CN112210082A - Europium/copper bimetallic modified zinc coordination polymer material and preparation method and application thereof - Google Patents

Europium/copper bimetallic modified zinc coordination polymer material and preparation method and application thereof Download PDF

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CN112210082A
CN112210082A CN202011085347.2A CN202011085347A CN112210082A CN 112210082 A CN112210082 A CN 112210082A CN 202011085347 A CN202011085347 A CN 202011085347A CN 112210082 A CN112210082 A CN 112210082A
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coordination polymer
europium
copper
dicarboxylic acid
phenanthroline
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赵典
韩雪
王硕
陆彦潼
刘静雯
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Abstract

The invention discloses a europium/copper bimetallic modified zinc coordination polymer material and a preparation method thereof, belonging to the field of composite material preparation. The composition of the coordination polymer disclosed by the invention is ZnxLy(G)n(x is 1-2, y is 2-4, n is 1-4), L is an organic ligand containing a nitrogen atom and a carboxylic acid group, and G represents a solvent molecule coordinated with a rare earth ion or in a crystal pore channel. The coordination polymer is synthesized by a hydrothermal method, has the characteristics of simple process, mild conditions, good and controllable crystal form, low production cost and high yield, and is suitable for industrial popularization and application; and the coordination polymer can react with H in solution2S carries out quantitative detection, has high response speed, high sensitivity, low detection line and strong anti-interference capability, and can effectively realize self-detectionCalibration as a new type of H2S probe materials are used for in vivo/environmental detection.

Description

Europium/copper bimetallic modified zinc coordination polymer material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite material preparation, and relates to a method strategy for detecting hydrogen sulfide. More particularly, relates to a europium/copper bimetallic modified zinc coordination polymer material, and a preparation method and application thereof.
Background
Hydrogen sulfide (H)2S) is not only a toxic gas in the environment, but also a third endogenous gas signal, in addition to Nitric Oxide (NO) and carbon monoxide (CO), associated with a variety of important physiological and pathological processes. Conventional hydrogen sulfide (H)2S) detection methods comprise gas chromatography, electrochemical analysis, colorimetric method and the like, and have the defects of high use cost, complex operation, time consumption and the like. In recent years, fluorescence sensing based on typical reaction characteristics of hydrogen sulfide, such as reduction reaction of hydrogen sulfide, nucleophilic addition reaction, precipitation reaction of metal sulfide, etc., has also appeared, but most of these methods are fluorescence data obtained based on fluorescent probes with single peak intensity, and are generally influenced by human environmental factors such as probe concentration, environment where the probe is located, excitation light intensity, etc. during detection, so it is important to develop ratio type fluorescent probes which realize self calibration by the ratio of the intensities of two emission peaks.
Coordination Polymers (CPs) are potential multifunctional luminescent materials as inorganic and organic hybrid materials, the optical properties of the CPs are closely related to the components of the structure, and also depend on the characteristics of the structure and the accumulation among molecules, so that the selection of organic ligands and the introduction of luminescent centers are particularly important because the CPs influence energy transfer. And because the coordination polymer contains abundant functional sites such as nitrogen, oxygen and the like, the coordination polymer can be used as a good post-functionalization modification material, and the lanthanide ion-doped coordination polymer is constructed through post-functionalization modification, so that the application of the coordination polymer is expanded.
By using Zn in the invention2+Synthesizing zero-dimensional coordination polymer by ions and organic ligand containing nitrogen and carboxylic acid oxygen simultaneously, and utilizing exposed carboxylic acid oxygen and Eu3+、Cu2+Coordination, constructing dual luminescent centers, not only to a high degreeThe method has the advantages that the hydrogen sulfide is selectively detected, and the high sensitivity is also realized, so that the high efficiency of the synthesized material in the aspect of detecting the hydrogen sulfide is demonstrated, the research direction is provided for further developing a new material for detecting the hydrogen sulfide, and the method is suitable for popularization and application.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a europium/copper bimetallic modified zinc coordination polymer material, which has a simple process and high sensitivity and can rapidly identify hydrogen sulfide, in order to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of coordination polymer, which comprises the following steps:
(1) dissolving zinc salt in deionized water to prepare a metal salt solution for later use;
(2) dissolving an organic ligand and acid in deionized water or an organic solvent to prepare a ligand solution for later use;
(3) and mixing the metal salt solution and the ligand solution, sealing and heating, cooling, filtering and washing to finally obtain the coordination polymer.
