CN105198737B - Rare earth-organic framework materials for the detection of high-temperature area fluorescence temperature and preparation method thereof - Google Patents
Rare earth-organic framework materials for the detection of high-temperature area fluorescence temperature and preparation method thereof Download PDFInfo
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- CN105198737B CN105198737B CN201510497544.8A CN201510497544A CN105198737B CN 105198737 B CN105198737 B CN 105198737B CN 201510497544 A CN201510497544 A CN 201510497544A CN 105198737 B CN105198737 B CN 105198737B
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000013384 organic framework Substances 0.000 title claims abstract description 41
- 238000001514 detection method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 229910052692 Dysprosium 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
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-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
- -1 rare-earth salts Chemical class 0.000 claims description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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 7
- 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 6
- 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
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 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
- 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 4
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 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 3
- 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
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 abstract description 2
- 229910052693 Europium Inorganic materials 0.000 abstract description 2
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 abstract description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract description 2
- 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
- 239000013078 crystal Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000005855 radiation 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
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- DDXIJGOPGMAOCY-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)O.[O] Chemical compound C(C1=CC=CC=C1)(=O)O.[O] DDXIJGOPGMAOCY-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 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 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement 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
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 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 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 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 present invention relates to a kind of rare earth-organic framework materials for the detection of high-temperature area fluorescence temperature, with following general structure LnLn, in formula, Ln is dysprosium, erbium, praseodymium, neodymium, ytterbium, the one kind in europium or samarium, and L is organic ligand, n=1～4；Its preparation method is that the salt containing rare earth ion and organic ligand are obtained the rare earth-organic framework materials by solvent thermal reaction, and synthesis technique is simple, and mild condition, raw material are easy to get, and yield is higher.Rare earth-the organic framework materials of acquisition have high heat endurance, and its thermal decomposition may be up to 500 DEG C.It is expected the temperature sensing for high-temperature area as a kind of new fluorescence temperature detection material.
Description
Technical field
The present invention relates to a kind of rare earth-organic framework materials and its preparation side for the detection of high-temperature area fluorescence temperature
Method.
Background technology
Temperature is a common and very important physical parameter, for temperature detection designed have devised each
The instrument of formula various kinds and material.In temperature sensing field, the optical temperature detection belonging to the material such as rare earth-organic framework materials
As new temperature detection method, the shortcomings of traditional temperature sensing measurement range is narrow, reaction speed is slow is breached, can be visited
The special environment such as pole low temperature environment or biological vivo environment is surveyed, and can be by fluorescence intensity come reaction temperature, with Gao Ling
The advantages such as sensitivity, highly-responsive, electromagnetism interference, non-cpntact measurement.
Metal-organic framework materials (metal-organic frameworks, MOFs) are one kind by metal ion or gold
Category cluster assembles the novel porous crystalline material to be formed with organic bridge ligand by coordination.Metal-organic framework materials have
There is the duct of special topological structure, the systematicness of internal arrangement and specific dimensions and shape, but frame material shows more
The physicochemical properties of big structurally variable, tunable characteristic and more horn of plenty.In luminescent metal-organic framework materials, no
Only inorganic metal ion and organic ligand can provide in luminescent properties, and frame material duct assemble guest molecule or from
Son can also produce luminous, additionally, the luminescent properties of frame material and chemical environment, coordination configuration, crystal structure and its and hole
In road, the interaction of guest molecule is also all closely related.So, with respect to other luminescent materials, luminescent metal-organic frame
The advantage of material is its various light emitting species, and its adjustable luminescent properties.Rare earth-organic framework materials
(lanthanide metal-organic frameworks) combines the excellent luminescent properties of rare earth ion and metal-have
The advantage of the various informative and luminous adjustable of machine frame material emission, in fluorescence detection, lighting is become with display and biomedicine
The fields such as picture all have great using value.
Temperature sensing is carried out using rare earth-organic framework materials has had many reports, but due to most of rare earths-have
Machine frame frame material heat endurance is poor, and the more commonly used double rare earth ratio type thermometers are in high-temperature area and insensitive, from
And make their application be confined to room temperature and following temperature range, therefore, high temperature is carried out using rare earth-organic framework materials
Fluorescence temperature detection is not also implemented.Searching can carry out the rare earth-organic framework materials of temperature detection at high temperature and compel
In the eyebrows and eyelashes.
Content of the invention
Simple, high-temperature stable is prepared and detect sensitively can be using rare earth ion it is an object of the invention to provide a kind of
Thermal coupling energy level carries out rare earth-organic framework materials of high-temperature area fluorescence temperature detection and preparation method thereof.
