure water washing, and then 50
oc is dried can obtain 9,10-diacrylate anthracene part;
(4) 9,10-diacrylate anthracene part and metal ion being dissolved in volume ratio according to the mol ratio of 1:2-1:10 is DMF: in the mixed solvent of water=1:1-10:1, add the acid-basicity that 0-5 drips the nitric acid regulator solution of pH=1,65-95
oc reacts 3-5 days, can obtain metal-organic self-luminescent material.
2. according to the preparation method of metal according to claim 1-organic self-luminescent material, it is characterized in that: described metal ion is cadmium ion (Cd
2+), mn ion (Mn
2+) or zine ion (Zn
2+).
3. the detection method of metal-organic self-luminescent material, is characterized in that: comprise the steps: two
(2,4,5-tri-chloro-salicylic acid n-pentyl ester) barkite (CPPO) is dissolved in dibutyl phthalate the solution A being mixed with 100 mg/mL, the hydrogen peroxide of the trimethyl carbinol of 100 μ L and 9 μ L is dissolved in 1.9-2.2 mL dibutyl phthalate and is mixed with solution B, get 0.2-0.5 mL solution A and to add in solution B mixing for mixing solutions, again mixing solutions is joined in the quartz colorimetric utensil having added metal-organic self-luminescent material and catalysis rank sodium-acetate in advance, Hitachi F-4600 luminoscope is chosen luminescence pattern 35
oits chemoluminescence performance is detected, the optimum chemistry illumination effect of test: relative luminous intensity is up to 66.73, and fluorescent lifetime reaches 241 minutes under C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510215400.9A CN104926885A (en) | 2015-04-30 | 2015-04-30 | Preparation method and testing method of metal-organic self-luminous material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510215400.9A CN104926885A (en) | 2015-04-30 | 2015-04-30 | Preparation method and testing method of metal-organic self-luminous material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104926885A true CN104926885A (en) | 2015-09-23 |
Family
ID=54114331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510215400.9A Pending CN104926885A (en) | 2015-04-30 | 2015-04-30 | Preparation method and testing method of metal-organic self-luminous material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104926885A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106908430A (en) * | 2017-03-28 | 2017-06-30 | 盐城工学院 | CO2Quantitative fluorescence sensing material, preparation method and application |
| CN106957643A (en) * | 2017-03-28 | 2017-07-18 | 盐城工学院 | Reversible stepless colour-changing material, preparation method and application |
| CN108084229A (en) * | 2017-12-27 | 2018-05-29 | 盐城工学院 | Difunctional water system object light sensing material, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217010A (en) * | 1996-04-30 | 1999-05-19 | 詹姆精细化学品公司 | Two-component chemilumineschent composition |
| CN1926216A (en) * | 2004-04-27 | 2007-03-07 | 株式会社乐美加 | Chemiluminescent compositions |
| US20100288984A1 (en) * | 2009-05-12 | 2010-11-18 | Bindra Perminder S | Chemiluminescent powders and methods of making and using thereof |
-
2015
- 2015-04-30 CN CN201510215400.9A patent/CN104926885A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217010A (en) * | 1996-04-30 | 1999-05-19 | 詹姆精细化学品公司 | Two-component chemilumineschent composition |
| CN1926216A (en) * | 2004-04-27 | 2007-03-07 | 株式会社乐美加 | Chemiluminescent compositions |
| US20100288984A1 (en) * | 2009-05-12 | 2010-11-18 | Bindra Perminder S | Chemiluminescent powders and methods of making and using thereof |
Non-Patent Citations (4)
| Title |
|---|
| FAN YU等: "Various crystal structures based on 4,4"-(diethynylanthracene-9,10-diyl) dibenzoic acid: from 0D dimer to 3D net framework", 《CRYSTENGCOMM》 * |
| JUN-JIE WANG等: "Cadmium(Ⅱ) and zinc(Ⅱ) metal-organic frameworks with anthracene-based dicarboxylic ligands: solvothermal synthesis, crystal structures, and luminescent properties", 《CRYSTENGCOMM》 * |
| SHENGQIAN MA等: "Metal-organic framework from an anthracene derivative containing nanoscopic cages exhibiting high methane uptake", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 史大斌: "基于延长配体的金属有机框架的合成、结构和性能研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106908430A (en) * | 2017-03-28 | 2017-06-30 | 盐城工学院 | CO2Quantitative fluorescence sensing material, preparation method and application |