Preferably, in the step (1), the zinc salt is zinc nitrate, zinc chloride or zinc sulfate, and the concentration of the metal salt solution is 0.05-0.005 mol/L.
Preferably, in the step (2), the organic ligand is 1, 10-phenanthroline-2, 9-dicarboxylic acid, [2,2' -bipyridine ] -6,6' -dicarboxylic acid, 1, 10-phenanthroline-2-carboxylic acid, [2,2 '; 6', 2' ] terpyridine-6, 6' -dicarboxylic acid, 4, 7-biphenyl-1, 10-phenanthroline-2, 9-dicarboxylic acid, 5-nitro-1, 10-phenanthroline-2, 9-dicarboxylic acid or 5-amino-1, 10-phenanthroline-2, 9-dicarboxylic acid, the organic solvent is at least one of methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide and acetonitrile, and the acid is glacial acetic acid with the mass concentration of 36%.
Further preferably, the concentration of the organic ligand in the ligand solution is 0.005-0.05 mol/L, and the volume ratio of the acid to the deionized water or the organic solvent is (0.07-0.7): 1.
preferably, in the step (3), the mixing ratio of the metal salt solution to the ligand solution is (1-10): 1, the heating temperature is 80-120 ℃, and the heating time is 2-5 days.
The invention also discloses a preparation method of the europium/copper bimetal modified zinc coordination polymer material, which comprises the following steps:
the coordination polymer prepared by the method is soaked in an organic solution containing europium salt and copper salt, and the europium/copper bimetallic modified zinc coordination polymer material can be obtained by heating.
The method comprises the following specific steps:
1) dissolving zinc salt in deionized water to prepare a metal salt solution with the total molar concentration of 0.005-0.05 mol/L;
2) dissolving an organic ligand and acid in deionized water or an organic solvent together to prepare a ligand solution, wherein the molar total amount of the organic ligand and metal ions is equal, the concentration of the organic ligand in the ligand solution is 0.05-0.005 mol/L, and the volume ratio of the acid to water or the organic solvent is 0.7-0.07; the acid is glacial acetic acid with the mass concentration of 36%;
3) and (2) placing the metal salt solution obtained in the step 1) and the ligand solution obtained in the step 2) into a 25mL glass bottle for mixing, performing ultrasonic treatment for 5-10min until the ligand is dissolved and uniformly dispersed, sealing, heating at 80-120 ℃ for 2-5 days, taking out, naturally cooling to room temperature, filtering, washing for 2-5 times by using an organic solvent, and washing away the uncoordinated metal salt and the ligand to obtain the colorless and transparent coordination polymer material.
4) Soaking the coordination polymer obtained in the step 3) in an organic solution of europium salt and copper salt, sealing, heating at 80 ℃ for 1-2 days while stirring, taking out, naturally cooling to room temperature, filtering, washing with an organic solvent for 2-5 times, and washing the uncoordinated europium salt and copper salt to obtain the bimetal modified coordination polymer material for rapidly identifying hydrogen sulfide.
Preferably, the europium salt is europium nitrate, europium chloride or europium acetate, and the copper salt is copper nitrate, copper chloride, copper acetate or copper acetate; the molar ratio of the europium salt to the copper salt is (0.5 to 3): 1.
in addition, the invention claims the europium/copper bimetallic modified zinc coordination polymer material prepared by the method and the application thereof in hydrogen sulfide monitoring in environment/biology.
