CN105198737A - Rare earth and organic frame material for detecting fluorescent temperature of high-temperature area and preparation method of rare earth and organic frame material - Google Patents
Rare earth and organic frame material for detecting fluorescent temperature of high-temperature area and preparation method of rare earth and organic frame material Download PDFInfo
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- CN105198737A CN105198737A CN201510497544.8A CN201510497544A CN105198737A CN 105198737 A CN105198737 A CN 105198737A CN 201510497544 A CN201510497544 A CN 201510497544A CN 105198737 A CN105198737 A CN 105198737A
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- rare earth
- carboxyphenoxy
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 19
- -1 rare earth ions Chemical class 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000013384 organic framework Substances 0.000 claims description 47
- 238000001514 detection method Methods 0.000 claims description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- DUXQSXACBMFRPZ-UHFFFAOYSA-N 2-(4-carboxyphenoxy)terephthalic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC(C(O)=O)=CC=C1C(O)=O DUXQSXACBMFRPZ-UHFFFAOYSA-N 0.000 claims description 5
- MPXQWLBCVYSZHL-UHFFFAOYSA-N 4-(3-carboxyphenoxy)phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=C(C(C(O)=O)=CC=2)C(O)=O)=C1 MPXQWLBCVYSZHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- DVENVBCPDCQQGD-UHFFFAOYSA-N dysprosium(3+);trinitrate Chemical compound [Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DVENVBCPDCQQGD-UHFFFAOYSA-N 0.000 claims description 5
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- CHCUFQXMTQHDBL-UHFFFAOYSA-N 2-(3-carboxyphenoxy)terephthalic acid Chemical compound C(=O)(O)C=1C=C(OC2=C(C(=O)O)C=CC(=C2)C(=O)O)C=CC=1 CHCUFQXMTQHDBL-UHFFFAOYSA-N 0.000 claims description 4
- OQHBPEZKDSWIIE-UHFFFAOYSA-N 4-(4-carboxyphenoxy)phthalic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 OQHBPEZKDSWIIE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 claims description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 2
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 230000008878 coupling Effects 0.000 description 17
- 238000010168 coupling process Methods 0.000 description 17
- 238000005859 coupling reaction Methods 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to a rare earth and organic frame material for detecting the fluorescent temperature of a high-temperature area. The rare earth and organic frame material has the general structure LnLn, wherein Ln is one of dysprosium, erbium, praseodymium, neodymium, ytterbium, europium and samarium, L is organic ligand, and n ranges from 1 to 4. A preparation method includes the steps of making salt with rare earth ions react with organic ligand in a thermal mode through solvent to obtain the rare earth and organic frame material. The rare earth and organic frame material is simple in synthesis process, mild in condition and high in yield, and raw materials are easy to obtain. The obtained rare earth and organic frame material has high thermal stability, and the thermal decomposition of the material can reach up to 500 DEG C. The rare earth and organic frame material can be expected to serve as a novel fluorescent temperature detecting material for detecting the temperature of the high-temperature area.
Description
Technical field
The present invention relates to a kind of rare earth-organic framework materials for the detection of high-temperature area fluorescence temperature and preparation method thereof.
Background technology
Temperature is a common and very important physical parameter, and the detection for temperature has designed and invented instrument miscellaneous and material.In temperature sensing field, the optical temperature detection belonging to material such as rare earth-organic framework materials is as novel temperature detection method, breach the shortcomings such as traditional temperature sensing useful range is narrow, speed of response is slow, the environment that pole low temperature environment or organism environment etc. are special can be detected, and carry out temperature of reaction by fluorescence intensity, there is the advantages such as highly sensitive, highly-responsive, electromagnetism interference, non-cpntact measurement.