Rare earth-the organic framework materials for the detection of high-temperature area fluorescence temperature of the present invention, its general structure is
LnLn, in formula, Ln is dysprosium (Dy), erbium (Er), praseodymium (Pr), neodymium (Nd), ytterbium (Yb), the one kind in europium (Eu) or samarium (Sm), n=1～
4, L is 4- (4- carboxyphenoxy) phthalic acid, and 4- (3- carboxyphenoxy) phthalic acid, between 5- (3- carboxyphenoxy)
Phthalic acid, 5- (2- carboxyphenoxy) M-phthalic acid, 5- (4- carboxyphenoxy) M-phthalic acid, 2- (3- carboxyl benzene oxygen
Base) terephthalic acid (TPA) or 2- (4- carboxyphenoxy) terephthalic acid (TPA).
The synthetic method of the rare earth-organic framework materials of the present invention, it is characterised in that step is as follows：
1) rare-earth salts is dissolved in deionized water, concentration is made for 0.01～0.2mol L-1Rare earths salt；
2) organic ligand is dissolved in organic solvent, concentration is made for 0.00125～0.025mol L-1Organic join
Liquid solution；
3) by step 1) rare earths salt and step 2) organic ligand solution by volume 1:4 are positioned in reactor
Mixing, reacts 1～3 day at 60～120 DEG C after sealing, naturally cools to room temperature, filters, obtains rare earth-organic frame material
Material.
In above-mentioned preparation method, it is characterised in that described rare-earth salts is dysprosium nitrate, erbium nitrate, praseodymium nitrate, neodymium nitrate, nitre
Sour ytterbium, europium nitrate, samaric nitrate, or dysprosium chloride, erbium chloride, praseodymium chloride, neodymium chloride, ytterbium chloride, Europium chloride, samarium trichloride.
In above-mentioned preparation method, it is characterised in that described organic ligand is 4- (4- carboxyphenoxy) phthalic acid,
4- (3- carboxyphenoxy) phthalic acid, 5- (3- carboxyphenoxy) M-phthalic acid, 5- (2- carboxyphenoxy) isophthalic two
Formic acid, 5- (4- carboxyphenoxy) M-phthalic acid, 2- (3- carboxyphenoxy) terephthalic acid (TPA) or 2- (4- carboxyl benzene oxygen
Base) terephthalic acid (TPA).
In above-mentioned preparation method, it is characterised in that described organic solvent is methyl alcohol, ethanol, dioxane, N, N- diformazan
Base formamide, DMA, N, in N- diethyl acetamide or acetonitrile, any one or a few is by the mixed of any ratio
Close.
Temperature sensing is carried out using the thermal coupling energy level of rare earth ion, very sensitive in high temperature, can just make up with
Toward rare earth-insensitive defect of organic framework materials high temperature.If the size of the energy difference between two energy levels of rare earth ion exists
200～2000cm-1In the range of, then the two energy levels are exactly thermal coupling energy level (Thermally coupled energy
Levels, TCELs), with the change of temperature, the population on two thermal coupling energy levels can produce quick thermal balance, therefore
Relative luminous intensity from the launching light of two thermal coupling energy levels can change, can be with the radiation transistion of the two energy levels
Luminous intensity is detecting temperature.
With respect to traditional inorganic material, absorbability of the part in rare earth-organic framework materials to excitation light intensity,
The luminescent properties (i.e. antenna effect) of rare earth ion can be effectively sensitized, be allowed to be more suitable for as temperature sensing material, and dilute
The rigidity that lattice in soil-organic framework materials has can make rare earth ion and organic ligand show which in free shape
Unexistent performance under state, for example, extend fluorescence lifetime and improve quantum efficiency, and these performances are all that traditional inorganic material cannot
Analogy.
Rare earth-organic frame the material for carrying out high temperature fluorescence temperature detection using rare earth ion thermal coupling energy level of the present invention
Material, not only heat endurance is good, and very sensitive in high temperature, not only combines thermal coupling temperature sensing and rare earth-have machine frame
The advantage of frame material, and the extraordinary defect for solving traditional inorganic material and conventional rare earth-organic framework materials of energy, be
The fluorescence temperature detection of rare earth-organic framework materials provides new thinking and direction.
The specific beneficial effect of the present invention is：
1st, double rare earth-organic framework materials of existing report are mainly passed using the energy between two kinds of different rare earth ions
Pass and detect to realize fluorescence temperature with associating for temperature, detection range primary limitation below room temperature, protect by the present patent application
Rare earth-organic framework materials, can realize the temperature detection of more than room temperature and room temperature in the range of 400 DEG C, and its reason is
The present patent application protection rare earth-organic framework materials be make use of complete with double rare earth-organic framework materials of existing report
Different temp measuring methods, i.e., carry out temperature detection using the thermal coupling energy level of rare earth ion entirely.
