CN110240707B - Post-modified metal-organic framework material for detecting iron ions and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a post-modified metal-organic framework material for detecting iron ions, and a preparation method and application thereof. The metal-organic framework material is metal ion Tb3+The metal-organic framework material Tb-HIA is prepared by taking 5-hydroxyisophthalic acid as an organic connecting ligand through a hydrothermal method, and is obtained by post-modifying Tb-HIA with acryloyl chloride, wherein the metal-organic framework material Tb-HIA has a chemical formula: [ M ] Am(L)n·(H2O)q(NO3)]Wherein L is 5-hydroxyisophthalic acid, M is a metal ion Tb3+(ii) a And m, n and q are the numbers of metal ions, organic linking ligands and water molecules respectively, wherein m is 1, n is 1 and q is 5. The material provided by the invention has high selectivity for detecting ferric ions, and can be used as a fluorescent probe for detecting the ferric ions; the preparation method disclosed by the invention is simple in preparation process, environment-friendly, low in cost and easy for large-scale preparation.
Description
Technical Field
The invention relates to the field of metal-organic framework materials, in particular to a post-modified metal-organic framework material for detecting iron ions and a preparation method and application thereof.
Background
Iron is one of essential elements of the human body, and as a metal commonly existing in cells, it plays an important role in various cellular functions, such as electron transfer in RNA and DNA synthesis and oxygen metabolism. However, excess and deficiency of iron in the human body can lead to various biological diseases, such as hereditary pigmentation, liver cirrhosis, anemia, etc., and only normal iron content can ensure the health of the human body. Therefore, the development of effective, high-sensitivity and specific iron ion probe materials has important guiding significance in clinic and biomedical science.
However, designing and synthesizing a detection technology that has high selectivity, high sensitivity and can effectively recognize iron ions is still a very challenging issue at present. Through the diligent efforts of scientists, traditional iron ion detection methods such as an atomic absorption method, a polarography method, a potassium dichromate method, a volumetric method, a spectrophotometry and the like are formed, but the methods are discovered to have the defects of complex operation, low sensitivity, incapability of detecting trace iron and the like. To realize to Fe3+Highly sensitive, selective and accurate detection of ions, many based on fluorescence and colorimetric detection of Fe3+The method of (2) is established. However, at present, most of fluorescent probe materials for iron ion recognition are really applied to real production life, and scientists need to solve the following problems:
1. some reported probe materials are often limited by other heavy metal ions, such as Cu2+，Al3+And Cr3+The interference to the identification process is avoided, the design and the simple and convenient preparation specificity are not slow, and the method has important significance;
2. most of small molecular probes can only be applied to an organic solvent system or an organic/water mixed system, but cannot be applied to a pure water system, so the development of probes capable of detecting iron ions in the pure water system is still to be improved in the current research;
3. the action mechanism of most of the iron ion probes with high selectivity is not completely clear at present.
Disclosure of Invention
One of the purposes of the invention is to provide a post-modified metal-organic framework material for detecting iron ions, which is low in price and can specifically detect the iron ions.
The invention also aims to provide a preparation method of the post-modified metal-organic framework material for detecting iron ions, which has a simple process and can be produced in a large scale.
In order to realize one of the purposes, the invention adopts the technical scheme that: post-modified metal-organic framework for detecting iron ionsMaterial of metal ion Tb3+As node, 5-hydroxyisophthalic acid (H)2HIA) is an organic linking ligand, a metal-organic framework material Tb-HIA is prepared by a hydrothermal method, and the Tb-HIA is post-modified by acryloyl chloride to obtain a three-dimensional metal-organic framework material Tb-HIAAC;
the reaction formula is as follows:
Tb3++H2HIA→Tb-HIA
the chemical formula of the metal-organic framework material Tb-HIA is as follows: [ M ] Am(L)n·(H2O)q(NO3)]In the formula (I), wherein,
l is an organic linking ligand H2HIA, 5-hydroxyisophthalic acid, the structural formula of which is shown in formula I;
m is a metal ion Tb3+；
And m, n and q are the numbers of metal ions, organic linking ligands and water molecules respectively, wherein m is 1, n is 1 and q is 5.