Metal-organic framework materials (metal-organicframeworks, MOFs) is a kind ofly assembled by metal ion or metal cluster and organic bridge ligand the novel porous crystalline material formed by coordination.Metal-organic framework materials has special topological framework, the systematicness of internal arrangement and the duct of specific dimensions and shape, but frame material shows the physicochemical property of larger structurally variable, tunable characteristic and more horn of plenty.In luminescent metal-organic framework materials, not only inorganic metal ion and organic ligand can provide luminescent properties, and in frame material duct assembling guest molecule or ion also can produce luminescence, in addition, the luminescent properties of frame material and chemical environment, coordination configuration, crystalline structure and also all closely related with the interaction of guest molecule in duct.So relative to other luminescent material, the advantage of luminescent metal-organic framework materials is its various light emitting species, and its adjustable luminescent properties.Rare earth-organic framework materials (lanthanidemetal-organicframeworks) combines the luminescent properties of rare earth ion excellence and metal-organic framework materials light emitting species is various and the advantage of luminous adjustable, all has great using value in fluorescence detection, luminescence and the field such as display and biomedical imaging.
Use rare earth-organic framework materials to carry out temperature sensing and have many reports, but because most of rare earth-organic framework materials thermostability is poor, and relatively conventional two rare earth ratio type thermometers are insensitive at high-temperature area, thus make their application be confined to room temperature and following temperature range, therefore, use rare earth-organic framework materials to carry out the detection of high temperature fluorescence temperature not also to be implemented.Rare earth-organic framework materials that searching at high temperature can carry out temperature detection is extremely urgent.
Summary of the invention
The object of this invention is to provide a kind of prepare simple and easy, high-temperature stable and detect the sensitive thermal coupling energy level of rare earth ion that can utilize carry out rare earth-organic framework materials of high-temperature area fluorescence temperature detection and preparation method thereof.
Rare earth-the organic framework materials detected for high-temperature area fluorescence temperature of the present invention, its general structure is LnL
nin formula, Ln is dysprosium (Dy), erbium (Er), praseodymium (Pr), neodymium (Nd), ytterbium (Yb), one in europium (Eu) or samarium (Sm), n=1 ~ 4, L is 4-(4-carboxyphenoxy) phthalic acid, 4-(3-carboxyphenoxy) phthalic acid, 5-(3-carboxyphenoxy) m-phthalic acid, 5-(2-carboxyphenoxy) m-phthalic acid, 5-(4-carboxyphenoxy) m-phthalic acid, 2-(3-carboxyphenoxy) terephthalic acid or 2-(4-carboxyphenoxy) terephthalic acid.
The synthetic method of rare earth-organic framework materials of the present invention, is characterized in that step is as follows:
1) be dissolved in deionized water by rare-earth salts, making concentration is 0.01 ~ 0.2molL
-1rare earths salt;
2) be dissolved in organic solvent by organic ligand, making concentration is 0.00125 ~ 0.025molL
-1organic ligand solution;
3) by step 1) rare earths salt and step 2) organic ligand solution by volume 1:4 be positioned in reactor and mix, react 1 ~ 3 day at 60 ~ 120 DEG C after sealing, naturally cool to room temperature, filter, obtain rare earth-organic framework materials.
In above-mentioned preparation method, it is characterized in that said rare-earth salts is Dysprosium trinitrate, Erbium trinitrate, praseodymium nitrate, neodymium nitrate, ytterbium nitrate, europium nitrate, samaric nitrate, or Dysprosium trichloride, Erbium trichloride, praseodymium chloride, Neodymium trichloride, Ytterbium trichloride, Europium trichloride, samarium trichloride.
In above-mentioned preparation method, it is characterized in that said organic ligand is 4-(4-carboxyphenoxy) phthalic acid, 4-(3-carboxyphenoxy) phthalic acid, 5-(3-carboxyphenoxy) m-phthalic acid, 5-(2-carboxyphenoxy) m-phthalic acid, 5-(4-carboxyphenoxy) m-phthalic acid, 2-(3-carboxyphenoxy) terephthalic acid or 2-(4-carboxyphenoxy) terephthalic acid.
In above-mentioned preparation method, it is characterized in that said organic solvent is the mixing that in methyl alcohol, ethanol, dioxane, DMF, N,N-dimethylacetamide, N, N-diethyl acetamide or acetonitrile, any one or a few presses any ratio.
