CN114410296B - Preparation method and application of MOF composite material based on isoleucine derivative ligand - Google Patents
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Abstract
The invention provides a preparation method of an MOF composite material based on isoleucine derivative ligand, which comprises the following steps: adding salicylaldehyde and NaBH into ethanol water solution of L-isoleucine and NaOH after stirring and dissolving 4 Adjusting pH, vacuum filtering, washing, drying to obtain isoleucine derivative ligand, adding anhydrous ethanol and Zn (NO) 3 ) 2 ·6H 2 O, stirring until the mixture is clear, subpackaging, adding N, N-dimethylformamide and NaOH aqueous solution, drying by blowing, washing, and drying by blowing to obtain the MOF material based on the isoleucine derivative ligand. The invention also provides application, which is used for detecting metal cations and aldehyde steam molecules after Luo Mingdan B is added. The MOF composite material based on the isoleucine acid derivative ligand has good fluorescence emission performance, can be applied to detection of steam small molecule benzaldehyde steam molecules after Luo Mingdan B is added, and is metal cation Cr 3+ The detection of (2) has good effect.
Description
Technical Field
The invention belongs to the technical field of metal-organic framework materials, and particularly relates to a preparation method and application of an MOF composite material based on isoleucine derivative ligands.
Background
Metal-organic framework Materials (MOFs) are crystalline porous materials formed by coordination of organic ligands and metal ions, and have been attracting attention in the fields of ion detection small molecule detection, catalysis, drug release, detection of explosives, etc. for decades due to their chemical composition diversity, structural designability, hole adjustability and material modifier properties. In particular, in the aspect of detecting cations and small molecules, the MOF material has strong modification property, and can realize targeted detection of characteristic ions by introducing different functional groups, and has strong targeting property, rich luminous characteristics and rich and various detection modes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of an MOF composite material based on isoleucine derivative ligand, the MOF composite material based on isoleucine derivative ligand has good fluorescence emission performance, and can be applied to detection of steam molecules of steam micromolecular benzaldehyde after Luo Mingdan B is added, and metal cations Cr 3+ The detection of (2) has good effect.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for preparing an isoleucine derivative ligand-based MOF composite material, which comprises the following steps:
s1, adding ethanol aqueous solution with the volume fraction of 50% into L-isoleucine and NaOH, stirring and dissolving, then adding salicylaldehyde, stirring for 2 hours at normal temperature, continuing stirring under the ice bath condition, and adding NaBH after the solution is stable 4 Stirring for 1h, regulating the pH value to 6 by using concentrated hydrochloric acid, precipitating, continuously stirring for 0.5h, carrying out suction filtration, washing by using diethyl ether and ethanol in sequence, and drying for 12h at the temperature of 65 ℃ to obtain the isoleucine derivative ligand; the molecular formula of the isoleucine derivative ligand is C 13 H 19 NO 3 The structural formula is as follows:
s2, synthesis of MOF composite materials based on isoleucine derivative ligands: adding absolute ethanol to the isoleucine derivative ligand obtained in S1 to obtain turbid solution, and then adding Zn (NO 3 ) 2 ·6H 2 O, stirring to clarify to obtain a mixed solution, adding N, N-dimethylformamide and 0.05mol/L NaOH aqueous solution into the mixed solution after sub-packaging, sealing, and air-drying at 65deg.C for 3d to obtain quadrilateral flaky crystalAfter washing 3 times with absolute ethanol, the MOF composite material based on the isoleucine derivative ligand is obtained by air drying for 12 hours at 65 ℃.
Preferably, the L-isoleucine, naOH, 50% by volume aqueous ethanol solution, salicylaldehyde and NaBH in S1 4 The dosage ratio of (2) is 0.131g:0.079g:5mL:0.121g:0.041g.
Preferably, the isoleucine derivative ligand, absolute ethanol and Zn (NO) in the mixture in S2 3 ) 2 ·6H 2 The dosage ratio of O is 400mg:100mL:600mg; the dosage ratio of the mixed solution after sub-packaging, N-dimethylformamide and the NaOH aqueous solution with the concentration of 0.05mol/L required in the preparation of the MOF material based on the isoleucine derivative ligand is 2mL: 400. Mu.L: 750 μl.
