CN103980322A - Preparation method of up-conversion luminescent material based on triplet-triplet annihilation - Google Patents
Preparation method of up-conversion luminescent material based on triplet-triplet annihilation Download PDFInfo
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- CN103980322A CN103980322A CN201410221572.2A CN201410221572A CN103980322A CN 103980322 A CN103980322 A CN 103980322A CN 201410221572 A CN201410221572 A CN 201410221572A CN 103980322 A CN103980322 A CN 103980322A
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- luminescent material
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- conversion luminescent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to a preparation method of an up-conversion luminescent material based on triplet-triplet annihilation and application of the material to a light-catalyzed reaction. The up-conversion luminescent material comprises a triplet photosensitizer, an energy receptor and a high-molecular polymer, wherein the molar ratio of the triplet photosensitizer to the energy receptor is 1 to (50-1) to 250. The triplet photosensitizer can be used for achieving strong absorption of visible spectrum, and visible light is converted into ultraviolet light by virtue of a triplet-triplet annihilation process, so that the utilization rate of sunlight is effectively increased and the light degradation efficiency of organic matters in water is improved.
Description
Technical field
The invention belongs to photochemical catalysis water-treatment technology field, be specifically related to preparation and the application in photochemical catalysis water treatment field thereof of the up-conversion luminescent material of a class based on T-T annihilation.
Background technology
Along with developing rapidly of industry, a large amount of waste water that contain organic pollutant enter nature, and the mankind's living environment is gone from bad to worse.Various pending Wastewater Dyes waste water accounts for significant proportion, and waste water from dyestuff colourity is dark, toxicity is large, and concentration is large, stable chemical nature, and being difficult to, with traditional chemical method and biological process degraded, becomes one of environmental pollutant urgently to be resolved hurrily.
At present, conventionally utilize semiconductor material (as: TiO
2, WO
3, C
3n
4) as photosensitizers dye wastewater treatment using.The advantages such as this type of semiconductor material has stable chemical nature, cheap and easy to get, nontoxic can produce hydroxyl radical free radical and the hole with strong oxidation capacity under UV-irradiation, and organic pollutant is completely oxidized to CO the most at last
2, H
2o and other SO
4 2-, NO
3 -, Cl
-deng mineral ion.Therefore, can carry out advanced treatment to the organic pollutant in waste water.As utility model patent CN201962161U Multi-selection photocatalytic dynamic controllable sewage treatment device, the preparation method of patent of invention CN101011660A high activity codoping titanium oxide catalyst and application method thereof, the preparation method of patent of invention CN101011754A activated carbon fibre loading titanium oxide thin film and application method thereof are all to use TiO
2as photocatalyst.
But there is certain defect in this type of photosensitizers: greater band gap, only can absorb UV-light, and to visible ray and infrared light, without response, sunlight utilization ratio is only 3-5%; Seriously restricted the effect of this type of semiconductor material in photochemical catalysis water treatment field.The solution that appears as this difficult problem of upper switch technology has brought hope.
The method that realizes upper conversion at present is mainly used three kinds: the one, and two-photon technology; The 2nd, in the frequency of rare earth ion, change; The 3rd, based on triplet state-triplet state-bury in oblivion upper conversion of (TTA, triplet-triplet--annihilation).On these three kinds, in switch technology, the above two need higher exciting light energy (10
6wcm
-2), far away higher than the quantity of radiant energy (100mWcm on sunlight earth's surface
-2, on ground, sun power standard adopts AM1.5G).
The required exciting light energy of the upper conversion of TTA is not high, and the general solar energy than showing radiation can meet; Triplet state photosensitizers and energy acceptor can select space large, and upper efficiency of conversion is high.Therefore, the upper conversion of TTA has huge applications value aspect photocatalytic degradation water pollutant.
TTA is upper to be changed detailed process and arrives its singlet excited after into triplet state sensitiser absorption photon, then through the arrival triplet excited state that jumps of leaping up between system, the photosensitizers of triplet excited state can by TTET process by transmission ofenergy the triplet state to acceptor, after acceptor density in triplet excited state acquires a certain degree, the acceptor of two triplet excited states collides the acceptor that produces a singlet excited mutually, another acceptor is got back to ground state, now in the acceptor of singlet excited, launches fluorescence and gets back to ground state.Here require the triplet energy level of triplet state photosensitizers higher than the triplet energy level of acceptor, and the first singlet excited of acceptor is lower than the first singlet excited of sensitizing agent, the wavelength ratio of the up-conversion fluorescence therefore obtaining excites light wavelength short.
