CN110144050B - With MnO4-Rare earth europium coordination polymer with detection function and preparation method thereof - Google Patents
With MnO4-Rare earth europium coordination polymer with detection function and preparation method thereof Download PDFInfo
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 69
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 69
- 238000001514 detection method Methods 0.000 title claims abstract description 22
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 16
- LTRYUAZFLOGRLJ-UHFFFAOYSA-N 4-cyano-3-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C#N LTRYUAZFLOGRLJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 230000005284 excitation Effects 0.000 claims abstract description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 12
- -1 rare earth europium ion Chemical class 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000000696 magnetic material Substances 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 description 6
- 0 CCC(C1C[C@@](C)C(*)CC1)SC(C1CC(C)C(*)CC1)*#C Chemical compound CCC(C1C[C@@](C)C(*)CC1)SC(C1CC(C)C(*)CC1)*#C 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000504 luminescence detection Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010057190 Respiratory tract infections Diseases 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940077449 dichromate ion Drugs 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material 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
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a method for preparing a high-performance magnetic material with MnO4 ‑A rare earth europium coordination polymer with detection function and a preparation method thereof, wherein the chemical formula of the coordination polymer is [ Eu (L)3(H2O)2]nWherein L is a ligand, in particular an anion of 3-methyl-4-cyanobenzoic acid, which coordination polymer belongs to the monoclinic system, P21A/c space group, an asymmetric unit containing an independent Eu3+Three L ligands and two coordinated H2O, each Eu3+The center is coordinated to nine oxygen atoms from seven carboxylic acid groups and two coordinated H groups in six L ligands, respectively2O, adjacent Eu3+Is bridged by L ligand to form chain coordination polymer, the excitation wavelength is 394nm, the emission wavelengths are 577nm, 591nm, 617nm, 652nm and 697nm, and bright red light observable by naked eyes is shown. The invention has the advantages that: the coordination polymer provided by the invention has MnO4 ‑Has good detection function, good selectivity, high sensitivity and low detection limit, and can simply, rapidly and accurately detect MnO in a water phase4 ‑。
Description
Technical Field
The invention relates to a coordination polymer and a preparation method thereof, in particular to a coordination polymer with MnO4 -A rare earth europium coordination polymer with a detection function and a preparation method thereof belong to the technical field of chemistry.
Background
Potassium permanganate (KMnO)4) As an important oxidant in laboratories and industrial production, the catalyst is widely applied to removing pollutants such As As (III) and harmful organic matters in sewage. When large-scale abuse and random discharge of KMnO are performed4In the meantime, the environmental water will contain excessive permanganate ions (MnO)4 -) This not only causes respiratory tract infection and skin irritation, but also causes environmental pollution, causing serious safety hazards.
Therefore, in the fields of analytical techniques and environmental science, rapid and sensitive detection of MnO has been sought4 -The method has very important significance for improving human health and protecting environment.
In the existing detection of MnO4 -In the method, the fluorescence method has the advantages of high detection speed, high sensitivity, low detection limit, simple and convenient operation, easy observation and the like, is widely and deeply researched, and has important application value in the aspect of detection and identification of metal cations, anions and organic molecules.
The coordination polymer assembled by rare earth metal ions and organic ligands has the characteristics of regular and ordered structure, adjustable pore surface, bright light-emitting color, long light-emitting service life and the like. Therefore, it is a material with unique advantages and important application prospects in luminescence detection and identification, and has attracted strong attention of researchers.
Currently, researchers have prepared a large number of coordination polymers having luminescent properties using various organic ligands reacting with some rare earth metal ions, although some of them exhibit chromate ion (CrO) resistance4 2-) Dichromate ion (Cr)2O7 2-) Fluorine ion (F)-) Luminescence detection Performance of plasma anions, however, MnO can be detected4 -The coordination polymer of (2) is extremely small.
Disclosure of Invention
To overcome the disadvantages of the prior art, the present invention provides a battery with MnO4 -A rare earth europium coordination polymer with a detection function and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical solutions:
with MnO4 -A rare earth europium coordination polymer having a detection function, characterized in that the coordination polymer has a chemical formula of [ Eu (L)3(H2O)2]nWherein L is a ligand, in particular to a negative univalent anion of 3-methyl-4-cyanobenzoic acid, and the structural formula is as follows:
the coordination polymer [ Eu (L)3(H2O)2]nBelonging to the monoclinic system, P21The europium ion structure comprises a/c space group, wherein one asymmetric unit comprises an independent rare earth europium ion, three L ligands and two coordinated water molecules, the center of each rare earth europium ion is coordinated with nine oxygen atoms, the nine oxygen atoms are respectively from seven carboxylic acid groups in six L ligands and two coordinated water molecules, and adjacent rare earth europium ions are bridged by the L ligands to form a chain coordination polymer;
the coordination polymer [ Eu (L)3(H2O)2]nHas an excitation wavelength of 394nm and emission wavelengths of 577nm, 591nm, 617nm, 652nm and 697nm, and shows bright red light observable with the naked eye.