The thermal coupling energy level of rare earth ion is utilized to carry out temperature sensing, very responsive when high temperature, just in time can make up rare earth-insensitive defect of organic framework materials high temperature in the past.If the energy extent between rare earth ion two energy levels is at 200 ~ 2000cm
-1in scope, so these two energy levels are exactly thermal coupling energy level (Thermallycoupledenergylevels, TCELs), along with the change of temperature, population on two thermal coupling energy levels can produce thermal equilibrium fast, therefore the radiative relative luminous intensity from two thermal coupling energy levels can change, and can carry out detecting temperature by the intensity of the radiative transition luminescence of these two energy levels.
Relative to traditional inorganic materials, part in rare earth-organic framework materials is to the receptivity of excitation light intensity, the luminescent properties (i.e. antenna effect) of the effective sensitization rare earth ion of meeting, make it more to be suitable as temperature sensing material, and the rigidity that the lattice in rare earth-organic framework materials has can make rare earth ion and organic ligand show its unexistent performance under unbound state, such as extend fluorescence lifetime and improve quantum yield, these performances are all that conventional inorganic material is incomparable.
Rare earth-the organic framework materials utilizing rare earth ion thermal coupling energy level to carry out the detection of high temperature fluorescence temperature of the present invention, not only Heat stability is good, and it is very responsive when high temperature, not only combine the advantage of thermal coupling temperature sensing and rare earth-organic framework materials, and can the defect of extraordinary solution conventional inorganic material and rare earth-organic framework materials in the past, the fluorescence temperature for rare earth-organic framework materials detects and provides new thinking and direction.
The concrete beneficial effect of the present invention is:
1, two rare earth-organic framework materials of existing report mainly utilize associating of the transmission ofenergy between two kinds of different rare earth ions and temperature to realize fluorescence temperature and detect, sensing range primary limitation is below room temperature, rare earth-the organic framework materials of the present patent application protection, more than room temperature and room temperature can be realized until temperature detection within the scope of 400 DEG C, its reason is that rare earth-organic framework materials that the present patent application is protected make use of the diverse temp measuring method of two rare earth-organic framework materials with existing report, namely the thermal coupling energy level of rare earth ion is utilized to carry out temperature detection.
Rare earth ion (the Dy that the present invention uses
3+, Er
3+, Pr
3+, Nd
3+, Yb
3+, Eu
3+, Sm
3+) all there is thermal coupling energy level, utilize their thermal coupling energy level to carry out temperature sensing, very responsive when high temperature.Rare earth-organic framework materials that the present invention synthesizes can send rare earth ion (Dy
3+, Er
3+, Pr
3+, Nd
3+, Yb
3+, Eu
3+, Sm
3+) characteristic luminescence, along with the change of temperature, strength ratio regular meeting from two characteristic peaks of two thermal coupling energy levels changes, thus self calibration temperature sensing can be realized, temperature-measuring range is 20 ~ 400 DEG C, covering temperature range is wide, and has highly sensitive, immunity from interference by force, responds feature rapidly.Effectively can solve rare earth-organic framework materials high temperature in the past unstable, the defects such as high-temperature measurement is insensitive, the temperature sensing for rare earth-organic framework materials provides new direction.
2, the organic ligand in rare earth-organic framework materials of using of the present invention can the luminescence of effective sensitization rare earth ion, and the light intensity sent is high, and identification is high, and the life-span is long, and quantum yield is high, is suitable as very much temperature detection material.
3, compared with inorganic rare earth compound, title complex or organic molecule, rare earth-organic framework materials of the present invention has the crystalline structure of long-range order, larger interionic distance can be obtained by the adjustment of the design of skeleton construction and pore size, thus be expected the quenching of fluorescence suppressing rare earth ion.And, the luminescence of rare earth-organic framework materials and associating of temperature can be regulated by the method for rear modification, thus realize the adjustment to temperature detection range and sensitivity.
4, rare earth of the present invention-organic framework materials crystallization degree is high, can obtain water white crystal, and Heat stability is good, and framework can be stablized to 500 DEG C; Preparation method is simple, and productive rate is higher; Possess the temperature sensing ability of high-temperature area, therefore the present invention has important potentiality in industrial application.
