CN105949224B - A kind of self calibration fluorescence temperature sensing material suitable for ultralow temperature - Google Patents
A kind of self calibration fluorescence temperature sensing material suitable for ultralow temperature Download PDFInfo
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- CN105949224B CN105949224B CN201610327743.9A CN201610327743A CN105949224B CN 105949224 B CN105949224 B CN 105949224B CN 201610327743 A CN201610327743 A CN 201610327743A CN 105949224 B CN105949224 B CN 105949224B
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- 239000011540 sensing material Substances 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims abstract description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical class CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 16
- 239000012621 metal-organic framework Substances 0.000 abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000001514 detection method Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 5
- 239000013110 organic ligand Substances 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- -1 rare earth ion Chemical class 0.000 description 8
- 238000012546 transfer Methods 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to a kind of suitable for self calibration fluorescence temperature sensing material of ultralow temperature and preparation method thereof.This material has following general structure [H2N(CH3)2]x[Eu(FOC)yLz], FOC is the diformazan acid group of 9 Fluorenone 2,7 in formula, H2N(CH3)2For Dimethyl Ammonium cation, L is nitrate anion or formate, x 2y z+3=0,0≤x≤1,1≤y≤2,0≤z≤2；Its preparation method is simple, be can be prepared by using containing inorganic salt of rare earth with organic ligand by hydro-thermal reaction, mild condition, and a step is completed, using single metal, high income.The single rare earth metal-organic framework material of acquisition has high detection temperature sensitivity, it is expected to is used for the temperature detection of low-temperature region as a kind of new fluorescence temperature that need not adulterate other metals detection material.
Description
Technical field
The present invention relates to the various fields such as TEMP, rare earth coordination chemistry and rare earth luminescent material, and in particular to a kind of
Self calibration fluorescence temperature sensing material for temperature sensing under low temperature and preparation method thereof.
Background technology
In scientific research and field of industrial production, temperature is an epochmaking physical parameter.Conventional temperature detector
Performance often seems awkward under various extreme environments (strong-electromagnetic field, extremely low temperature, target of high-speed mobile etc.), therefore grinds
The positive active development New temperature detection method of the person of studying carefully.Wherein, varied with temperature using the luminous intensity or life-span of fluorescent material
Characteristic realizes the method for temperature sensing in starting to attract attention in recent years.Compared to conventional temperature detector, fluorescence temperature detection
Utensil has high sensitivity, highly-responsive, electromagnetism interference, the advantage of non-cpntact measurement, is expected to meet pole low temperature environment, biology
In vivo, the requirement under the specific condition such as target temperature detection of high-speed mobile.
Metal organic frame (Metal-Organic Frameworks, MOFs) material is the one kind developed rapidly in recent years
The novel porous crystalline material being self-assembly of by metal ion or metal cluster with organic bridge ligand by coordination.MOFs
Have inorganic material and the characteristic of organic material concurrently, therefore it has more diversified physicochemical property.Researcher has by introducing
There are the metal center of luminosity and organic ligand to obtain the MOFs with luminescent properties.Luminous MOFs is a kind of great development
The functional material of prospect, it leads in nonlinear optics, photocatalysis, electroluminescent device, biomedical imaging, fluorescent optical sensor etc.
Domain has potential application.Compared with simple organic or inorganic luminescent material, luminous MOFs shows outstanding luminescent properties.
From structure, this is due to the loose structure that MOFs has crystalline state, can by adjusting pore size and change ligand structure
To obtain abundant combination.
Contain rare earth ion and organic ligand in the structure of rare earth metal organic framework materials simultaneously, wherein organic ligand can
By " antenna effect " by rare earth ion of the energy transfer of excitation state to level-density parameter, so as to improve the luminous effect of rare earth ion
Rate.When the energy level difference of part triplet and rare earth ion highest emission level is very greatly or less than 1850cm-1When, energy transfer
Efficiency is all than relatively low.For the latter, its energy transfer efficiency is influenceed quite big by temperature change.By selecting energy level suitably organic
Part and rare earth ion, the thermally sensitive self calibration with organic ligand transmitting and rare earth ion characteristic emission can be obtained
Fluorescence temperature sensing material, this provides new convenient way to develop the new fluorescence temperature sensing material with self aligning characteristic
Footpath.It is also seldom that the report of the fluorescence temperature sensing characteristicses of rare earth metal organic framework materials is explored at present, the performance of its fluorescence spectrum
For double emission spectrum of single rare earth transmitting or more metals (majority use Eu and Tb) doping realization, temperature sensitive close range and
The space being greatly improved.
The content of the invention
It is an object of the invention to provide a kind of temperature under low temperature environment that is used for higher fluorescence temperature sensitivity to visit
Self calibration fluorescence temperature sensing material of survey and preparation method thereof.