Rare earth ion (the Dy that the present invention is used3+, Er3+, Pr3+, Nd3+, Yb3+, Eu3+, Sm3+) thermal coupling energy level is respectively provided with,
Temperature sensing is carried out using their thermal coupling energy level, very sensitive in high temperature.The rare earth that the present invention synthesizes-have machine frame
Frame material can send rare earth ion (Dy3+, Er3+, Pr3+, Nd3+, Yb3+, Eu3+, Sm3+) characteristic luminescence, with changing for temperature
Become, the intensity from two characteristic peaks of two thermal coupling energy levels can change such that it is able to realize self calibration temperature
Detection, temperature-measuring range is 20～400 DEG C, covers temperature range width, and with high sensitivity, strong antijamming capability, responds fast
The feature of speed.Can effectively solve the problem that conventional rare earth-organic framework materials high temperature is unstable, the defect such as high-temperature measurement is insensitive, be
The temperature sensing of rare earth-organic framework materials provides new direction.
2nd, the organic ligand in rare earth-organic framework materials that the present invention is used can effectively be sensitized sending out for rare earth ion
Light, the luminous intensity for sending are high, and identification is high, life-span length, and quantum efficiency is high, is highly suitable as temperature detection material.
3rd, compared with inorganic rare earth compound, complex or organic molecule, the rare earth-organic framework materials tool of the present invention
There is the crystal structure of long-range order, larger interionic can be obtained by the regulation of the design of frame structure and pore size
Away from so as to be expected to suppress the fluorescent quenching of rare earth ion.Furthermore, it is possible to adjust rare earth-organic frame by the method for rear modification
Lighting for material and associating for temperature, so as to realize the regulation to temperature detection range and sensitivity.
4th, the rare earth of the present invention-organic framework materials crystallization degree is high, can obtain water white crystal, Er Qiere
Good stability, framework can be stablized to 500 DEG C；Preparation method is simple, and yield is higher；Possesses the temperature sensing energy of high-temperature area
Power, therefore the present invention there are important potentiality in industrial application.
Description of the drawings
Fig. 1 is used for the thermal multigraph of the rare earth-organic framework materials of high-temperature area fluorescence temperature detection；
Fig. 2 be used for high-temperature area fluorescence temperature detection rare earth-organic framework materials monocrystalline simulation X-ray diffraction and
X-ray diffractogram of powder；
Fig. 3 is used for the emission spectrum of the rare earth-organic framework materials in different temperatures of high-temperature area fluorescence temperature detection；
Fig. 4 is used for I in rare earth-organic framework materials emission spectrum that high-temperature area fluorescence temperature is detected455nm/I485nmWith
The variation relation of temperature.
Specific embodiment
Embodiment 1：
1) dysprosium nitrate is dissolved in deionized water, concentration is made into for 0.08mol L-1Dysprosium nitrate solution；
2) DMF for being dissolved in 5- (4- carboxyphenoxy) M-phthalic acid, being made into concentration is
0.01mol·L-1Organic ligand solution；
3) by 3mL step 1) dysprosium nitrate solution and 12mL step 2) organic ligand solution be placed in reactor mix,
36 hours are incubated at 80 DEG C after sealing, room temperature is naturally cooled to, filter, obtain for the dilute of high-temperature area fluorescence temperature detection
Soil-organic framework materials.
Rare earth-the organic framework materials for the detection of high-temperature area fluorescence temperature for obtaining have excellent heat endurance,
From its thermal multigraph (Fig. 1), its framework can keep stable until 500 DEG C.
Rare earth-the organic framework materials of acquisition are colourless transparent crystal, and crystalline size 0.2-2mm, with long-range order
Crystal structure, single crystal X-ray diffraction experiment show that the material belongs to anorthic system, and space group is PAnd determine its structural formula
For DyL (L is 5- (4- carboxyphenoxy) M-phthalic acid).The X-ray diffraction of its monocrystalline simulation and x-ray diffractogram of powder
Spectrum is shown in Fig. 2, and both extraordinary can coincide, it was demonstrated that the material has the crystal structure of long-range order.
The part for using can effectively be sensitized Dy3+Ionoluminescence.In the emission spectrum of powder product 455nm and 485nm this
Two peaks be by Dy3+Two thermal coupling energy level radiation transistions of ion and produce.Using Dy3+The thermal coupling energy level particle of ion
The characteristic that number is varied with temperature, when temperature is during 20～400 DEG C of changes, Dy3+In 455nm luminous intensity with temperature
Raise and significantly raised, substantially reduce (see Fig. 3) with the rising of temperature in the luminous intensity of 485nm.Use I455nmRepresent 441
The integrated intensity of～462nm, I485nmRepresent 462～500nm integrated intensity, T represents temperature, then I455nm/I485nmPresent with temperature
Go out good functional relation, it is possible to be fitted with equation below：
I455nm/I485nm=4.65exp (- 1837.14/T)+0.091 (see Fig. 4).