Inventor's discovery, TTA up-conversion does not also have successful Application sewage disposal at present, especially uses the semiconductor material (TiO of ultraviolet excitation
2, C
3n
4etc.) as photosensitizers degraded water pollutant.
For this reason, the inventor, through studying for a long period of time, successfully adopts multiple upper conversion dyestuff to solve visible ray as photosensitizers and utilizes a difficult problem, and immobilized in high molecular polymer by up-conversion, by convex lens principle, effectively strengthens upper conversion light intensity.By the organic content in degradation of sewage that successfully constructs of upper transfer equipment.
Summary of the invention
For effectively utilizing sunlight, the object of this invention is to provide a kind of novel TTA up-conversion, and first this TTA up-conversion is applied in to Degradation of Organo-pollutants in Water with Photo-catalysis.
Photosensitizers in the upper conversion of TTA the present invention relates to, its structural formula is as follows:
By alkynyl mode of connection to platinum complex parent m-1
r
1=Cl and m-2
r
2=Cl introduces different fluorophore parts, can obtain corresponding platinum complex (Pt-1~Pt-6) and can effectively strengthen triplet state photosensitizers at visible region photon absorbing intensity, extends the triplet excited state life-span.After the photosensitizers of this Series Properties excellence is mixed with energy acceptor, immobilized in high molecular polymer, be conducive to the utilization of photosensitizers to visible ray, preparation method is simple, is easy to commercialization.
In the present invention, energy acceptor Ke Xuan Ze perylene or 9,10-diphenylanthrancene etc.
In the present invention, the mol ratio of triplet state photosensitizers and energy acceptor is between 1:50-1:250.
High molecular polymer can be selected polyvinyl alcohol, polyoxyethylene glycol, polyethylene, polymethylmethacrylate, urethane, polypropylene etc.In present method, to account for the mass percent of high molecular polymer be 0.01%-5.0% to triplet state photosensitizers.
Prepare polymeric mold and can select cylindricality, flat board, semisphere etc.
Triplet state photosensitizers in the present invention can be realized the strong absorption of visible spectrum, by T-T annihilation process, converts visible ray to UV-light, effectively strengthens sunlight utilization ratio, and then improves organic matter efficiency in photodegradation water.
TTA up-conversion preparation method and performance specification thereof are as follows:
1. platinum complex parent m-1 and m-2's is synthetic
A, m-1's is synthetic
Step (1): 2,6-dibromo pyridine (2.35g, 10mmol), pyrazoles (0.816g, 12mmol) and excessive hydrogen potassium oxide are dissolved in the diglyme of 50ml.Then this mixture heated and stirred reaction 24h. is spin-dried for solvent and obtains white solid, and thick product is purified with column chromatography chromatogram, and eluent is methylene dichloride: sherwood oil=1/1, and v/v, obtains white solid 1.328g, and productive rate is 9.6%.
Step (2): by the product (223.0mg, 1.0mmol) of step (1), phenylo boric acid (160.0mg, 1.3mmol), Pd (PPh3) 4 (45.2mg, 0.03mmol) and K
2cO
3(180.4mg, 1.3mmol) is dissolved in (toluene/ethanol/water=2/2/1v/v/v) in 25ml mixed solvent, is heated with stirring to 80 ℃ under nitrogen protection, reaction 8h.After reaction finishes, be cooled to room temperature, be spin-dried for solvent.Thick product is purified by column chromatography, and eluent is methylene dichloride: sherwood oil=2/1v/v, obtains white solid 154.2mg, and productive rate is 69.7%.
Step (3) m-1's is synthetic: by product (110.6mg, 0.5mmol) and the K of step (2)
2ptCl
4(207.6mg, 0.5mmol) is dissolved in the Glacial acetic acid of 20mL, heating reflux reaction 22h under argon shield.After reaction finishes, be cooled to room temperature, obtain orange sedimentation and filtration, filter cake washes with water and at air drying.Thick product is separated with silica gel chromatographic column, and eluent is methylene dichloride.This product can obtain orange solids 126.9mg with methylene dichloride and normal hexane recrystallization, and productive rate is 56.4%.