Wherein the structural general formula of the polymer material is Eu3+/Cu2+@ZnxLy(G)n；
G represents a solvent molecule coordinated with a rare earth ion or in a crystal pore channel, and L is 1, 10-phenanthroline-2, 9-dicarboxylic acid, [2,2' -bipyridyl ] -6,6' -dicarboxylic acid, 1, 10-phenanthroline-2-carboxylic acid, [2,2 '; 6', 2 "] terpyridine-6, 6" -dicarboxylic acid, 4, 7-biphenyl-1, 10-phenanthroline-2, 9-dicarboxylic acid, 5-nitro-1, 10-phenanthroline-2, 9-dicarboxylic acid or 5-amino-1, 10-phenanthroline-2, 9-dicarboxylic acid;
and x is 1 to 2, y is 2 to 4, and n is 1 to 4.
And the europium/copper bimetallic modified zinc coordination polymer material prepared by the method can quantitatively detect H in vivo/environment2The concentration of S is 1.45-1800 mmol/L, and the detection limit is as low as 1.45 mu M, so that the polymer material has good acid and alkali resistance, water stability and thermal stability, and H is in the environment/organism2The S detection aspect has application potential.
According to the technical scheme, compared with the prior art, the europium/copper bimetallic modified zinc coordination polymer material and the preparation method and application thereof have the following excellent effects:
1. the ligand used in the invention contains both nitrogen atoms and carboxylic acid oxygen, and the synthesized framework material contains oxygen atoms which are not coordinated, so that the ligand can be used as a site for post-functional modification, and the lanthanide ion-doped coordination polymer is constructed through the post-functional modification.
Specifically, the invention is prepared by soaking the synthesized coordination polymer in an organic solution of europium salt and copper salt, and during heating, the metal ion Eu3+And Cu2+Successfully coordinated to ZnxLy(G)nTo the oxygen of the uncomplexed carboxylic acid to give Eu3+/Cu2+@ZnxLy(G)nA material. Using Eu3+And Cu2+For ZnxLy(G)nPost-functional modification of (1) to make Eu3+/Cu2+@ZnxLy(G)nThe material shows sharp Eu3+Characteristic emission peak and broad ligand emission peak due to Cu2+To Eu3+Quenching of fluorescence, so that the material shows strong ligand luminescence and weak Eu3+Ion emission at H2In the presence of S, using S2-Ions and Cu2+The strong affinity between ions produces a CuS precipitate, Cu2+Ion pair Eu3+Fluorescence inhibition of ions being released, Eu3+The fluorescence emission of the ions is enhanced, the fluorescence emission of the ligand is weakened, and the ligand is shown to move to Eu3+The energy transfer of the ions is enhanced, so that H with strong selectivity, low detection limit (1.45 mu M) and fast response time (the response time is less than 1min) is obtained2And (5) an S sensor.
2. The invention discloses a bimetal modified coordination polymer material Eu3+/Cu2+@ZnxLy(G)nCan realize specific recognition to hydrogen sulfide, and can not be affected by glutathione, cysteine, serine, NaF, NaCl, NaBr, NaI and NaNO3、Na2SO4、Na2SO3、Na2S2O3、NaHSO3、Na2S2O4、Na2HPO4、KH2PO4、NaClO、CH3COONa、NaHCO3、NaAc、Na2CO3And the coordination polymer material shows excellent selectivity for detecting hydrogen sulfide.
3. The invention discloses a bimetal modified coordination polymer material Eu3+/Cu2+@ZnxLy(G)nHas good H2S identification ability, which can be determined by the intensity ratio of the europium characteristic peak to the emission peak of the ligand to H2The functional relation between S concentration realizes self-calibration detection, overcomes the defect that the traditional coordination polymer material only passes single-peak detection, has high sensitivity and detection limit as low as 1.45 mu M, andit is to H2The detection range of S is 1.45-1800 mu M, and the probe can be used for H in vivo/environment2And (4) quantitatively detecting the concentration of S.
Wherein, the detection limit calculation formula is as follows:
Figure BDA0002720149630000051
LOD＝3δ/S
delta is the standard deviation, N is the number of tests, 20 replicates were tested in the course of the experiment, F0Is Eu3+/Cu2+@ZnxLy(G)nFluorescence intensity in aqueous solution, F1Is Eu3+/Cu2+@ZnxLy(G)nThe mean value of the fluorescence intensity in aqueous solution, S is the slope of the linear fit equation.