Embodiment 2：
1) praseodymium nitrate is dissolved in deionized water, concentration is made into for 0.01mol L-1Praseodymium nitrate solution；
2) 2- (4- carboxyphenoxy) terephthalic acid (TPA) is dissolved in DMF, being made into concentration is
0.00125mol·L-1Organic ligand solution；
3) by 4mL step 1) praseodymium nitrate solution and 16mL step 2) organic ligand solution be placed in reactor mix,
3 days are incubated at 60 DEG C after sealing, room temperature is naturally cooled to, filter, obtain for the dilute of high-temperature area fluorescence temperature detection
Soil-organic framework materials.
Rare earth-the organic framework materials for the detection of high-temperature area fluorescence temperature for obtaining are colourless transparent crystal, crystal
Size 0.2-2mm, the crystal structure with long-range order, and with excellent heat endurance.
The part for using can effectively be sensitized Pr3+Ionoluminescence.In the emission spectrum of powder product 520nm and 546nm this
Two peaks be by Pr3+Two thermal coupling energy level radiation transistions of ion and produce.Using Pr3+The thermal coupling energy level particle of ion
The characteristic that number is varied with temperature, when temperature is during 20～400 DEG C of changes, Pr3+In 520nm luminous intensity with temperature
Raise and significantly raised, substantially reduce with the rising of temperature in the luminous intensity of 546nm.The intensity rate at the two peaks with
Temperature presents good functional relation, such that it is able to realize the detection of the fluorescence temperature in the high-temperature area.
Embodiment 3：
1) samaric nitrate is dissolved in deionized water, concentration is made into for 0.2mol L-1Samarium nitrate solution；
2) 4- (3- carboxyphenoxy) phthalic acid is dissolved in DMA and N, N- diethyl acetamide
With volume ratio 1:The solution of 1 mixing, is made into concentration for 0.025mol L-1Organic ligand solution；
3) by 5mL step 1) samarium nitrate solution and 20mL step 2) organic ligand solution be placed in reactor mix,
1 day is incubated at 120 DEG C after sealing, room temperature is naturally cooled to, filter, obtain for the dilute of high-temperature area fluorescence temperature detection
Soil-organic framework materials.
It is colourless transparent crystal for high-temperature area fluorescence temperature detection rare earth-organic framework materials to obtain, crystal chi
Very little 0.2-2mm, the crystal structure with long-range order, and with excellent heat endurance.
The part for using can effectively be sensitized Sm3+Ionoluminescence.In the emission spectrum of powder product 527nm and 570nm this
Two peaks be by Sm3+Two thermal coupling energy level radiation transistions of ion and produce.Using Sm3+The thermal coupling energy level particle of ion
The characteristic that number is varied with temperature, when temperature is during 20～400 DEG C of changes, Sm3+In 527nm luminous intensity with temperature
Raise and significantly raised, substantially reduce with the rising of temperature in the luminous intensity of 570nm.The intensity rate at the two peaks with
Temperature presents good functional relation, such that it is able to realize the detection of the fluorescence temperature in the high-temperature area.
Claims (1)
1. a kind of for fluorescence temperature detection rare earth-organic framework materials preparation method, the material structure formula be LnLn,
In formula, Ln is the one kind in dysprosium, praseodymium or samarium, and L is 4- (3- carboxyphenoxy) phthalic acid, between 5- (4- carboxyphenoxy)
Phthalic acid, or 2- (4- carboxyphenoxy) terephthalic acid (TPA), n=1 ~ 4；Characterized in that, its preparation methods steps are as follows：
1) rare-earth salts is dissolved in deionized water, concentration is made for 0.01 ~ 0.2 mol L-1Rare earths salt；
2) organic ligand is dissolved in organic solvent, concentration is made for 0.00125 ~ 0.025 mol L-1Organic ligand molten
Liquid；
3) by step 1) rare earths salt and step 2) organic ligand solution by volume 1:4 are placed in mixing in reactor,
React 1 ~ 3 day at 60 ~ 120 DEG C after sealing, room temperature is naturally cooled to, filter, obtain rare earth-organic framework materials；
Described rare-earth salts is dysprosium nitrate, praseodymium nitrate, samaric nitrate, dysprosium chloride, praseodymium chloride or samarium trichloride；Described organic ligand
It is 4- (3- carboxyphenoxy) phthalic acid, 5- (4- carboxyphenoxy) M-phthalic acid or 2- (4- carboxyphenoxy)
Terephthalic acid (TPA)；Described organic solvent is methyl alcohol, ethanol, dioxane, DMF, N, N- dimethylacetamide
Amine, N, in N- diethyl acetamide or acetonitrile, any one or a few is by the mixing of any ratio.
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