The invention also provides an application of the prepared MOF composite material based on the isoleucine derivative ligand, luo Mingdan B is added into the MOF composite material based on the isoleucine derivative ligand to obtain MOF composite material@rho based on the isoleucine derivative ligand, and the MOF composite material based on the isoleucine derivative ligand is applied to selectively identifying Cr 3+ And detecting benzaldehyde steam molecules.
Preferably, the MOF composite @ Rho based on isoleucine derivative ligand recognizes the Cr 3+ At the same time, the ratio of the luminous peak intensities at 450nm and 580nm is obviously enhanced, and the luminous intensities at the two positions are obviously quenched.
Preferably, the MOF composite based on isoleucine derivative ligand @ Rho exhibits a quenching effect when the benzaldehyde vapor molecule is identified at a wavelength of 370 nm.
Compared with the prior art, the invention has the following advantages:
the MOF composite material based on the isoleucine derivative ligand has good fluorescence emission performance, can be applied to detection of steam small molecule benzaldehyde steam molecules after Luo Mingdan B is added, and is metal cation Cr 3+ The detection of (2) has good effect.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
FIG. 1 is a single crystal structure diagram of an isoleucine derivative ligand-based MOF material prepared in example 1 of the present invention.
Fig. 2 is a thermal weight loss curve and PXRD pattern of an isoleucine derivative ligand-based MOF material prepared in example 1 of the present invention under nitrogen atmosphere.
FIG. 3 is a graph showing fluorescence emission spectra of isoleucine derivative ligand-based MOF materials prepared in example 1 of the present invention in DMF solvent and solid state fluorescence emission spectra of isoleucine derivative ligand-based MOF materials.
FIG. 4 is a microscopic image of the isoleucine derivative ligand-based MOF material of example 2 of the present invention and the resulting isoleucine derivative ligand-based MOF material @ Rho at different Rho concentrations.
FIG. 5 is an ultraviolet absorption spectrum of an isoleucine derivative ligand-based MOF material and Rho of example 2 of the present invention and a standard curve of Rho in a 0.1mol/L nitric acid solution.
FIG. 6 is a graph of solid state fluorescence emission spectra of the compounds of example 2 of the present invention and a graph of solid state fluorescence emission spectra of MOF material @ Rho based on isoleucine derivative ligands under ultraviolet excitation at different wavelengths.
FIG. 7 shows the fluorescence emission spectra of MOF material @ Rho based on isoleucine derivative ligand under 370nm ultraviolet excitation obtained at different Rho concentrations and the PXRD pattern of MOF material @ Rho based on isoleucine derivative ligand at different Rho concentrations (B) obtained in example 2 of the present invention.
FIG. 8 is a solid state fluorescence emission spectrum (A), a peak height (B) of a ligand and Rho, and a two-part peak height comparison (C) of the compound 2-A of example 2 of the present invention after being immersed in a solution containing different metal ions for 12 hours.
FIG. 9 is a graph showing the concentration of Cr at various concentrations of Compound 2-A of example 2 of the present invention 3+ Fluorescence emission spectrum (A) after soaking for 12h, and Cr with different concentrations of compound 2-A 3+ Peak height ratio chart (B) after soaking in water for various times, 10mM Cr 3+ pXRD spectrum (C) of compound 2-A and S-V spectrum (D) of compound 2-A after soaking for 12 h.
FIG. 10 is a graph showing fluorescence emission spectra (A), peak heights (B) of a ligand and Rho, and a two-part peak height comparison graph (C) of Compound 2-A of example 2 of the present invention after being placed in an aldehyde organic solvent vapor for 12 hours.
FIG. 11 is a graph showing solid phase fluorescence emission spectra of Compound 2-A of example 2 of the present invention after being left in benzaldehyde vapor (A) or salicylaldehyde vapor (D) for various periods of time, a graph showing peak height ratio (B) of Compound 2-A after being left in benzaldehyde vapor environment for various periods of time, and PXRD spectra (C) of Compound 2-A after being left in benzaldehyde vapor and salicylaldehyde vapor for 12 hours.