4. The invention discloses a coordination polymer material ZnxLy(G)nThe preparation method is simple, the crystallization degree is high, the yield and the stability are high, the acid and alkali resistance is good, the stability is still achieved after the preparation method is soaked in water for 3 days, and the thermal stability can reach 450 ℃, so that the preparation method has important potential in the field of environmental/biological research.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows a coordination polymer material Zn of the present inventionxLy(G)nThe crystal structure of (1);
FIG. 2 shows a coordination polymer material Zn of the present inventionxLy(G)nStability curve (PXRD test);
FIG. 3 shows a coordination polymer material Zn of the present inventionxLy(G)nThermogravimetric analysis curve (TGA);
FIG. 4 shows a coordination polymer material Zn of the present inventionxLy(G)nRespectively soaking Eu in3+And Cu2+After ionization and Eu3+/Cu2 +@ZnxLy(G)nFor detecting H2Phase purity after S concentration (PXRD test);
FIG. 5 shows a bimetal modified coordination polymer Eu according to the invention3+/Cu2+@ZnxLy(G)nFluorescence intensity ratio I of medium rare earth europium and ligandEu/ILAnd H2A graph showing the relationship between the change in fluorescence intensity of S concentration;
FIG. 6 shows Eu3+/Cu2+@ZnxLy(G)nThe fluorescence intensity ratio of the material at 614nm and 386nm is plotted against the concentration of different NaHS solutions (the concentration of NaHS is 0-1800 mu M);
FIG. 7 shows a bimetal modified coordination polymer Eu according to the invention3+/Cu2+@ZnxLy(G)nThe results of experiments on the selectivity of materials to other interferents.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a europium/copper bimetallic modified zinc coordination polymer material which is simple to prepare, high in sensitivity and capable of rapidly identifying hydrogen sulfide.
Wherein the structural general formula of the polymer material is Eu3+/Cu2+@ZnxLy(G)n；
G represents a solvent molecule coordinated with a rare earth ion or in a crystal pore channel, and L is 1, 10-phenanthroline-2, 9-dicarboxylic acid, [2,2' -bipyridyl ] -6,6' -dicarboxylic acid, 1, 10-phenanthroline-2-carboxylic acid, [2,2 '; 6', 2 "] terpyridine-6, 6" -dicarboxylic acid, 4, 7-biphenyl-1, 10-phenanthroline-2, 9-dicarboxylic acid, 5-nitro-1, 10-phenanthroline-2, 9-dicarboxylic acid or 5-amino-1, 10-phenanthroline-2, 9-dicarboxylic acid;
and x is 1 to 2, y is 2 to 4, and n is 1 to 4.
And, the above coordination polymer material ZnxLy(G)nThe crystal structure of (2) is shown in FIG. 1.
With Zn (NO)3)2·6H2O and 1, 10-phenanthroline-2, 9-dicarboxylic acid (H)2padc) diamond crystals synthesized by solvothermal reaction are exemplified. The coordination polymer is a 0D framework crystallized in a triclinic system of P-1 space group by single crystal x-ray diffraction analysis (SXRD), consisting of [ Zn ]2(padc)2(H2O)3]·2H2The O unit forms a supermolecular coordination polymer formed by the interaction of hydrogen bonds and interlaminar dislocation pi-pi. With two Zn (II) atoms, two padc in the asymmetric unit2-An anion and three coordinated water molecules. In addition, 3 water molecules and carboxylic acid oxygens from an asymmetric unit form hydrogen bonds with water molecules and carboxylic acid oxygens of an adjacent asymmetric unit, thereby creating a long chain in a 1D zigzag shape. The adjacent benzene and pyridine rings form rigid 3D supermolecular coordination polymers through face-to-face pi-pi stacking interaction.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
1) Dissolving zinc nitrate with the molar weight of 0.05mmol in 10mL of deionized water to obtain a zinc nitrate solution with the molar concentration of 0.005 mol/L;
2) dissolving 0.05mmol of 1, 10-phenanthroline-2, 9-dicarboxylic acid and 700 mu L of 36% glacial acetic acid in 10mLN, N-dimethylformamide together to obtain a ligand solution, wherein the concentration of the organic ligand in the ligand solution is 0.004673mol/L, and the volume ratio of the glacial acetic acid to the N, N-dimethylformamide is 0.07;
3) mixing the two solutions in a 25mL glass bottle with a cover, sealing, keeping the temperature in an oven at 80 ℃ for 3 days, naturally cooling to room temperature, filtering, washing with N, N-dimethylformamide for several times to remove uncomplexed ligand and metal salt to obtain coordination polymer material [ Zn ]2L2(H2O)3]·2H2O, yield 51%.