Accompanying drawing explanation
Fig. 1 is used for the thermal multigraph of rare earth-organic framework materials that high-temperature area fluorescence temperature detects;
Fig. 2 is used for monocrystalline simulation X-ray diffraction and the x-ray diffractogram of powder of rare earth-organic framework materials that high-temperature area fluorescence temperature detects;
Fig. 3 is used for the emmission spectrum of rare earth-organic framework materials in differing temps of high-temperature area fluorescence temperature detection;
Fig. 4 is used for I in the rare earth-organic framework materials emmission spectrum of high-temperature area fluorescence temperature detection
455nm/ I
485nmwith the variation relation of temperature.
Embodiment
Embodiment 1:
1) be dissolved in deionized water by Dysprosium trinitrate, being made into concentration is 0.08molL
-1dysprosium trinitrate solution;
2) by the DMF that 5-(4-carboxyphenoxy) m-phthalic acid is dissolved in, being made into concentration is 0.01molL
-1organic ligand solution;
3) by 3mL step 1) Dysprosium trinitrate solution and 12mL step 2) organic ligand solution be placed in reactor and mix, at 80 DEG C, 36 hours are incubated after sealing, naturally cool to room temperature, filter, obtain the rare earth-organic framework materials detected for high-temperature area fluorescence temperature.
Rare earth-the organic framework materials for the detection of high-temperature area fluorescence temperature obtained has excellent thermostability, and from its thermal multigraph (Fig. 1), its framework can keep stable until 500 DEG C.
Rare earth-the organic framework materials obtained is colourless transparent crystal, and crystalline size 0.2-2mm, has the crystalline structure of long-range order, and single crystal X-ray diffraction experiment shows, this material belongs to triclinic(crystalline)system, and spacer is P
and determine that its structural formula is DyL (L is 5-(4-carboxyphenoxy) m-phthalic acid).X-ray diffraction and the x-ray diffractogram of powder spectrum of the simulation of its monocrystalline are shown in Fig. 2, and both can extraordinaryly coincide, and prove that this material has the crystalline structure of long-range order.
The part used can effective sensitization Dy
3+ionoluminescence.In the emmission spectrum of powder product, these two peaks of 455nm and 485nm are by Dy
3+two thermal coupling energy level radiative transitions of ion and producing.Utilize Dy
3+the temperature variant characteristic of thermal coupling energy level population of ion, when temperature is in the process of 20 ~ 400 DEG C of changes, Dy
3+obviously raise along with the rising of temperature in 455nm luminous intensity, obviously reduce along with the rising of temperature (see Fig. 3) in the luminous intensity of 485nm.Use I
455nmrepresent the integrated intensity of 441 ~ 462nm, I
485nmrepresent 462 ~ 500nm integrated intensity, T represents temperature, then I
455nm/ I
485nmpresent good funtcional relationship with temperature, and matching can be carried out with following equation:
I
455nm/ I
485nm=4.65exp (-1837.14/T)+0.091 (see Fig. 4).
Embodiment 2:
1) be dissolved in deionized water by praseodymium nitrate, being made into concentration is 0.01molL
-1praseodymium nitrate solution;
2) 2-(4-carboxyphenoxy) terephthalic acid is dissolved in DMF, being made into concentration is 0.00125molL
-1organic ligand solution;
3) by 4mL step 1) praseodymium nitrate solution and 16mL step 2) organic ligand solution be placed in reactor and mix, at 60 DEG C, 3 days are incubated after sealing, naturally cool to room temperature, filter, obtain the rare earth-organic framework materials detected for high-temperature area fluorescence temperature.
Rare earth-the organic framework materials for the detection of high-temperature area fluorescence temperature obtained is colourless transparent crystal, and crystalline size 0.2-2mm, has the crystalline structure of long-range order, and has excellent thermostability.
The part used can effective sensitization Pr
3+ionoluminescence.In the emmission spectrum of powder product, these two peaks of 520nm and 546nm are by Pr
3+two thermal coupling energy level radiative transitions of ion and producing.Utilize Pr
3+the temperature variant characteristic of thermal coupling energy level population of ion, when temperature is in the process of 20 ~ 400 DEG C of changes, Pr
3+obviously raise along with the rising of temperature in 520nm luminous intensity, obviously reduce along with the rising of temperature in the luminous intensity of 546nm.The intensity rate at these two peaks and temperature present good funtcional relationship, thus the fluorescence temperature that can be implemented in high-temperature area detects.