To achieve the above object, the present invention is used for the self calibration fluorescence temperature sensing material of temperature sensing, its general structure
For：[H2N(CH3)2]x[Eu(FOC)yLz], FOC in formula2-For 9-Fluorenone -2,7- diformazan acid group, [H2N(CH3)2]+For Dimethyl Ammonium
Cation, L are nitrate anion or formate, x-2y-z+3=0, the 0 ＜ ＜ of x≤1,1≤y≤2,0 z≤2.
The preparation method of self calibration fluorescence temperature sensing material of the present invention, is by hydro-thermal or solvent thermal reaction system
It is standby, comprise the following steps that：First, inorganic salts containing europium are added in the A class solvents of certain volume, by 9-Fluorenone -2,7- dioctyl phthalate
Add in the B class solvents of certain volume, the mol ratio of inorganic salts containing europium and 9-Fluorenone -2,7- dioctyl phthalate is 1:1；Secondly, by two
The mixing of part solution and then stirring are so that raw material is well mixed；Finally mixture is put into closed water heating kettle at 50-200 DEG C
Fully reaction, it can obtain self calibration fluorescence temperature sensing material after cooling.B classes solvent be pure N,N-dimethylformamide or
Collectively constituted by N,N-dimethylformamide and less than a kind compound：DMA, N, N- diethylformamides,
1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
In preparation process of the present invention, described inorganic salts containing europium are six nitric hydrate europiums.
Described its structural formula of 9-Fluorenone -2,7- dioctyl phthalate is as follows in preparation process of the present invention：
In preparation process of the present invention described described A classes solvent by the following compound group of 1-2 kinds into：Water, methanol, second
Alcohol, normal propyl alcohol, isopropanol, acetonitrile, acetic acid.
Beneficial effect
(1) the advantages that self calibration fluorescence temperature sensing material crystallinity of the invention is high, and crystalline size is big, and yield is high.
(2) self calibration fluorescence temperature sensing material preparation technology of the invention is simple, without preparing double rare earth metals in the past
Used rear-earth-doped technique during organic framework materials.
(3) self calibration fluorescence temperature sensing material luminous efficiency of the invention is high, while has the glimmering of rare-earth europium and part
Light emitting peak, and the integral area ratio at two peaks has good linear relationship with temperature, sensitivity is up to 4.78%K-1, can be achieved
Self calibration temperature sensing, empirical factor can be avoided to be influenceed as caused by excitation source and detector, be expected to as a kind of novel warm
Spend sensing material and obtain practical application in low temperature field of detecting.
Brief description of the drawings
Fig. 1 is two peak integral area ratio (S of self calibration fluorescence temperature sensing materialEu/SFOC) linearly closed between temperature
System；
Fig. 2 is the sensitivity at different temperatures of self calibration fluorescence temperature sensing material.
Embodiment
Embodiment 1：
(1) 0.1mmol six nitric hydrate europiums are added in 1mL water, ultrasound makes its dissolving；
(2) 0.1mmol 9-Fluorenone -2,7- dioctyl phthalate is added in 6mL dimethyl acetamide, added after its dissolving
Enter 0.5mL dimethylformamide；
(3) it is well mixed by what above-mentioned two parts of solution was mixed and stirred for, then solution is put into water heating kettle, it is closed
Reactor；
(4) reactor is placed at 50-200 DEG C and reacted 3 days, through being filtrated to get self calibration fluorescence temperature sensing material after cooling
Material.
Embodiment 2：
(1) 0.1mmol six nitric hydrate europiums are added in 1mL water, 1mL ethanol is added after its dissolving；
(2) 0.1mmol 9-Fluorenone -2,7- dioctyl phthalate is added in 4mL dimethylformamide, added after its dissolving
Enter 1mL 1-METHYLPYRROLIDONE；
(3) it is well mixed by what above-mentioned two parts of solution was mixed and stirred for, then solution is put into water heating kettle, it is closed
Reactor；
(4) reactor is placed at 50-200 DEG C and reacted 3 days, through being filtrated to get self calibration fluorescence temperature sensing material after cooling
Material.
Embodiment 3：
(1) 0.1mmol six nitric hydrate europiums are added in 0.3mL water, 25 μ L acetic acid is added after its dissolving；
(2) 0.1mmol 9-Fluorenone -2,7- dioctyl phthalate is added in 5mL dimethylformamide, ultrasound makes its molten
Solution；
(3) it is well mixed by what above-mentioned two parts of solution was mixed and stirred for, then solution is put into water heating kettle, it is closed
Reactor；
(4) reactor is placed at 50-200 DEG C and reacted 3 days, through being filtrated to get self calibration fluorescence temperature sensing material after cooling
Material.