The coordination polymer material Zn obtained in the above way2L2(H2O)3Has good water stability, thermal stability and acid-base stability, and the test results are shown in attached figures 2 and 3.
Specifically, a coordination polymer Zn obtained by a hydrothermal methodxLy(G)nPlacing in deionized water, PBS buffer solution, boiling water, HCl solution with pH of 2, NaOH solution with pH of 10, taking out after 2 days, air drying, and performing powder X-ray diffraction (PXRD) analysis, as shown in FIG. 2, wherein all PXRD spectra are similar to simulated ZnxLy(G)nThe PXRD patterns can be well matched, and Zn is shownxLy(G)nHas good water stability and acid-base stability.
As can be seen from FIG. 3, in the first stage, from 100 ℃ to about 150 ℃, the free solvent on the crystal surface and in the pore channels is mainly lost, and the weight loss is about 8.7%; the second stage is carried out at the temperature of between 350 and 430 ℃, mainly the separation of the rare earth ion axial coordination solvent and the weight loss is about 12.4 percent; the third stage occurs after 450 ℃, which is mainly the decomposition and carbonization of the organic ligand. TGA Curve illustrates ZnxLy(G)nThe structure stability can be maintained at 450 ℃, and the thermal stability is good.
And as can be seen from FIG. 4 by single crystal X-ray diffraction analysis, Zn was synthesizedxLy(G)nPXRD pattern of (A) and Single Crystal simulated ZnxLy(G)nThe PXRD patterns can be well matched, and meanwhile, Eu is3+@ZnxLy(G)nAnd Eu3+/Cu2+@ZnxLy(G)nPXRD pattern of (A) and Synthesis of ZnxLy(G)nThe PXRD patterns of the samples are the same, and the stability of the framework is not damaged after the coordination of the metal cations. In Eu3 +/Cu2+@ZnxLy(G)nAfter the NaHS detection is finished, the material remains intact.
And, the coordination polymer material [ Zn ]2L2(H2O)3]·2H2O is formed by stacking a structural unit, a large number of exposed sites exist, and the structural units are connected with each other by O-H … O hydrogen bonds and interlayer pi-pi bonds.
In addition, because the synthesized coordination polymer material has oxygen atoms which are not coordinated, the coordination polymer material can be used as a site for post-functional modification, and the lanthanide ion-doped coordination polymer is constructed through the post-functional modification, which is specifically as follows:
soaking the synthesized coordination polymer in an organic solution of europium nitrate and copper nitrate, and heating to obtain Eu as a metal ion3+And Cu2+Successfully coordinated to [ Zn ]2L2(H2O)3]·2H2Oxygen of the non-coordinated carboxylic acid of O to finally obtain Eu3+/Cu2 +@[Zn2L2(H2O)3]·2H2And (3) O material.
Among them, FIG. 5 shows that the coordination polymer Eu modified by bimetal3+/Cu2+@ZnxLy(G)nIn the passage of H2The ligand before S treatment showed strong ligand luminescence at 386nm and weak rare earth Eu at 614nm3+Characteristic emission of ions, addition of H2After S, using S2-Ions and Cu2+The strong affinity between ions produces a CuS precipitate, Cu2+Ion pair Eu3+Fluorescence inhibition of ions being released, Eu3+The fluorescence emission of the ion at 614nm is enhanced, and the fluorescence emission of the ligand at 386nm is weakened, indicating that the ligand is towards Eu3+The energy transfer of the ions is enhanced.