Detailed Description
Example 1
The present example is a method for preparing an isoleucine derivative ligand-based MOF material, comprising:
s1, adding 5mL of 50% ethanol water solution with volume fraction to 0.131g (1.0 mmol) of L-isoleucine and 0.079g (2 mmol) of NaOH, stirring and dissolving, adding 0.121g (1.0 mmol) of salicylaldehyde, stirring at normal temperature for 2h, continuing stirring under ice bath condition, adding 0.041g of NaBH after the solution is stable 4 Stirring for 1h, regulating the pH value to 6 by using concentrated hydrochloric acid, precipitating, continuously stirring for 0.5h, carrying out suction filtration, washing by using diethyl ether and ethanol in sequence, and drying for 12h at the temperature of 65 ℃ to obtain the isoleucine derivative ligand; the molecular formula of the isoleucine derivative ligand is C 13 H 19 NO 3 The structural formula is as follows:
s2, synthesis of MOF composite materials based on isoleucine derivative ligands: to 400mg of the isoleucine derivative ligand obtained in S1 was added 100mL of absolute ethanol to obtain a turbid solution, followed by addition of 600mg of Zn (NO) 3 )2·6H 2 O, stirring to clarify to obtain clarified mixed solution, subpackaging in 5mL refined seed bottle, adding 400 μL of N, N-dimethylformamide and 750 μL of 0.0 to 2mL clarified mixed solution after subpackagingSealing with 5mol/L NaOH aqueous solution, drying by air blast at 65 ℃ for 3d to obtain quadrilateral flaky crystals, collecting the quadrilateral flaky crystals in a precision seed bottle, washing the quadrilateral flaky crystals with absolute ethyl alcohol for 3 times, and drying by air blast at 65 ℃ for 12h to obtain an isoleucine derivative ligand-based MOF material; the molecular formula of the MOF material based on the isoleucine derivative ligand is C 26 H 34 N 2 O 6 Zn 2 This is designated compound 1.
(1) Compound1 crystal structure:
crystal structure data for the MOF composites based on isoleucine derivative ligands were collected using a Agilent Technologies Super Nova single crystal diffractometer at low temperature of 100K. Cu-Ka as X-ray sourceThe single crystal structure was resolved and refined using the SHELXL-97 procedure. The crystal structure parameters of the MOF composite based on isoleucine derivative ligands are shown in table 1.
TABLE 1 Crystal structure parameters of MOF composite based on Isolignotic acid derivative ligands
Analysis of the single crystal structure showed that: crystallization of Compound1 in monoclinic System, P2 (1) The space group has a two-dimensional layered structure. As shown in FIG. 1, FIG. 1 (a) shows Zn 2+ Is a coordinated environment diagram of (1); (b) is an overlay along the a-axis; (c) a two-dimensional grid pattern along the c-axis. Each asymmetric structural unit contains 2 ligands and 2 Zn 2+ Ions, each Zn 2+ Five coordination is adopted for the ions, the five coordination zinc ions are respectively coordinated with a phenolic hydroxyl oxygen atom, a carboxylic acid oxygen atom, an amino N atom of the same ligand, a carboxyl oxygen atom in another ligand and a phenolic hydroxyl oxygen atom in a third ligand, the five coordination zinc ions are connected into a dinuclear unit by two phenolic hydroxyl oxygen atoms, and carboxylate groups are connected with 5 dinuclear units to form a two-dimensional network structure, and layers are connected with each other by Van der Waals force.
(2) X-ray diffraction and thermogravimetric analysis of compound 1:
as shown in FIG. 2 (A), the thermal weight loss curve (TG) of the compound1 in the nitrogen atmosphere shows that the compound1 loses weight by 1.14% in the temperature range of 40-340 ℃, and can be attributed to the loss of water molecules. When the temperature is higher than 338 ℃, the material has obvious weightlessness process, which is caused by collapse of the framework and decomposition of the ligand. As can be seen from the comparison of the X-ray powder diffraction of the compound1 obtained by synthesis with the PXRD pattern simulated by the single crystal X-ray diffraction analysis data software, the diffraction peaks of the compound1 and the PXRD pattern correspond well, the characteristic peaks coincide with the software simulation, the peak shape is sharp, and the purity of ligands based on isoleucine derivatives prepared by mass synthesis is reliable (figure 2 (B)).