Embodiment 3:
1) be dissolved in deionized water by samaric nitrate, being made into concentration is 0.2molL
-1samarium nitrate solution;
2) 4-(3-carboxyphenoxy) phthalic acid is dissolved in the solution that N,N-dimethylacetamide and N, N-diethyl acetamide mix with volume ratio 1:1, being made into concentration is 0.025molL
-1organic ligand solution;
3) by 5mL step 1) samarium nitrate solution and 20mL step 2) organic ligand solution be placed in reactor and mix, at 120 DEG C, 1 day is incubated after sealing, naturally cool to room temperature, filter, obtain the rare earth-organic framework materials detected for high-temperature area fluorescence temperature.
What obtain is colourless transparent crystal for high-temperature area fluorescence temperature detection rare earth-organic framework materials, and crystalline size 0.2-2mm, has the crystalline structure of long-range order, and has excellent thermostability.
The part used can effective sensitization Sm
3+ionoluminescence.In the emmission spectrum of powder product, these two peaks of 527nm and 570nm are by Sm
3+two thermal coupling energy level radiative transitions of ion and producing.Utilize Sm
3+the temperature variant characteristic of thermal coupling energy level population of ion, when temperature is in the process of 20 ~ 400 DEG C of changes, Sm
3+obviously raise along with the rising of temperature in 527nm luminous intensity, obviously reduce along with the rising of temperature in the luminous intensity of 570nm.The intensity rate at these two peaks and temperature present good funtcional relationship, thus the fluorescence temperature that can be implemented in high-temperature area detects.
Claims (5)
1., for rare earth-organic framework materials that high-temperature area fluorescence temperature detects, it is characterized in that general structure is LnL
nin formula, Ln is the one in dysprosium, erbium, praseodymium, neodymium, ytterbium, europium or samarium, L is 4-(4-carboxyphenoxy) phthalic acid, 4-(3-carboxyphenoxy) phthalic acid, 5-(3-carboxyphenoxy) m-phthalic acid, 5-(2-carboxyphenoxy) m-phthalic acid, 5-(4-carboxyphenoxy) m-phthalic acid, 2-(3-carboxyphenoxy) terephthalic acid or 2-(4-carboxyphenoxy) terephthalic acid, n=1 ~ 4.
2., as claimed in claim 1 for the preparation method of the rare earth-organic framework materials of high-temperature area fluorescence temperature detection, it is characterized in that step is as follows:
1) be dissolved in deionized water by rare-earth salts, making concentration is 0.01 ~ 0.2molL
-1rare earths salt;
2) be dissolved in organic solvent by organic ligand, making concentration is 0.00125 ~ 0.025molL
-1organic ligand solution;
3) by step 1) rare earths salt and step 2) organic ligand solution by volume 1:4 be placed in reactor and mix, react 1 ~ 3 day at 60 ~ 120 DEG C after sealing, naturally cool to room temperature, filter, obtain rare earth-organic framework materials.
3. the preparation method of rare earth-organic framework materials according to claim 2, is characterized in that said rare-earth salts is Dysprosium trinitrate, Erbium trinitrate, praseodymium nitrate, neodymium nitrate, ytterbium nitrate, europium nitrate, samaric nitrate, Dysprosium trichloride, Erbium trichloride, praseodymium chloride, Neodymium trichloride, Ytterbium trichloride, Europium trichloride or samarium trichloride.
4. the preparation method of rare earth-organic framework materials according to claim 2, is characterized in that said organic ligand is 4-(4-carboxyphenoxy) phthalic acid, 4-(3-carboxyphenoxy) phthalic acid, 5-(3-carboxyphenoxy) m-phthalic acid, 5-(2-carboxyphenoxy) m-phthalic acid, 5-(4-carboxyphenoxy) m-phthalic acid, 2-(3-carboxyphenoxy) terephthalic acid or 2-(4-carboxyphenoxy) terephthalic acid.
5. the preparation method of rare earth-organic framework materials according to claim 2, it is characterized in that said organic solvent is methyl alcohol, ethanol, dioxane, N, dinethylformamide, N, in N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide or acetonitrile, any one or a few is by the mixing of any ratio.
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