B, m-2's is synthetic
Step (1): 2,6-dibromo pyridine (2.35g, 10mmol), pyrazoles (0.816g, 12mmol) and excessive hydrogen potassium oxide are dissolved in the diglyme of 50ml.Then this mixture heated and stirred reaction 24h. is spin-dried for solvent and obtains white solid, and thick product is purified with column chromatography chromatogram, and eluent is methylene dichloride: sherwood oil=1/1, and v/v, obtains white solid 1.328g, and productive rate is 9.6%.
Step (2): by the product (445.94mg of step (1), 2.0mmol), diphenylamine (508mg, 3mmol), Pd (dba) 2 (46mg, 0.08mmol), DPPF (44mg, 0.08mmol), sodium tert-butoxide (463mg, 4.8mmol) and toluene (15mL) mix, this mixture heating reflux reaction 24h, after finishing, reaction is cooled to room temperature, reaction mixture is imported in water, water is extracted with ethyl acetate (3 * 35mL), collecting organic phase water (50mL) and salt solution (50mL) washs respectively, use anhydrous sodium sulfate drying organic phase, mixture filters, be spin-dried for, thick product is purified by column chromatography, eluent is that methylene dichloride obtains white solid 204.9mg, productive rate is 33.4%.
Step (3) m-2's is synthetic: by product (97.8mg, 0.5mmol) and the K of above-mentioned steps (2)
2ptCl
4(207.6mg, 0.5mmol) is dissolved in the Glacial acetic acid of 20mL, heating reflux reaction 22h under argon shield.After reaction finishes, be cooled to room temperature, obtain orange sedimentation and filtration, filter cake washes with water and at air drying.Thick product is separated with silica gel chromatographic column, and eluent is methylene dichloride.This product can obtain orange solids 227.6mg with methylene dichloride and normal hexane recrystallization, and productive rate is 84.2%.
2. platinum complex is synthetic:
Alkynyl part R
1and R
2synthetic method: under argon shield, by 1-bromine pyrene (2.0g, 3.57mmol), Pd (PPh3)
2cl
2(100mg, 0.14mmol), PPh3 (triphenyl phosphorus) (74.6mg, 0.28mmol) and CuI (54.3mg, 0.28mmol) join in the mixed solvent of THF (20mL) and triethylamine (60mL).Vacuumize displacement argon gas, then add trimethylsilyl acetylene (414mg, 4.2mmol), at 90 ℃, react 6h.Reaction mixture is cooled to room temperature, filters, collect filtrate, be spin-dried for filtrate, obtain yellow oil.This yellow oil solution, in the mixed solvent of 20mL ether and 40mL methyl alcohol, is then added to salt of wormwood (3.2g), under room temperature, stir 3h.Filter, collect filtrate, be spin-dried for, thick product is purified by column chromatography, and eluent is normal hexane/methylene dichloride=50/1, obtains gray solid (600mg, productive rate: 40.0%).MS(EI):calcd.([C18H10]+)m/z=226.0783,found?m/z=226.0790。
Alkynyl part R
3and R
4synthetic method: under argon shield, by the bromo-N-of 4-(2-ethylhexyl)-1,8-naphthalimide (4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide) (776.3mg, 2mmol) Pd (PPh3)
2cl
2(100mg, 0.14mmol), PPh3 (triphenyl phosphorus) (74.6mg, 0.28mmol) and CuI (54.3mg, 0.28mmol) join in the mixed solvent of THF (20mL) and triethylamine (60mL).Vacuumize displacement argon gas, then add trimethylsilyl acetylene (246mg, 2.5mmol), at 90 ℃, react 6h.Reaction mixture is cooled to room temperature, filters, collect filtrate, be spin-dried for filtrate, obtain yellow oil.This yellow oil solution, in the mixed solvent of 20mL ether and 40mL methyl alcohol, is then added to salt of wormwood (3.2g), under room temperature, stir 3h.Filter, collect filtrate, be spin-dried for, thick product is purified and is obtained faint yellow solid (400mg, productive rate: 60.0%) by column chromatography.EI-MS[M]+measured value: 333.1732; Theoretical value: 333.1729.