| CN106957643A (en) * | 2017-03-28 | 2017-07-18 | 盐城工学院 | Reversible stepless colour-changing material, preparation method and application |
| US20180282619A1 (en) * | 2017-03-28 | 2018-10-04 | Yancheng Institute Of Technology | Reversible Continuous Variable Chromogenic Material, Preparation Method and Application thereof |
| CN106908430B (en) * | 2017-03-28 | 2019-07-05 | 盐城工学院 | CO2Quantitative fluorescence sensing material, preparation method and application |
| CN106957643B (en) * | 2017-03-28 | 2019-09-24 | 盐城工学院 | The application of reversible stepless colour-changing material |
| US10746656B2 (en) | 2017-03-28 | 2020-08-18 | Yancheng Institute Of Technology | CO2 quantitative fluorescent sensing material, preparation method and application thereof |
| CN108084229A (en) * | 2017-12-27 | 2018-05-29 | 盐城工学院 | Difunctional water system object light sensing material, preparation method and application |
| CN108084229B (en) * | 2017-12-27 | 2020-05-05 | 盐城工学院 | Difunctional water-based substance optical sensing material, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103483332B (en) | There is the piezoluminescence material of hot activation delayed fluorescence and aggregation-induced emission performance and synthetic method thereof and application | |
| KR102124227B1 (en) | Metal compounds, methods, and uses thereof | |
| CN103374040A (en) | Alcohol soluble cathode buffer layer molecular material containing triaryl phosphonium oxygen and nitrogen heterocyclic functional groups as well as synthetic method and application thereof | |
| CN104926885A (en) | Preparation method and testing method of metal-organic self-luminous material | |
| CN106590629B (en) | A kind of raising MAPbBr3The method of perovskite quantum dot stability | |
| CN112679518B (en) | Pure organic room temperature phosphorescent material based on thiochromanone derivative and preparation method and application thereof | |
| CN106749094A (en) | 42 (2` hydroxy phenyls) benzoxazole compounds and its preparation method and purposes containing substituted base | |
| CN103242298A (en) | 1,2,4-triazole derivative, preparation method and application thereof and organic electroluminescent device | |
| CN105086996A (en) | Luminescent material with cyclotriphosphazene cross-linked rare-earth complexes and method for preparing luminescent material | |
| CN104140808A (en) | Tetrahedral cuprous complex luminescent material containing oxazolyl pyridine ligands | |
| CN108752368A (en) | A kind of zinc-containing metal organic framework materials and its synthetic method and application with fluorescence identifying performance | |
| CN105153207A (en) | Porous rare-earth-cluster metal organic anion framework and preparation method and application thereof | |
| CN105542751A (en) | Metal organic framework material capable of emitting white light, and synthetic method and application thereof | |
| CN104178131A (en) | Mixed cuprous complex luminescent material containing oxazolyl pyridine ligand | |
| CN108358957B (en) | Preparation method of rare earth-polymer nanospheres emitting white light | |
| CN107722291B (en) | Rare earth-organic framework material with organic dye introduced and preparation method thereof | |
| CN112779002B (en) | Pure organic material with near-infrared phosphorescence emission, and preparation method and application thereof | |
| CN109054810A (en) | Using diphenylsulfide as the thermal excitation delayed fluorescence material of main part of parent and its preparation and application | |
| CN110746423B (en) | Synthesis of aryl imidazophenanthroline fluorescent dye and identification of metal ions | |
| CN105199714A (en) | Diphenyl anthracene cocrystallization material with electrochemiluminescence characteristics and preparation method thereof | |
| CN102584686A (en) | Water soluble terpyridyl fluorescent compound and preparation method thereof | |
| CN104910897B (en) | A kind of Cu3I2 cationic cuprous cluster compound green phosphorescent material | |
| CN105949225B (en) | A method of preparing the luminescent material of liquid containing rare-earth europium ion | |
| CN102719237A (en) | Zn(II) complex luminescent material and its preparation method | |
| CN105838356B (en) | A kind of cuprous complex orange light emitting materials of CuBrN2P types based on benzoxazole yl pyridines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150923 |
|
| RJ01 | Rejection of invention patent application after publication |