The above-mentioned MnO4 -The preparation method of the rare earth europium coordination polymer with the detection function is characterized by comprising the following steps of:
step 1: mixing europium nitrate hexahydrate, 3-methyl-4-cyanobenzoic acid and water in a molar ratio of 1:1: 400-500, and uniformly stirring to obtain a mixed solution;
step 2: sealing the mixed solution in a reaction kettle, heating to 140-160 ℃, and keeping for 60-96 h;
step 3: the reaction kettle was slowly cooled to room temperature to obtain colorless massive crystals.
The preparation method is characterized in that in Step3, the temperature reduction speed of the reaction kettle is controlled to be 5-8 ℃/h.
The invention has the advantages that:
(1) the invention provides a coordination polymer [ Eu (L)3(H2O)2]nHaving MnO of4 -Good selectivity, high sensitivity, and low limit of detection as low as 8.44 × 10-4mol/L, can simply, quickly and accurately detect MnO in the water phase4 -；
(2) The invention provides a coordination polymer [ Eu (L)3(H2O)2]nThe thermal stability temperature is high and reaches 380 ℃, which provides necessary conditions for the subsequent application;
(3) the invention provides a coordination polymer [ Eu (L)3(H2O)2]nThe red light can be emitted to the naked eye, and the color is bright and easy to observe;
(4) the invention provides a coordination polymer [ Eu (L)3(H2O)2]nThe preparation method has simple process, mild reaction conditions and cheap and easily obtained raw materials;
(5) the invention provides a coordination polymer [ Eu (L)3(H2O)2]nThe preparation method uses water as the solvent, avoids the use of toxic organic solvents and is more environment-friendly;
(6) the invention provides a coordination polymer [ Eu (L)3(H2O)2]nThe yield of the obtained product is high and reaches more than 60 percent by the preparation method.
Drawings
FIG. 1 shows a coordination polymer [ Eu (L)3(H2O)2]nSchematic diagram of the coordination environment of (a);
FIG. 2 shows a coordination polymer [ Eu (L)3(H2O)2]nA schematic view of the one-dimensional chain structure of (a);
FIG. 3 shows coordinationPolymer [ Eu (L)3(H2O)2]nX-ray powder diffractogram of;
FIG. 4 shows a coordination polymer [ Eu (L)3(H2O)2]nA weight loss curve graph under nitrogen atmosphere;
FIG. 5 shows a coordination polymer [ Eu (L)3(H2O)2]nFluorescence emission spectrum of (a);
FIG. 6 shows a coordination polymer [ Eu (L)3(H2O)2]nA comparison of the luminescence intensity in different anionic potassium salt aqueous solutions;
FIG. 7 shows a coordination polymer [ Eu (L)3(H2O)2]nFor MnO of different concentrations4 -Luminescence response graph of the solution;
FIG. 8 shows a coordination polymer [ Eu (L)3(H2O)2]nLuminous intensity of and MnO4 -Fitted graph of concentration.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
A first part: with MnO4 -Structure of rare earth europium coordination polymer with detection function
The invention provides a battery with MnO4 -The rare earth europium coordination polymer with the detection function has the chemical formula of [ Eu (L)3(H2O)2]nWherein L is a ligand, in particular to a negative univalent anion of 3-methyl-4-cyanobenzoic acid, and the structural formula is as follows:
to the coordination polymer [ Eu (L)3(H2O)2]nThe crystal of (a) is structurally characterized and resolved, and the unit cell and space structure thereof are determined as follows:
the coordination polymer [ Eu (L)3(H2O)2]nBelonging to a monoclineCrystal system, P21The/c space group comprises an asymmetric unit which comprises an independent rare earth europium ion, three L ligands and two coordinated water molecules, as shown in figure 1, the center of each rare earth europium ion is coordinated with nine oxygen atoms, the nine oxygen atoms are respectively from seven carboxylic acid groups in six L ligands and two coordinated water molecules, adjacent rare earth europium ions are bridged by the L ligands to form a chain coordination polymer, and the structure is shown in figure 2.