(3) Fluorescent Properties of Compound1
The concentration is 1.0X10 -2 、1.0×10 -3 、1.0×10 -4 、1.0×10 -5 、1.0×10 -6 mol/L isoleucine derivative ligand (C) 13 H 19 NO 3 ) The fluorescence emission spectrum of DMF solution of (C) under 370nm ultraviolet light is shown as 3 (A), from which we can see that the concentration of ligand is increased from 1.0X10 -2 mol/L to 1.0X10 -4 The fluorescence intensity of the mol/L ligand solution tends to increase gradually, because the ligand has aggregation-induced quenching effect, and the ligand concentration is larger or the ligand can quench self fluorescence when in an aggregation state. The concentration is 1.0X10 -4 To 1.0X10 -6 The fluorescence intensity of the mol/L ligand solution gradually decreases, since the concentration of the ligand decreases, resulting in a decrease in fluorescence. Compound1 (compound 1) and isoleucine derivative ligand (C) 13 H 19 NO 3 ) The solid fluorescence emission spectrum under 370nm ultraviolet excitation is shown in FIG. 3 (B), from which it is known that the solid fluorescence of the ligand is weak when the ligand passes through Zn metal 2+ After coordination, the fluorescence intensity is obviously enhanced. The main reason that the fluorescence intensity of the compound1 is stronger than that of the ligand is that the ligand forms a framework material in a crystallization induction mode, so that ligand molecules are orderly arranged, and aggregation induction quenching effect of the molecules can be eliminated after the rigidity of the ligand molecules is increased. Compound1 is based on ligand luminescence and can be attributed to pi→pi or pi→n transitions in the ligand.
Example 2
This example shows the application of the isoleucine derivative ligand-based MOF material (Compound 1) prepared in example 1, in which Luo Mingdan B was added to the isoleucine derivative ligand-based MOF composite material to give isoleucine derivative ligand-based MOF composite material @ Rho, designated Compound 2, for selective Cr identification 3+ And detecting benzaldehyde steam molecules.
The MOF composite material@rho based on isoleucine derivative ligand recognizes the Cr 3+ When the fluorescent dye is used, the fluorescent dye has obvious quenching at 450nm and 580nm luminescence peak intensity, and other metal ions have no quenching or weak quenching and no Cr 3+ The quenching effect on MOF composite material @ Rho is obvious.
The MOF composite @ Rho based on the isoleucine derivative ligand exhibits a quenching effect when recognizing the benzaldehyde vapor molecule at a wavelength of 370 nm.
(1) Synthesis of Compound 2 and determination of Rho content:
ultraviolet spectroscopy of Compounds 1 and Rho: a certain amount of Rho and compound1 are weighed separately in a precise day, dissolved by nitric acid of 0.1000mol/L respectively, and fixed to 100.00mL. And establishing a base line by taking 0.1000mol/L nitric acid as a blank, and carrying out ultraviolet full-wave band scanning on the two groups of solutions within the ultraviolet range of 200-800 nm.
Establishment of the bid-marked koji by Rho in 0.1000mol/L nitric acid: 0.0013g of Rho is weighed by a precision balance, dissolved by 50.00mL 0.1000mol/L of nitric acid, and diluted to 100.00mL to obtain 13.00 mu g/mL of Rho nitric acid solution, 80.00mL of 13.00 mu g/mL of Rho nitric acid solution is taken, and 10.40 mu g/mL of Rho nitric acid solution is obtained by diluting the solution to 100.00mL of Rho nitric acid solution with different concentrations. The absorbance was measured at 556nm, and a standard curve was drawn.
Determination of Rho content in Compound 2: 30.0000mg of Compound 2 was dissolved in 1.00mL of 1.0000mol/L nitric acid, water was added to a volume of 10.00mL, and the absorbance was measured at 556nm. The Rho content of compound 2 was calculated.
Compounds 2-A and 2 obtained at different Rho concentrationsThe photographs of-B, 2-C, 2-D, 2-E are shown in FIG. 4, where a is compound1 and B-E in FIG. 4 are shown in the order of 6.60×10 -2 mol/L、1.32×10 -1 mol/L、1.98×10 -1 mol/L、2.64×10 -1 mol/L，3.30×10 -1 mol/L, g in FIG. 4 is 6.60×10 -2 Compound 2 was collected in large amounts at mol/L, and h in FIG. 4 is a photograph of compound 2 collected at various Rho concentrations. As can be seen from fig. 4, the red color of compound 2 gradually deepens as the concentration of Rho increases.