M-1 (or m-2) (0.2mmol) is dissolved in appropriate dichloromethane solution; under nitrogen protection, add corresponding alkynyl part (0.2mmol-0.4mmol), CuI (0.02mmol-0.04mmol) and Diisopropylamine (1ml), under room temperature, stir 24 hours.Thick product is purified by column chromatography.
3. the preparation of up-conversion:
By a certain amount of polymer dissolution in solvent, being mixed with mass content is the high polymers solution of 1%-10%, and (mol ratio of platinum complex and energy acceptor is 1:50-1:250 to add appropriate above-mentioned platinum complex and energy acceptor, the mass percent that accounts for high molecular polymer is 0.01%-5.0%), be uniformly mixed, this mixture is poured in glass mold, mould is put into and is full of the vacuum drying oven of argon gas and at 90 ℃, heats after five minutes cooling until then room temperature heats 24 hours except desolventizing in vacuum drying oven.
Embodiment
Embodiment 1.
1, the preparation of triplet state photosensitizers Pt-1
M-1 (90mg, 0.20mmol) is joined in 10mL methylene dichloride, under nitrogen protection, add R-1 (30mg, 0.26mmol), CuI (7.0mg, 0.036mmol) and i-Pr
2nH (1mL).Mixture at room temperature stirs 24 hours, column chromatography purification (developping agent: methylene dichloride), obtain yellow solid 69.0mg, productive rate is 53.2% for thick product.MALDI-HRMS:calcd([C
32H
20N
3Pt+H]
+)m/z=641.1305,found?m/z=641.1343.
2, utilize the up-conversion of preparing of triplet state photosensitizers Pt-1 and energy acceptor 9,10 diphenylanthrancenes (DPA)
2g polymethylmethacrylate (PMMA) is dissolved in N ' dinethylformamide (DMF), in mixing solutions, adds 0.1mmol triplet state photosensitizers Pt-1 and 19mmol DPA to be stirred to homogeneous solution.Will add photosensitizers and the solution of burying in oblivion agent DPA pour in glass mold, mould is put into and is full of the vacuum drying oven of argon gas and at 90 ℃, heats after five minutes cooling until then room temperature heats 24 hours except desolventizing in vacuum drying oven.
Comparative example 1. utilizes TiO
2degraded tropeolin-D
By TiO
2join in the methyl orange solution that 250mL is housed, tropeolin-D starting point concentration is 20mg/L.Light source is 35W xenon lamp.After illumination reaction 6 hours, the decolouring of tropeolin-D is without considerable change.
Embodiment 2. utilizes the upper transfer equipment of the Pt-1 of embodiment 1 preparation and TiO
2degraded tropeolin-D
Utilize the xenon lamp of 35W as light source, the up-conversion of preparation is positioned between light source and photocatalyst reaction vessel, the visible ray that now xenon lamp sends, by after up-conversion, makes visible ray be converted to UV-light, excites TiO
2degraded tropeolin-D.By TiO
2join in the methyl orange solution that 250mL is housed, first class orange starting point concentration is 20mg/L.Light source is 35W xenon lamp.After illumination reaction 5 hours, the percent of decolourization of tropeolin-D reaches 100%, degradable.
The upper transfer equipment of Pt-2 and TiO that embodiment 3. is prepared according to embodiment 1 method
2degraded tropeolin-D
Utilize the xenon lamp of 35W as light source, the up-conversion of preparation is positioned between light source and photocatalyst reaction vessel, the visible ray that now xenon lamp sends, by after up-conversion, makes visible ray be converted to UV-light, excites TiO
2degraded tropeolin-D.By TiO
2join in the methyl orange solution that 250mL is housed, first class orange starting point concentration is 20mg/L.Light source is 35W xenon lamp.After illumination reaction 6 hours, the percent of decolourization of tropeolin-D reaches 100%, degradable.
The upper transfer equipment of Pt-3 and TiO that embodiment 4. is prepared according to embodiment 1 method
2degraded tropeolin-D
Utilize the xenon lamp of 35W as light source, the up-conversion of preparation is positioned between light source and photocatalyst reaction vessel, the visible ray that now xenon lamp sends, by after up-conversion, makes visible ray be converted to UV-light, excites TiO
2degraded tropeolin-D.By TiO
2join in the methyl orange solution that 250mL is housed, first class orange starting point concentration is 20mg/L.Light source is 35W xenon lamp.After illumination reaction 5.5 hours, the percent of decolourization of tropeolin-D reaches 100%, degradable.