To the coordination polymer [ Eu (L)3(H2O)2]nX-ray powder diffraction tests were performed and the diffraction results are shown in figure 3, which show that: coordination polymer [ Eu (L)3(H2O)2]nHas good purity.
To the coordination polymer [ Eu (L)3(H2O)2]nThermogravimetric analysis was carried out and the weight loss curve under nitrogen atmosphere is shown in fig. 4, which shows: coordination polymer [ Eu (L)3(H2O)2]nCan be stabilized to 380 ℃ under nitrogen atmosphere and has excellent thermal stability.
To the coordination polymer [ Eu (L)3(H2O)2]nPerforming fluorescence spectrum analysis, and when the excitation wavelength is 394nm, performing coordination polymer [ Eu (L)3(H2O)2]nHas excellent luminescence characteristics, and has Eu at 577nm, 591nm, 617nm, 652nm and 697nm3+As shown in fig. 5, and exhibits a bright red light observable to the naked eye.
The coordination polymer [ Eu (L) is detected3(H2O)2]nThe luminescence lifetime of (a) was 412.9ms, and the quantum yield was 3.06%.
Based on the coordination polymer [ Eu (L)3(H2O)2]nHas excellent luminescence property, and researches on coordination polymer [ Eu (L) ] with excitation wavelength of 394nm3(H2O)2]nIn the presence of different anionic potassium salts (K)2S2O3、KBr、CH3COOK、K3PO4、K2S、K2CO3、KNO3、K2SO4、 KClO4、KMnO4) The emission intensity in the aqueous solution is shown in FIG. 6. The comparison shows that: MnO4 -Coordination polymers [ Eu (L) ]having the most pronounced quenching effect on luminescence in solution3(H2O)2]nFor MnO4 -Has excellent selective luminescence detection performance.
In addition, we utilized the coordination polymer [ Eu (L)3(H2O)2]nFor MnO in water phase4 -Luminescence detection has been further explored extensively.
Coordination polymer [ Eu (L)3(H2O)2]nTo the aqueous solution of (A) was added different amounts of KMnO4Aqueous solution, emission spectrum was measured, and the measurement results are shown in fig. 7. As can be seen from FIG. 7, with MnO4 -The fluorescence intensity gradually weakens when the concentration is continuously increased and is MnO4 -The concentration is 2.857 × 10-3At mol/L, the coordination polymer [ Eu (L)3(H2O)2]nThe fluorescence intensity of (a) is completely quenched.
Fitting the luminous intensity data to obtain the coordination polymer [ Eu (L)3(H2O)2]nFor MnO4 -The detection quantitative relation and the quenching constant of (1), wherein the detection quantitative relation is I0/I＝1+2.665×103[MnO4 -]The quenching constant was 2665L/mol, as shown in FIG. 8.
The detection limit calculated from the quenching constant was 8.44X 10-4mol/L。
Thus, it can be seen that the coordination polymer [ Eu (L)3(H2O)2]nWith MnO4 -Good selectivity, high sensitivity, and low limit of detection as low as 8.44 × 10-4mol/L, can simply, quickly and accurately detect MnO in the water phase4 -The concentration of (c).
A second part:coordination polymer [ Eu (L)3(H2O)2]nPreparation method of (1)
The invention provides a coordination polymer [ Eu (L)3(H2O)2]nThe preparation method has simple process, mild reaction conditions, cheap and easily obtained raw materials, uses water as a solvent, and does not pollute the environment, and the preparation method specifically comprises the following steps:
step 1: mixing europium nitrate hexahydrate, 3-methyl-4-cyanobenzoic acid and water in a molar ratio of 1:1: 400-500, and uniformly stirring to obtain a mixed solution;
step 2: sealing the mixed solution in a reaction kettle, heating to 140-160 ℃, and keeping for 60-96 h;
step 3: and cooling the reaction kettle to room temperature at a cooling speed of 5-8 ℃/h to obtain colorless blocky crystals.
Example 1
Step 1: mixing europium nitrate hexahydrate, 3-methyl-4-cyanobenzoic acid and water in a molar ratio of 1:1:400, and uniformly stirring to obtain a mixed solution;
step 2: sealing the mixed solution in a reaction kettle, heating to 140 ℃, and keeping for 96 hours;
step 3: and cooling the reaction kettle to room temperature at the cooling speed of 5 ℃/h to obtain colorless blocky crystals.