The ultraviolet spectra of the compound1 and Rho with certain concentrations are shown in the figure 5 (A), the ultraviolet absorption range of the compound1 is 200nm-300nm, and the maximum ultraviolet absorption wavelength is 215nm. Rho has an ultraviolet absorption of 200nm to 600nm and a maximum ultraviolet absorption wavelength of 556nm. The standard curve of Rho in 0.1mol/L nitric acid solution is shown in FIG. 5 (B), the standard curve equation of Rho in 0.1mol/L nitric acid is Y=0.1247C+0.00951, R 2 0.99985, rhodamine contained in the compounds 2-a, 2-B, 2-C, 2-D, 2-E were 0.00328%,0.00879%,0.01127%,0.06985%,0.07601%, respectively, by standard curve method.
(2) Compound 2 fluorescent Properties and powder X-ray diffraction
Fluorescence test: the solid fluorescent properties of the material compound1 and compound 2 were tested at room temperature and 370nm ultraviolet excitation wavelength. During the measurement, 10.00mg of solid sample is added to 2X 5mm 2 In the cylindrical quartz tank of (2), the voltage of a photomultiplier is 950V, the scanning speed is 30nm/min, the width of a slit for excitation and emission is 10nm, and the detection mode is fluorescence.
The solid fluorescence emission spectra of compound1, compound 2-A, compound 1+rho, and Rho under 370nm ultraviolet excitation are shown in FIG. 6 (A), solid Rho is a molecule with aggregation-induced quenching effect, so that the solid does not fluoresce under 370nm ultraviolet excitation. Compound1 has a fluorescence peak of the ligand at 450nm under 370nm uv excitation, compound1 is based primarily on ligand luminescence. In-situ synthesized compound 2-A has ligand fluorescence peak at 450nm and fluorescence characteristic peak at 580nm, and compound1 and Rho are mechanically stirred and mixed to obtain compound 1+rho with ligand fluorescence only at 450nmThe fluorescence characteristic peak of Rho is not found at 580nm, which shows that the compound 2-A obtained by the in-situ method can effectively overcome the aggregation-induced quenching effect of Rho to generate the fluorescence characteristic peak of Rho. At Rho concentration of 6.60×10 -2 The emission spectrum of the compound 2 obtained by mol/L under the excitation of ultraviolet light with different wavelengths is shown in figure 6 (B).
The fluorescence emission spectra of the compounds 2-A, 2-B, 2-C, 2-D, 2-E obtained at different Rho concentrations under excitation by 370nm ultraviolet excitation are shown in FIG. 7 (A), when the Rho concentration is gradually increased, the fluorescence peak attributed to Rho at 580nm is slightly red-shifted, and when the Rho concentration is 2.64×10 -1 mol/L、3.30×10 -1 The fluorescence intensity of the ligand in the 2-D and 2-E compounds obtained at mol/L was weakened together with Rho. The reason for this was inferred to be the aggregation of Rho after too much Rho was contained in compound1, resulting in fluorescence quenching. During the synthesis of compound 2, it was found that as the concentration of Rho increased, the time required for compound 2 to grow was longer and the yield was gradually decreased. The growth time of the compounds 2-D and 2-E is about two weeks, and the reason for this phenomenon is probably that the Rho molecule itself has carboxyl groups, and the compound 2 can compete with the ligand for coordination during the synthesis process, so that the synthesis time of the compound 2 under the condition of high concentration Rho can be prolonged. Based on this, we performed PXRD testing on compound 2 obtained at different concentrations to determine if compound 2 had not changed its structure compared to compound 1. As can be seen from the X-ray powder diffraction pattern (FIG. 7 (B)) of compound 2 synthesized in situ, the diffraction peaks of compound 2 obtained under different concentration conditions can be in one-to-one correspondence with the diffraction peaks of compound1, and the peak shape is relatively sharp even at rhodamine concentration of 2.64×10 -1 mol/L、3.30×10 -1 The mol/L of the obtained compounds 2-D and 2-E also correspond to diffraction peaks of the compound1, which indicates that the structures of the compounds 2-D and 2-E and the compound1 are not changed greatly. Based on this we selected a Rho concentration of 6.60×10 -2 And carrying out subsequent detection experiments on the compound 2-A obtained under the mol/L condition.
(3) Detection of metal cations:
detection of metal cations: is provided with 1Into 5mL glass bottles of 0.00mg of Compound 2, 3.00mL of 10 were each added - 2 Nitrate (Cd) in mol/L 2+ 、Al 3+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Co 2+ 、La 3+ 、Cr 3+ ) The solution is soaked for 12 hours at normal temperature in a sealing way, the supernatant is removed, the solution is washed by absolute ethyl alcohol and naturally dried, and solid fluorescence detection is carried out.