The self calibration fluorescence temperature sensing material of acquisition is yellow transparent crystal, and crystalline size is in 0.1-1mm.9-Fluorenone-
2,7- dioctyl phthalate are sensitized luminous very capable of trivalent europium ion under 12K, and then on the contrary at room temperature.With temperature
The luminous intensity of rise trivalent europium ion weakens rapidly, and part emissive porwer raises with temperature and extremely slowly reduction is presented.
Its main glow peak is located at 525 and 614nm respectively, this at two glow peak integral area ratio and temperature present it is good linear
Relation (see Fig. 1), wherein T are absolute temperature, SEuFor the integral area of rare earth emission peak in the range of 605-640nm, SFOCFor 430-
The integral area of part emission peak in the range of 575nm, the linear relationship can be fitted with equation below：
SEu/SFOC=19.5-0.155T.The relation of sensitivity and temperature under relevant temperature is as shown in Fig. 2 with temperature
Rise sensitivity gradually reduce.In the range of 12-110K, two peak integral area ratios of the self calibration fluorescence temperature sensing material
Sensitivity to temperature is up to 4.78%K-1.So the material can realize the fluorescence temperature detection in low-temperature region.
Above-mentioned embodiment is used for illustrating the present invention, but the present invention should not be limited to the embodiment and accompanying drawing institute
Disclosure.So every do not depart from the lower equivalent or modification completed of spirit disclosed by the invention, the guarantor of the present invention is both fallen within
Protect scope.
Claims (4)
1. a kind of self calibration fluorescence temperature sensing material suitable for ultralow temperature, its general structure are：[H2N(CH3)2]x[Eu
(FOC)yLz], FOC in formula2-For 9-Fluorenone -2,7- diformazan acid group, [H2N(CH3)2]+For Dimethyl Ammonium cation, L is nitrate anion
Or formate, x-2y-z+3=0, the 0 ＜ ＜ of x≤1,1≤y≤2,0 z≤2.
2. the preparation method of material according to claim 1, comprises the following steps：
First, inorganic salts containing europium are added in the A class solvents of certain volume, 9-Fluorenone -2,7- dioctyl phthalate is added into certain volume
B class solvents in, the mol ratio of inorganic salts containing europium and 9-Fluorenone -2,7- dioctyl phthalate is 1:1；Secondly, two parts of solution are mixed right
Stirring is so that raw material is well mixed afterwards；Finally mixture is put into closed water heating kettle and fully reacted at 50-200 DEG C, treated
Self calibration fluorescence temperature sensing material is can obtain after cooling；B classes solvent is for pure N,N-dimethylformamide or by N, N- diformazans
Base formamide collectively constitutes with less than a kind compound：DMA, N, N- diethylformamides, N- methylpyrroles
Alkanone, dimethyl sulfoxide (DMSO).
3. the preparation method of material according to claim 2, it is characterised in that described inorganic salts containing europium are six hydration nitre
Sour europium.
4. the preparation method of material according to claim 2, it is characterised in that described A classes solvent below 1-2 kinds by changing
Compound forms：Water, methanol, ethanol, normal propyl alcohol, isopropanol, acetonitrile, acetic acid.
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| CN112326059A (en) * | 2018-06-27 | 2021-02-05 | 广东省计量科学研究院（华南国家计量测试中心） | Method for measuring temperature by fluorescence using fluorescent composite material |
| CN108864156B (en) * | 2018-07-25 | 2020-09-04 | 汕头大学 | Luminescent organic metal silver complex with binary emission, and preparation and application thereof |
| CN114133924B (en) * | 2021-10-27 | 2023-12-29 | 天津大学 | Material for measuring microscopic hot spots in microwave field, application and method |
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|---|---|---|---|---|
| CN102584873A (en) * | 2012-02-15 | 2012-07-18 | 浙江大学 | Double rare earth metal-organic framework material for temperature detection and synthesis method thereof |
| CN103319509A (en) * | 2013-06-09 | 2013-09-25 | 浙江大学 | Dual-rare-earth-metal organic frame material used in temperature detection and preparation method of dual-rare-earth-metal organic frame material |
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| CN102584873A (en) * | 2012-02-15 | 2012-07-18 | 浙江大学 | Double rare earth metal-organic framework material for temperature detection and synthesis method thereof |
| CN103319509A (en) * | 2013-06-09 | 2013-09-25 | 浙江大学 | Dual-rare-earth-metal organic frame material used in temperature detection and preparation method of dual-rare-earth-metal organic frame material |
| CN104031638A (en) * | 2014-06-24 | 2014-09-10 | 浙江大学 | Dye/rare earth organic framework composite material for physiological temperature detection and preparation method of composite material |
Non-Patent Citations (2)
| Title |
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| Syntheses, structures, tunable emission and white light emitting Eu3+ and Tb3+ doped lanthanide metal–organic framework materials;Shuang-Quan Zang et al.;《Dalton Trans.》;20130513;第42卷;第10579-10586页 * |
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