The colorless blocky crystal is detected to be coordination polymer [ Eu (L)3(H2O)2]n。
Calculated, the coordination polymer [ Eu (L)3(H2O)2]nThe yield of (a) was 63%.
Example 2
Step 1: mixing europium nitrate hexahydrate, 3-methyl-4-cyanobenzoic acid and water in a molar ratio of 1:1:450, and uniformly stirring to obtain a mixed solution;
step 2: sealing the mixed solution in a reaction kettle, heating to 150 ℃, and keeping for 80 hours;
step 3: and cooling the reaction kettle to room temperature at the cooling speed of 5 ℃/h to obtain colorless blocky crystals.
Upon detection, the color is colorlessBulk crystals are coordination polymers [ Eu (L)3(H2O)2]n。
Calculated, the coordination polymer [ Eu (L)3(H2O)2]nThe yield of (a) was 65%.
Example 3
Step 1: mixing europium nitrate hexahydrate, 3-methyl-4-cyanobenzoic acid and water in a molar ratio of 1:1:500, and uniformly stirring to obtain a mixed solution;
step 2: sealing the mixed solution in a reaction kettle, heating to 160 ℃, and keeping for 96 hours;
step 3: and cooling the reaction kettle to room temperature at the cooling speed of 8 ℃/h to obtain colorless blocky crystals.
The colorless blocky crystal is detected to be coordination polymer [ Eu (L)3(H2O)2]n。
Calculated, the coordination polymer [ Eu (L)3(H2O)2]nThe yield of (3) was 68%.
Thus, it can be seen that the present invention provides coordination polymers [ Eu (L) ]3(H2O)2]nThe yield of the obtained product is high and reaches more than 60 percent, and the method is a feasible preparation method.
It should be noted that the above-mentioned embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the protection scope of the present invention.
Claims (1)
1. Rare earth europium coordination polymer in MnO4 -The application of the coordination polymer in detection is characterized in that the chemical formula of the coordination polymer is [ Eu (L)3(H2O)2]nWherein L is a ligand, in particular to a negative univalent anion of 3-methyl-4-cyanobenzoic acid, and the structural formula is as follows:
the coordination polymer [ Eu (L)3(H2O)2]nBelonging to the monoclinic system, P21The europium ion structure comprises a/c space group, wherein one asymmetric unit comprises an independent rare earth europium ion, three L ligands and two coordinated water molecules, the center of each rare earth europium ion is coordinated with nine oxygen atoms, the nine oxygen atoms are respectively from seven carboxylic acid groups in six L ligands and two coordinated water molecules, and adjacent rare earth europium ions are bridged by the L ligands to form a chain coordination polymer;
the coordination polymer [ Eu (L)3(H2O)2]nHas an excitation wavelength of 394nm, emission wavelengths of 577nm, 591nm, 617nm, 652nm and 697nm, and shows bright red light observable with naked eyes;
the preparation method of the polymer comprises the following steps:
step 1: mixing europium nitrate hexahydrate, 3-methyl-4-cyanobenzoic acid and water in a molar ratio of 1:1: 400-500, and uniformly stirring to obtain a mixed solution;
step 2: sealing the mixed solution in a reaction kettle, heating to 140-160 ℃, and keeping for 60-96 hours;
step 3: slowly cooling the reaction kettle to room temperature to obtain colorless blocky crystals;
in Step3, the temperature reduction speed of the reaction kettle is controlled to be 5-8 ℃/h.
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| CN101003733A (en) * | 2006-01-20 | 2007-07-25 | 中国科学院福建物质结构研究所 | Fluorescence radiation material of rare earth metal |
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| CN101531672A (en) * | 2008-03-12 | 2009-09-16 | 安徽大学 | Metal-organic framework material with nano pores and preparation method and application thereof |
| CN105503915A (en) * | 2015-12-16 | 2016-04-20 | 西北大学 | Europium metal-organic framework compound with fluorescent recognition function and preparation method and application |
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| CN101087767A (en) * | 2004-12-23 | 2007-12-12 | 马林克罗特公司 | Fluorescent pyrazine derivatives and methods of using the same in assessing renal function |
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| CN101531672A (en) * | 2008-03-12 | 2009-09-16 | 安徽大学 | Metal-organic framework material with nano pores and preparation method and application thereof |
| CN105503915A (en) * | 2015-12-16 | 2016-04-20 | 西北大学 | Europium metal-organic framework compound with fluorescent recognition function and preparation method and application |
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