The solid fluorescence emission spectrum (FIG. 8 (A)), the two-part peak height (FIG. 8 (B)), and the two-part peak height ratio (FIG. 8 (C)) of compound 2-A at an excitation wavelength of 370nm after immersing in aqueous solutions of metal nitrate salts having different concentrations of 10.00mM for 12 hours are shown in the figure. From the figure, cd can be seen 2+ 、Co 2+ 、Al 3+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、La 3+ Has certain quenching effect on the fluorescence peak intensity of ligand and rhodamine fluorescence intensity in the compound 2-A, wherein Cr 3+ Quenching effect on luminescence peaks of 450nm and 580nm in compound 2-A is strongest, and Cr 3+ The quenching effect on 580nm peak is far greater than 450nm, and Cr can be specifically identified by the ratio of the intensities of the two peaks 3+ Ions. The light-emitting peak intensity at 450nm and 580nm has obvious quenching, while other metal ions have no quenching or weak quenching, and no Cr 3+ The quenching effect on MOF composite material @ Rho is obvious.
To further understand Cr 3+ Relationship between ion concentration and quenching effect. To investigate Cr with different concentrations 3+ Effect on compound 2-a. Compound 2-A at various concentrations of Cr 3+ The fluorescence intensity is along with Cr after being soaked in the ion aqueous solution for 12 hours 3+ The ion concentration was increased and gradually decreased (fig. 9 (a)). Compound 2-A is subjected to Cr with different concentrations 3+ The fluorescence intensities of the ligand and Rho portions after soaking are shown in FIG. 9 (B). Compound 2-A is subjected to Cr 3+ Powder X-ray diffraction pattern (FIG. 9 (C)) after ion soaking treatment for 12 hours shows that diffraction peaks can be in one-to-one correspondence and peak shape is sharp, which indicates that the compound 2-A passes through Cr 3+ The structure can still be kept intact after ion treatment. By the Stern-Volmer (SV) equation: i 0 /I＝1+K SV XC assay quench sensitivity, wherein I 0 And I are respectivelyIs free of Cr 3+ Fluorescence intensity and Cr in ion 3+ Fluorescence intensity, K SV For quenching efficiency, C is Cr 3+ The concentration of (2) is obtained by a curve equation SV ＝8.25×10 -1 M (FIG. 9 (D)).
(4) Detection of aldehyde vapor molecules
After the compound 2-A is respectively stood for 12 hours in aldehyde organic matter steam (valeraldehyde, hexanal, heptanal, octanal, nonanal, decanal, salicylaldehyde and benzaldehyde), the fluorescence emission spectrum of the material is shown as a graph (10A), and the graph (10C) shows that the ratio of valeraldehyde, hexanal, heptanal, octanal, nonanal and decanal to the fluorescence intensity of ligand and rhodamine in the composite material is not greatly influenced. Salicylaldehyde vapor enhances the fluorescence of the ligand in compound 2-a, rhodamine reduces the fluorescence intensity, and the relative fluorescence intensity ratio of the two increases (fig. 10 (C)); the benzaldehyde vapor showed quenching effect on both the ligand and rhodamine luminescence in compound 2-a, compared to the stronger quenching effect on rhodamine (fig. 10 (a)). Other aldehydes do not quench or quench significantly the luminescence peak intensity of compound 2-A at 450nm and 580nm, while benzaldehyde quench significantly compound 2-A.
The solid fluorescence emission spectrum of the composite material compound 2-A is detected in the benzaldehyde steam environment for different times, as shown in the graph (A) of fig. 11, when the compound 2-A is in rest for 1-2h in the benzaldehyde steam environment, the fluorescence intensity of the ligand in the compound 2-A is obviously enhanced; after standing for 4 hours, the fluorescence intensity of the ligand in the compound 2-A is the same as that of the ligand in the initial material, but the fluorescence intensity of Rho is obviously reduced, and then, the fluorescence intensity of the ligand and rhodamine in the compound 2-A is obviously reduced along with the extension of the standing time. The peak intensity of the two parts of the compound 2-A after being kept stand in the benzaldehyde steam environment for different times is obviously enhanced as shown in the graph (B) of FIG. 11, and the peak intensity ratio of the compound 2-A after being treated by the benzaldehyde steam is obviously enhanced. As can be seen from the PXRD analysis results of compound 2-A after 12 hours of standing in salicylaldehyde and benzaldehyde steam environment (FIG. 11 (C)), compound 2-A after 12 hours of standing in salicylaldehyde and benzaldehyde steam environment corresponds well to the peak form of original compound 2-A, which shows that the structure of compound 2-A after 12 hours of standing in salicylaldehyde and benzaldehyde steam environment is not changed.