And, as shown in FIG. 6, Eu3+/Cu2+@[Zn2L2(H2O)3]·2H2Fluorescence intensity ratio I of rare earth europium and ligand in O materialEu/IL(IEuAnd ILThe luminous intensity of characteristic peaks of europium and ligand, the peak positions are 614nm and 386nm respectively) and H2The S concentration (0-1800 mu M) has a good exponential relationship and can be fitted by the following equation:
I614/I386＝-13.32*exp(-0.002*CNaHS) +13.14, thus indicating that Eu3+/Cu2+@ZnxLy(G)nThe material can be used for quantitatively detecting hydrogen sulfide.
And, to examine the double-metal modified coordination polymer Eu3+/Cu2+@[Zn2L2(H2O)3]·2H2The O material responds selectively to hydrogen sulfide, and different interfering substances can be added to the system and the change in fluorescence detected (as shown in fig. 7). Other interferents added thereto: glutathione, cysteine, serine, NaF, NaCl, NaBr, NaI, NaNO3、Na2SO4、Na2SO3、Na2S2O3、NaHSO3、Na2S2O4、Na2HPO4、KH2PO4、NaClO、CH3COONa、NaHCO3、NaAc、Na2CO3Then, hydrogen sulfide solution with the same concentration is added, and the fluorescence intensity emitted at 614nm is far higher than that of other interferents, so that the specific recognition of the hydrogen sulfide is realized.
Specifically, to test the probe Eu3+/Cu2+@ZnxLy(G)nWhether the sensing response to hydrogen sulfide is maintained in the presence of environmental and biologically relevant substances, the probe (0.5mg/mL) is added to a solution containing hydrogen sulfide and other interferents. All the tested interferents had essentially no effect on the detection of sulfide, indicating that even thoughEu in the presence of interferents3+/Cu2+@ZnxLy(G)nCan still be used for selective detection of hydrogen sulfide.
Example 2:
1) dissolving zinc chloride with the molar weight of 0.01mmol in 5mL of deionized water to obtain a zinc chloride solution with the molar concentration of 0.002 mol/L;
2) dissolving 0.01mmol of 1, 10-phenanthroline-2-carboxylic acid and 300 mu L of 36% glacial acetic acid in 5mL of N, N-dimethylacetamide to obtain a ligand solution, wherein the concentration of an organic ligand is 0.001887mol/L, and the volume ratio of the glacial acetic acid to the N, N-dimethylformamide is 0.06;
3) mixing the two solutions in a 25mL glass bottle with a cover, sealing, keeping the temperature in an oven at 100 ℃ for 2 days, naturally cooling to room temperature, filtering, washing with N, N-dimethylacetamide for several times to remove uncomplexed ligand and metal salt, and obtaining the coordination polymer material [ Zn ]2L2(DMF)2]·H2O, yield 48%.
Coordination polymer material [ Zn ] obtained as described above2L2(DMF)2]·H2O has good water stability, thermal stability and acid-base stability.
And the coordination polymer material [ Zn ] can be known by single crystal X-ray diffraction analysis2L2(DMF)2]·H2O is formed by stacking a structural unit, a large number of exposed sites exist, and the structural units are connected with each other by O-H … O hydrogen bonds and interlayer staggered pi-pi bonds.
In addition, because the synthesized coordination polymer material has exposed carboxyl oxygen, the coordination polymer material can be used as a site for post-functional modification, and the lanthanide ion-doped coordination polymer is constructed through the post-functional modification, which is specifically as follows:
soaking the synthesized coordination polymer in organic solution of europium chloride and copper chloride, and heating to obtain Eu metal ion3+And Cu2+Successfully coordinated to [ Zn ]2L2(DMF)2]·H2Oxygen of the non-coordinated carboxylic acid of O to give Eu3+/Cu2+@[Zn2L2(DMF)2]·H2And (3) O material.