In order to achieve the second purpose, the invention adopts the technical scheme that: a preparation method of post-modified metal-organic framework material for detecting iron ions comprises the following steps:
s1, mixing the components according to a molar ratio of 1: 1.4-1.6 respectively weighing soluble salts of 5-hydroxyisophthalic acid and terbium, placing the soluble salts into a glass sample bottle, adding water as a solvent, adding sodium hydroxide to adjust the pH of the system to 8-9, and uniformly stirring;
s2, placing the glass sample bottle in a hydro-thermal synthesis reaction kettle, and carrying out heat preservation reaction for 72-75 h at the temperature of 110-112 ℃;
s3, cooling to obtain colorless blocky crystals after the reaction is finished, and then sequentially filtering, washing and drying in the air to obtain the metal-organic framework material Tb-HIA;
s4, dropwise adding acryloyl chloride into the anhydrous dichloromethane solution of Tb-HIA, dropwise adding triethylamine to adjust the pH value of the system to 8-9 after all the acryloyl chloride is completely dripped, stirring at room temperature overnight, and obtaining a colorless product after the reaction is finished; filtering, washing and drying in the air to obtain the metal-organic framework material Tb-HIAAC.
Preferably, the molar ratio of the soluble salt of 5-hydroxyisophthalic acid and terbium is 1: 1.5.
preferably, the soluble salt of terbium is terbium nitrate hexahydrate.
Preferably, in step S4, the mass-to-volume ratio of Tb-HIA to acryloyl chloride is 54: 0.05 g/mL.
Preferably, in step S3, the washing condition is washing with water for 3 to 5 times.
Preferably, in step S4, the washing condition is washing with dichloromethane for 3 to 5 times.
The chemical reaction equation for preparing Tb-HIAAC is as follows:
the invention also aims to provide application of the post-modified metal-organic framework material for detecting iron ions.
The metal-organic framework material provided by the invention can be used as a fluorescent probe and is applied to the specific detection of ferric ions in aqueous solution.
Because Metal-organic Frameworks (MOFs) are formed by self-assembly of Metal ions and organic linkers through coordination bonds, a fluorescence function is easily introduced through the Metal ions, ligands or guest molecules and the like. The method comprises the steps of expanding the design range of an iron ion recognition material by adopting a ligand which is rich in hydroxyl and has dicarboxylic acid groups as coordination sites, carrying out one-step hydrothermal reaction on the ligand and terbium ions to obtain a metal-organic framework material, carrying out post-modification on the metal-organic framework material rich in hydroxyl by using acryloyl chloride to obtain a three-dimensional and macroporous metal-organic framework material with acrylate groups, wherein the material can stably exist in an aqueous solution and has a fluorescence emission peak based on rare earth ions, so that the detection of the iron ions by the metal-organic framework material in a fluorescence quenching mode can be realized, and the specificity of the detection of the iron ions is embodied in alkali metals, alkaline earth metals, transition metals and other heavy metal ions.
The starting raw materials used in the invention are low in price and environment-friendly, and the used ligand can be synthesized by a simple method, has high yield, stable chemical properties, simple preparation process and low cost, and is easy for large-scale preparation.
Drawings
FIG. 1 is a structural diagram of a metal-organic framework material Tb-HIA prepared in example 1 of the present invention;
fig. 2 is a structural view of a metal-organic framework material Tb-HIAAC prepared in example 2 of the present invention;
FIG. 3 is a fluorescence titration chart of the detection process of iron ions by the metal-organic framework material prepared in example 2 of the present invention;
FIG. 4 is a bar graph of the experimental selection of iron ions by the metal-organic framework material prepared in example 2 of the present invention;
FIG. 5 is a PXRD diagram of the iron ion detection mechanism of the metal-organic framework material prepared in example 2 of the present invention;
FIG. 6 is an infrared spectrum of the detection mechanism of iron ions by the metal-organic framework material prepared in example 2 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
The starting materials and reagents used in the following examples are all conventional commercial products unless otherwise specified.
Example 1: synthesis of metal-organic framework material Tb-HIA
5.5mg of 5-hydroxyisophthalic acid (H) are weighed2HIA)(0.03mmol)，20mg Tb(NO3)3·6H2O (0.045mmol) is put into a 10mL glass sample bottle, 2mL water is added as a solvent, and thenAdding sodium hydroxide to adjust the pH value of the system to 8-9, placing a glass sample bottle into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle into an electric heating air blowing drying oven, keeping the temperature at 110 ℃, reacting for 72 hours, cooling after the reaction is finished to obtain colorless blocky crystals, filtering, collecting, washing with water for 3-5 times, and drying in the air to obtain the metal-organic framework material Tb-HIA, wherein the yield is as follows: 94 percent. C8H14NO13Tb: 19.56% of C, 2.87% of H and 42.35% of O; found is C19.57%, H2.90% and O42.33%. As shown in FIG. 1, the 1-dimensional chain formed by 5-hydroxyisophthalic acid and Tb forms a 2-position layered structure through the accumulation of nitrate and pi … pi.