The upper transfer equipment of Pt-4 and TiO that embodiment 5. is prepared according to embodiment 1 method
2degraded tropeolin-D
Utilize the xenon lamp of 35W as light source, the up-conversion of preparation is positioned between light source and photocatalyst reaction vessel, the visible ray that now xenon lamp sends, by after up-conversion, makes visible ray be converted to UV-light, excites TiO
2degraded tropeolin-D.By TiO
2join in the methyl orange solution that 250mL is housed, first class orange starting point concentration is 20mg/L.Light source is 35W xenon lamp.After illumination reaction 6 hours, the percent of decolourization of tropeolin-D reaches 100%, degradable.
Claims (6)
1. the structure based on T-T annihilation up-conversion luminescent material, is characterized in that: in described up-conversion luminescent material, relate to a kind of photosensitizers, its structural formula of described photosensitizers is as follows:
2. the structure based on T-T annihilation up-conversion luminescent material according to claim 1, is characterized in that: described photosensitizers passes through alkynyl mode of connection to platinum complex parent m-1
r
1=Cl and m-2
r
2=Cl introduces different fluorophore parts, can obtain corresponding platinum complex (Pt-1~Pt-6) and can effectively strengthen triplet state photosensitizers at visible region photon absorbing intensity, extends the triplet excited state life-span.
3. the structure based on T-T annihilation up-conversion luminescent material according to claim 1, it is characterized in that: described up-conversion luminescent material is comprised of photosensitizers claimed in claim 1, energy acceptor and high molecular polymer, the mol ratio of wherein said triplet state photosensitizers and energy acceptor is between 1:50-1:250.
4. the structure based on T-T annihilation up-conversion luminescent material according to claim 3, is characterized in that: described up-conversion luminescent material energy acceptor Wei perylene or 9,10-diphenylanthrancene.
5. the structure based on T-T annihilation up-conversion luminescent material according to claim 3, is characterized in that: described high molecular polymer can be selected polyvinyl alcohol, polyoxyethylene glycol, polyethylene, polymethylmethacrylate, urethane, polypropylene etc.; The mass percent that described triplet state photosensitizers accounts for high molecular polymer is 0.01%-5.0%.
6. the construction process based on T-T annihilation up-conversion luminescent material of claim 3, it is characterized in that: high molecular polymer is dissolved in solvent, being mixed with mass content is the high polymers solution of 1%-10%, and add appropriate above-mentioned triplet state photosensitizers and energy acceptor, be uniformly mixed, this mixture is poured in glass mold, mould is put into and is full of the vacuum drying oven of argon gas and at 90 ℃, heats after five minutes cooling until then room temperature heats 24 hours except desolventizing in vacuum drying oven.
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Cited By (5)
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CN105368444A (en) * | 2015-10-26 | 2016-03-02 | 苏州科技学院 | Efficient green dim light upconversion system based on protic solvent |
CN106799238A (en) * | 2016-12-30 | 2017-06-06 | 南京信息工程大学 | Converting photocatalysis material and preparation method thereof on a kind of CdS bases green glow |
CN109913199A (en) * | 2019-01-28 | 2019-06-21 | 广东工业大学 | A kind of immobilized object of up-conversion luminescent material and its preparation method and application |
CN110845495A (en) * | 2019-12-03 | 2020-02-28 | 齐齐哈尔大学 | Triplet photosensitizers and methods of synthesis |
CN113619112A (en) * | 2021-08-25 | 2021-11-09 | 北京京东方技术开发有限公司 | Photocuring 3D printing device and photocuring 3D printing method |
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CN109913199A (en) * | 2019-01-28 | 2019-06-21 | 广东工业大学 | A kind of immobilized object of up-conversion luminescent material and its preparation method and application |
CN109913199B (en) * | 2019-01-28 | 2022-09-16 | 广东工业大学 | Up-conversion luminescent material solid carrier and preparation method and application thereof |
CN110845495A (en) * | 2019-12-03 | 2020-02-28 | 齐齐哈尔大学 | Triplet photosensitizers and methods of synthesis |
CN110845495B (en) * | 2019-12-03 | 2022-01-18 | 齐齐哈尔大学 | Synthesis method of triplet photosensitizer |
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