Wherein, Eu3+/Cu2+@[Zn2L2(DMF)2]·H2Fluorescence intensity ratio I of rare earth europium and ligand in O materialEu/IL(IEuAnd ILThe luminous intensity of characteristic peaks of europium and ligand, the peak positions are 614nm and 386nm respectively) and H2The S concentration has a good exponential relationship.
And, to examine the double-metal modified coordination polymer Eu3+/Cu2+@[Zn2L2(DMF)2]·H2The O material is selectively responsive to the hydrogen sulfide, different interfering substances can be added into the system, and the fluorescence change of the system can be detected. Other interferents added thereto: glutathione, cysteine, serine, NaF, NaCl, NaBr, NaI, NaNO3、Na2SO4、Na2SO3、Na2S2O3、NaHSO3、Na2S2O4、Na2HPO4、KH2PO4、NaClO、CH3COONa、NaHCO3、NaAc、Na2CO3Then, hydrogen sulfide solution with the same concentration is added, and the fluorescence intensity emitted at 614nm is far higher than that of other interferents, so that the specific recognition of the hydrogen sulfide is realized.
Example 3:
1) dissolving zinc sulfate with the molar weight of 0.025mmol in 7mL of deionized water to obtain a zinc sulfate solution with the molar concentration of 0.00357 mol/L;
2) dissolving 0.025mmol of [2,2 '-bipyridyl ] -6,6' -dicarboxylic acid and 500 mu L of 36% glacial acetic acid in 7mL of acetonitrile to obtain a ligand solution with the concentration of organic ligand of 0.00333mol/L and the volume ratio of the glacial acetic acid to the acetonitrile amine of 0.071;
3) mixing the two solutions in 25mL glass bottle with cover, sealing, keeping in oven at 120 deg.C for 4 days, naturally cooling to room temperature, filtering, washing with acetonitrile for several times to remove uncomplexed ligand and metal salt to obtain coordinationPolymeric material [ Zn ]2L4(DMA)]·2H2O, yield 47%.
The above-mentioned resulting coordination polymer material Zn2L4(DMA) has good water stability, thermal stability and acid-base stability.
And the coordination polymer material [ Zn ] can be known by single crystal X-ray diffraction analysis2L4(DMA)]·2H2O is formed by stacking a structural unit, a large number of exposed sites exist, and the structural units are connected with each other by O-H … O hydrogen bonds and interlayer staggered pi-pi bonds.
In addition, because the synthesized coordination polymer material has naked carboxylic acid oxygen, the coordination polymer material can be used as a site for post-functionalization modification, and a lanthanide ion-doped coordination polymer is constructed through the post-functionalization modification, which is specifically as follows:
soaking the synthesized coordination polymer in organic solution of europium chloride and copper chloride, and heating to obtain Eu metal ion3+And Cu2+Successfully coordinated to [ Zn ]2L4(DMA)]·2H2Oxygen of the non-coordinated carboxylic acid of O to finally obtain Eu3+/Cu2+@[Zn2L4(DMA)]·2H2And (3) O material.
Wherein, Eu3+/Cu2+@[Zn2L4(DMA)]·2H2Fluorescence intensity ratio I of rare earth europium and ligand in O materialEu/IL(IEuAnd ILThe luminous intensity of characteristic peaks of europium and ligand, the peak positions are 614nm and 386nm respectively) and H2The S concentration has a good exponential relationship.
And, to examine the double-metal modified coordination polymer Eu3+/Cu2+@[Zn2L4(DMA)]·2H2The O material is selectively responsive to the hydrogen sulfide, different interfering substances can be added into the system, and the fluorescence change of the system can be detected. Other interferents added thereto: glutathione, cysteine, serine, NaF, NaCl, NaBr, NaI, NaNO3、Na2SO4、Na2SO3、Na2S2O3、NaHSO3、Na2S2O4、Na2HPO4、KH2PO4、NaClO、CH3COONa、NaHCO3、NaAc、Na2CO3Then, hydrogen sulfide solution with the same concentration is added, and the fluorescence intensity emitted at 614nm is far higher than that of other interferents, so that the specific recognition of the hydrogen sulfide is realized.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The preparation method of the coordination polymer is characterized by comprising the following steps:
(1) dissolving zinc salt in deionized water to prepare a metal salt solution for later use;
(2) dissolving an organic ligand and acid in deionized water or an organic solvent to prepare a ligand solution for later use;
(3) and mixing the metal salt solution and the ligand solution, sealing and heating, cooling, filtering and washing to finally obtain the coordination polymer.