Example 2: synthesis of metal-organic framework material Tb-HIAAC
Adding 54mg of Tb-HIA into 5mL of anhydrous dichloromethane, then dropwise adding 0.05mL of acryloyl chloride (purity is 96%), dropwise adding triethylamine to adjust the pH value of the system to 8-9 after all the components are completely added, stirring the obtained mixture at room temperature overnight after all the components are completely added, and obtaining a colorless product after the reaction is finished. And (3) filtering, collecting, washing with dichloromethane for 3-5 times, and drying in air to obtain the metal-organic framework material Tb-HIAAC with the yield of 75%. The structure is shown in FIG. 2, and the structure that partial hydroxyl groups on Tb-HIA are modified by acetyl chloride can be seen.
Detection experiment for iron ions
Weighing Tb-HIAAC as the material in example 2, preparing a standard suspension of 0.20mM water, putting 3mL of the suspension in a quartz cuvette, and sequentially dropwise adding 0.02M iron ion Fe3+In the aqueous solution, until the fluorescence intensity did not change any more, the total iron ion concentration was 0.2mM and the excitation wavelength was 305nm, and the fluorescence emission peaks at 491nm,545nm,586nm and 622nm were recorded. The results are shown in FIG. 3, and it can be seen that Fe is associated with iron ion3+The fluorescence of Tb-HIAAC is remarkably quenched with the increase of the concentration, and the quenching degree reaches 98%.
Selectivity test for iron ion
In the selectivity test experiment, 3mL of probe standard suspension is taken to be put into a quartz cuvette, and other ions (Ag) are added+,Li+,Na+,K+,Ca2+,Ba2+,Sr2+,Mg2+,Mn2+,Cd2+,Co2+,Hg2+,Fe2+,Ni2+,Al3+,Cr3+,Zn2+,Cu2+,Pb2+)0.2mM, excited at 305nm, and the change of fluorescence intensity thereof was measured, with the metal ion species as abscissa and the relative fluorescence intensity as ordinate, to obtain a selectivity graph. Then adding 0.2mM of iron ions Fe into the solution3+The solution, also excited at 305nm, was tested for fluorescence intensity changes to obtain a competition graph, and the results are shown in FIG. 4, where other selected cations can be seen for Fe3+Has no influence on the detection, and shows that Tb-HIAAC has no influence on Fe3+Has good specificity.
Research on iron ion detection mechanism
2 parts of the material from example 2, 5mg, were weighed out and 0.3mM Fe ion added to one part3+The solution was stirred for 5 minutes, another portion was untreated, filtered, and the filter cake was subjected to PXRD test and infrared spectroscopy (IR) test. The results are shown in FIGS. 5 and 6, respectively. As can be seen from fig. 5, the PXRD pattern of the sample with Tb-HIAAC adsorbing iron ions shows several new peaks compared to the original sample, which indicates that there may be new species generated, but the overall skeleton structure is maintained; as can be seen from fig. 6, compared with Tb-HIAAC, the stretching vibration peak of C ═ O in the infrared spectrum adsorbing iron ions undergoes a significant red shift, indicating that C ═ O and iron ions undergo coordination, and by integrating PXRD and IR spectrum, it is indicated that Tb-HIAAC detects iron ions because Tb-HIAAC coordinates iron ions through carbonyl groups and iron ions.
Example 3: synthesis of metal-organic framework material Tb-HIAAC
5.5mg of 5-hydroxyisophthalic acid (H) are weighed2HIA)(0.03mmol)，19mg Tb(NO3)3·6H2Adding O (0.042mmol) into a 10mL glass sample bottle, adding 2mL water as a solvent, adding sodium hydroxide to adjust the pH of the system to 8-9, placing the glass sample bottle into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle into an electric heating air drying oven, and keeping the temperature at 110 DEG CReacting for 72 hours, cooling to obtain colorless blocky crystals after the reaction is finished, filtering and collecting, washing for 3-5 times by using water, and drying in the air to obtain the metal-organic framework material Tb-HIA, wherein the yield is as follows: 90%, the structure is the same as that of example 1.
Adding 54mg of Tb-HIA into 5mL of anhydrous dichloromethane, then dropwise adding 0.05mL of acryloyl chloride (with the purity of 96%) into the anhydrous dichloromethane, dropwise adding triethylamine into the anhydrous dichloromethane after all the acryloyl chloride is completely dropwise added to adjust the pH value of the system to be 8-9, stirring the obtained mixture at room temperature after all the acryloyl chloride is completely dropwise added, standing overnight, and obtaining a colorless product after the reaction is finished. The metal-organic framework material Tb-HIAAC is prepared by filtering, collecting, washing with dichloromethane for 3-5 times, and drying in air, wherein the yield is 73%, and the structure is the same as that of example 2.