The solid fluorescence emission spectrum of the compound 2-A detected in the salicylaldehyde steam environment for different times is shown in the figure 11 (D), when the compound 2-A is in rest in the benzaldehyde steam environment for 1-2 hours, the fluorescence intensity of the ligand in the compound 2-A is obviously enhanced, and the luminescence intensity of Rho is not obviously changed; after standing for 4 hours, the fluorescence intensity of the ligand part of the compound 2-A is obviously reduced, but the fluorescence intensity of Rho is not obviously changed compared with the original compound 2-A with a certain enhancement. As the standing time is prolonged, the fluorescence intensity of the ligand and Rho in the compound 2-A is not obviously changed compared with that of the compound for 4 hours.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (3)
1. The application of the MOF composite material based on the isoleucine derivative ligand is characterized in that the preparation method of the MOF composite material based on the isoleucine derivative ligand comprises the following steps:
s1, adding ethanol aqueous solution with the volume fraction of 50% into L-isoleucine and NaOH, stirring and dissolving, then adding salicylaldehyde, stirring for 2 hours at normal temperature, continuing stirring under the ice bath condition, and adding NaBH after the solution is stable 4 Stirring for 1h, regulating the pH value to 6 by using concentrated hydrochloric acid, precipitating, continuously stirring for 0.5h, carrying out suction filtration, washing by using diethyl ether and ethanol in sequence, and drying for 12h at the temperature of 65 ℃ to obtain the isoleucine derivative ligand; the molecular formula of the isoleucine derivative ligand is C 13 H 19 NO 3 The structural formula is as follows:the L-isoleucine, naOH, ethanol water solution with the volume fraction of 50%, salicylaldehyde and NaBH 4 The dosage ratio of (2) is 0.131g:0.079g:5mL:0.121g:0.041g;
s2, synthesis of MOF composite materials based on isoleucine derivative ligands: adding absolute ethanol to the isoleucine derivative ligand obtained in S1 to obtain turbid solution, and then adding Zn (NO 3 ) 2 ·6H 2 O, stirring until the mixture is clarified, obtaining a mixed solution, adding N, N-dimethylformamide and NaOH aqueous solution with the concentration of 0.05mol/L into the mixed solution after split charging, sealing, carrying out forced air drying for 3d at the temperature of 65 ℃ to obtain quadrilateral flaky crystals, washing 3 times with absolute ethyl alcohol, and carrying out forced air drying for 12h at the temperature of 65 ℃ to obtain the MOF composite material based on the isoleucine derivative ligand; isoleucine derivative ligand, absolute ethanol and Zn (NO) in the mixed solution 3 ) 2 ·6H 2 The dosage ratio of O is 400mg:100mL:600mg; the dosage ratio of the mixed solution after sub-packaging, N-dimethylformamide and the NaOH aqueous solution with the concentration of 0.05mol/L required in the preparation of the MOF material based on the isoleucine derivative ligand is 2mL: 400. Mu.L 750. Mu.L;
luo Mingdan B is added into the MOF composite material based on the isoleucine derivative ligand to obtain MOF composite material @ Rho based on the isoleucine derivative ligand, and the MOF composite material is applied to selectively identifying Cr 3+ And detecting benzaldehyde steam molecules.
2. The use of an isoleucine derivative ligand-based MOF composite according to claim 1, wherein said isoleucine derivative ligand-based MOF composite @ Rho recognizes said Cr 3+ At this time, the luminescence peak intensities at the wavelength of 450nm and 580nm were quenched.
3. The use of an isoleucine derivative ligand-based MOF composite material as claimed in claim 1, wherein said isoleucine derivative ligand-based MOF composite material @ Rho exhibits a quenching effect when recognizing said benzaldehyde vapor molecule at a wavelength of 370 nm.
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