2. The method of claim 1, wherein the zinc salt is zinc nitrate, zinc chloride or zinc sulfate, and the concentration of the metal salt solution is 0.005-0.05 mol/L.
3. The method of claim 1, wherein the organic ligand is 1, 10-phenanthroline-2, 9-dicarboxylic acid, [2,2' -bipyridine ] -6,6' -dicarboxylic acid, 1, 10-phenanthroline-2-carboxylic acid, [2,2 '; 6', 2' ] terpyridine-6, 6' -dicarboxylic acid, 4, 7-biphenyl-1, 10-phenanthroline-2, 9-dicarboxylic acid, 5-nitro-1, 10-phenanthroline-2, 9-dicarboxylic acid or 5-amino-1, 10-phenanthroline-2, 9-dicarboxylic acid, wherein the organic solvent is at least one of methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide and acetonitrile, and the acid is glacial acetic acid with the mass concentration of 36%.
4. The method of claim 3, wherein the concentration of the organic ligand in the ligand solution is 0.005-0.05 mol/L, and the volume ratio of the acid to the deionized water or the organic solvent is (0.07-0.7): 1.
5. the method for preparing a coordination polymer according to claim 1, wherein in the step (3), the mixing ratio of the metal salt solution and the ligand solution is (1-10): 1, the heating temperature is 80-120 ℃, and the heating time is 2-5 days.
6. A preparation method of a zinc coordination polymer material modified by europium/copper bimetallic is characterized by comprising the following steps:
the europium/copper bimetallic modified zinc coordination polymer material can be obtained by soaking the coordination polymer prepared by the method of claim 1 in an organic solution containing europium salt and copper salt and heating.
7. The method for preparing a europium/copper bimetal modified zinc coordination polymer material according to claim 6, wherein the europium salt is europium nitrate, europium chloride or europium acetate, and the copper salt is copper nitrate, copper chloride, copper acetate or copper acetate; the molar ratio of the europium salt to the copper salt is (0.5 to 3): 1.
8. a europium/copper bimetal modified zinc coordination polymer material prepared by the method of claim 6, wherein the structure of the polymer materialGeneral formula is Eu3+/Cu2+@ZnxLy(G)n；
Wherein G represents a solvent molecule coordinated with a rare earth ion or in a crystal pore channel, and L is 1, 10-phenanthroline-2, 9-dicarboxylic acid, [2,2' -bipyridyl ] -6,6' -dicarboxylic acid, 1, 10-phenanthroline-2-carboxylic acid, [2,2 '; 6', 2 "] terpyridine-6, 6" -dicarboxylic acid, 4, 7-biphenyl-1, 10-phenanthroline-2, 9-dicarboxylic acid, 5-nitro-1, 10-phenanthroline-2, 9-dicarboxylic acid or 5-amino-1, 10-phenanthroline-2, 9-dicarboxylic acid;
and x is 1 to 2, y is 2 to 4, and n is 1 to 4.
9. Use of the europium/copper-bimetallic-modified zinc coordination polymer material as defined in claim 6 or the europium/copper-bimetallic-modified zinc coordination polymer material as defined in claim 8 for monitoring hydrogen sulfide in the environment/organism.
10. The use of claim 9, further comprising: the europium/copper bimetallic modified zinc coordination polymer material is H in a living body/environment2And (3) quantitatively detecting the concentration of S, wherein the detection concentration range is 1.45-1800 mmol/L.
CN202011085347.2A 2020-10-12 2020-10-12 Europium/copper bimetallic modified zinc coordination polymer material and preparation method and application thereof Pending CN112210082A (en)

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