Example 4: synthesis of metal-organic framework material Tb-HIAAC
5.5mg of 5-hydroxyisophthalic acid (H) are weighed2HIA)(0.03mmol)，21.7mg Tb(NO3)3·6H2Adding 2mL of water as a solvent into 10mL of O (0.048mmol) in a glass sample bottle, adding sodium hydroxide to adjust the pH value of the system to be 8-9, placing the glass sample bottle in a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in an electrothermal blowing drying oven, keeping the temperature at 112 ℃, reacting for 75 hours, cooling to obtain colorless blocky crystals after the reaction is finished, filtering and collecting, washing with water for 3-5 times, and drying in the air to obtain a metal-organic framework material Tb-HIA, wherein the yield is as follows: 91%, the structure is the same as example 1.
Adding 54mg of Tb-HIA into 5mL of anhydrous dichloromethane, then dropwise adding 0.05mL of acryloyl chloride (purity is 96%), dropwise adding triethylamine to adjust the pH value of the system to 8-9 after all the components are completely added, stirring the obtained mixture at room temperature overnight after all the components are completely added, and obtaining a colorless product after the reaction is finished. Filtering and collecting, washing 3-5 times by using dichloromethane, and drying in the air to prepare the metal-organic framework material Tb-HIAAC with the yield of 76%, wherein the structure is the same as that of example 2.
Claims (7)
1. A post-modified metal-organic framework material for detecting iron ions is characterized in that metal ions Tb are used3+As a node, with 5-hydroxym-phenylenediFormic acid is used as an organic linking ligand, a metal-organic framework material Tb-HIA is prepared by a hydrothermal method, and the Tb-HIA is subjected to post-modification by using acryloyl chloride to prepare the metal-organic framework material Tb-HIA; the chemical formula of the metal-organic framework material Tb-HIA is as follows: [ M ] Am(L)n·(H2O)q(NO3)]Wherein L is 5-hydroxyisophthalic acid radical, M is metal ion Tb3+(ii) a m, n and q are the number of metal ions, organic linking ligands and water molecules respectively, wherein m =1, n =1, q = 5; the preparation method comprises the following specific steps:
s1, mixing the components according to a molar ratio of 1: 1.4-1.6 respectively weighing soluble salts of 5-hydroxyisophthalic acid and terbium, placing the soluble salts into a glass sample bottle, adding water as a solvent, adding sodium hydroxide to adjust the pH of the system to 8-9, and uniformly stirring;
s2, placing the glass sample bottle in a hydro-thermal synthesis reaction kettle, and carrying out heat preservation reaction for 72-75 h at the temperature of 110-112 ℃;
s3, cooling to obtain colorless blocky crystals after the reaction is finished, and then sequentially filtering, washing and drying in the air to obtain the metal-organic framework material Tb-HIA;
s4, dropwise adding acryloyl chloride into the anhydrous dichloromethane solution of Tb-HIA, dropwise adding triethylamine to adjust the pH value of the system to 8-9 after all the acryloyl chloride is completely dripped, stirring at room temperature overnight, and obtaining a colorless product after the reaction is finished; filtering, washing and drying in the air to obtain the metal-organic framework material Tb-HIAAC.
2. The post-modified metal-organic framework material for detecting iron ions of claim 1, wherein in step S1, the molar ratio of the soluble salt of 5-hydroxyisophthalic acid and terbium is 1: 1.5.
3. the class of post-modified metal-organic framework materials for detecting iron ions of claim 1, wherein the soluble salt of terbium is terbium nitrate hexahydrate.
4. The post-modified metal-organic framework material for detecting iron ions according to claim 1, wherein in step S4, the mass-to-volume ratio of Tb-HIA to acryloyl chloride is 54: 0.05 g/mL.
5. The post-modified metal-organic framework material for detecting iron ions according to claim 1, wherein in step S3, the washing condition is washing with water for 3-5 times.
6. The post-modified metal-organic framework material for detecting iron ions according to claim 1, wherein in step S4, the washing condition is washing with dichloromethane for 3-5 times.
7. Use of a class of post-modified metal-organic framework materials for the detection of ferric ions according to any one of claims 1 to 6 as a fluorescent probe for the detection of ferric ions in aqueous solutions.
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