CN114146686A - Preparation method and application of magnetic metal organic framework material - Google Patents
Preparation method and application of magnetic metal organic framework material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 42
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- 239000012924 metal-organic framework composite Substances 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 239000013144 Fe-MIL-100 Substances 0.000 claims abstract description 9
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- 239000002086 nanomaterial Substances 0.000 claims description 20
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
The invention relates to a preparation method and application of a magnetic metal organic framework material, which comprises the following steps of (a) preparing ferroferric oxide Fe by means of a solvothermal method3O4Magnetic nanoparticles and surface citric acid functionalization are carried out; (b) fe functionalized in citric acid3O4The surface of the magnetic nano-particle is coated with MIL-100(Fe) metal organic framework to obtain Fe3O4@ MIL-100(Fe) composite material and application thereof to pollutants in drinking waterThe enrichment detection of (1). The invention has the beneficial effects that: the magnetic metal organic framework composite material is successfully prepared, the synthetic method is simple, the nano composite material is complete in appearance and uniform in size, has a good core-shell structure and a large specific surface area, and can be applied to rapid and convenient enrichment detection of pollutants in drinking water by a magnetic solid-phase extraction method.
Description
Technical Field
The invention belongs to the research field of enrichment detection of pollutants in drinking water, and relates to a preparation method of a magnetic metal organic framework material and application of the magnetic metal organic framework material in sample pretreatment.
Background
With the continuous progress and development of science and technology, the safety problem of food and drinking water is more and more concerned by people. At present, contaminants in drinking water are generally chemical substances of synthetic or natural origin, and the continued long-term exposure of these contaminants can have adverse effects on the ecological environment and on human health. These contaminants come from a variety of sources, including pesticides, veterinary drugs, industrial by-products, food additives, and engineering materials, among others. Under normal conditions, pollutants in drinking water are relatively stable and are not easily decomposed, and even if the pollutants are treated by a water treatment plant, the pollutants are still difficult to completely remove from the water. Wherein the bottled drinking water has an important share in the consumer market, and has certain potential safety hazard due to the sanitary standard and low quality.
In view of the potential risk of such contaminants, the authorities in some countries have in turn issued laws and regulations to protect human health. Therefore, establishing a rapid analysis method with simple pretreatment, high sensitivity and high accuracy is crucial to ensuring the safety of drinking water, and more methods for rapidly and effectively removing pollutants in drinking water are also in force. The current common methods for removing contaminants from drinking water include coagulation-flocculation, adsorption, chlorination, electrochemical oxidation, ozonation, and photocatalytic oxidation, but the above pretreatment methods still have certain problems and drawbacks, such as cumbersome pretreatment steps, long analysis time, high price, and the need to use large amounts of organic solvents.
The pretreatment method based on magnetic solid phase extraction is considered to be the most suitable choice for removing pollutants from drinking water, because the process has the advantages of excellent removal capability, simple and convenient system operation, simple design, minimum energy consumption, high cost efficiency and the like compared with other methods. Among these, the selection of suitable adsorbent materials is a key parameter to ensure process feasibility. Metal organic framework Materials (MOFs) are a class of organic-inorganic hybrid materials, which are three-dimensional structural materials formed by the self-assembly of organic ligands and metal ions through coordination bonds. It has many excellent characteristics, and thus can be widely used in various fields. MIL-100(Fe) is a type of MOF, and MIL-100(Fe) has many properties compared to other types of MOFs, such as chemical stability, physical robustness, thermal stability, uniform and appropriate pore size, large surface area and pore volume, and the presence of unsaturated metal sites to absorb environmental contaminants, etc., and thus it can be used to enrich and detect contaminants in various environments. In addition, the MOF is relatively time-saving and labor-saving in the synthesis method, and the conditions are relatively mild, and these excellent properties make MOF a hot spot of recent research.
Disclosure of Invention
In the work, ferroferric oxide magnetic nanoparticles are used as a magnetic core and seeds for the continuous growth of a later-stage metal organic framework material, and the metal organic framework material is used as a functional surface to prepare a magnetic metal organic framework composite material Fe with a large specific surface area and a porous structure3O4@ MIL-100(Fe), simple synthetic method, intact morphology of the nano composite material, uniform size, typical core-shell structure and good chemical stability, and can be applied to enrichment detection of pollutants in drinking water. Compared with the traditional nano material, the magnetic metal organic framework material prepared by the invention has better structural stability and chemical stability, the synthetic process is simple and environment-friendly, and the sample can be subjected to rapid enrichment adsorption treatment by a magnetic solid phase extraction technology. The specific technical scheme provided by the invention is as follows:
a preparation method of a magnetic metal organic framework material comprises the following steps:
(a) preparation of ferroferric oxide Fe by means of solvothermal method3O4Magnetic nanoparticles and citric acid functionalization are carried out;
(b) in Fe3O4The surface of the magnetic nano-particle is coated with MIL-100(Fe) metal organic framework to obtain Fe3O4The @ MIL-100(Fe) composite material is applied to enrichment detection of pollutants in drinking water.
Further, the step (a) prepares the ferroferric oxide Fe by means of a solvothermal method3O4The magnetic nanoparticles and the citric acid functionalization process are as follows:
3.24g FeCl was accurately weighed3·6H2Dissolving O in 80mL of glycol, and stirring vigorously for 30min to completely dissolve the O until the O is clear and transparent. Then, adding anhydrous sodium acetate and sodium citrate under the condition of vigorous stirring, fully stirring to obtain an orange solution, then transferring the orange solution into a hydrothermal reaction kettle for reaction for 8 hours, washing a product for five times by using anhydrous ethanol to obtain citric acid functionalized ferroferric oxide Fe3O4Magnetic nanoparticles.
Further, the amounts of anhydrous sodium acetate and sodium citrate added in the step were 4.8g and 0.8g, respectively.
Further, the hydrothermal reaction temperature in the step is 200 ℃.
Further, said step (b) is carried out in Fe3O4The surface of the magnetic nano-particle is coated with MIL-100(Fe) metal organic framework to obtain Fe3O4The process of the @ MIL-100(Fe) composite material applied to the enrichment detection of pollutants in drinking water is as follows:
(1)Fe3O4preparation of @ MIL-100(Fe) nanomaterial precursor: accurately weigh 0.10g citric acid functionalized Fe3O4Magnetic nanoparticles in 5mL FeCl3·6H2Dispersing in ethanol O solution for 15min, then magnetically separating and washing with ethanol 3 times. Secondly, dispersing the Fe-Fe3O4@ MIL-100(Fe) precursor;
(2)Fe3O4preparation of @ MIL-100(Fe) nano material: mixing Fe3O4@ MIL-100(Fe) nanomaterial precursor dispersed in 60mL FeCl3·6H2O and trimesic acid in ethanol solution, then transferring the solution into a hydrothermal reaction kettle for reaction for 24 hours, washing the product with absolute ethyl alcohol for three times, and then drying the product in vacuumDrying for 12h to obtain Fe3O4@ MIL-100(Fe) nanomaterial;
(3) and (3) enriching and detecting the pollutants: using the Fe obtained above3O4The @ MIL-100(Fe) magnetic composite nano material is used as an adsorbent, added into a sample solution to be detected containing a target substance, vibrated for 60min, subjected to magnetic separation to remove supernatant, added with an eluant to the obtained mixed material to recover the target substance, and subjected to ultraviolet spectrometry.
Further, FeCl in the step (1)3·6H2The contents of O and trimesic acid are 0.027g and 0.021g respectively.
Further, the temperature of the dispersion in the step (1) is 70 ℃.
Further, FeCl in the step (2)3·6H2The contents of O and trimesic acid were 0.27g and 0.21g, respectively.
Further, the hydrothermal reaction temperature in the step (2) is 70 ℃.
Further, the application of the invention is the prepared Fe3O4The @ MIL-100(Fe) nano material is used as a pretreatment material of pollutants in drinking water, and can adsorb, enrich and detect the pollutants in the drinking water by a magnetic solid-phase extraction method.
The existing methods for adsorbing and removing pollutants have certain problems and defects. The process of synthesizing materials in the method reported at present is complicated, time-consuming and labor-consuming, and a large amount of organic solvent is used, so that the method does not conform to the green chemical concept advocated at present. Meanwhile, since the materials synthesized by the reported methods have no magnetism, the solid phase extraction technique is required, the step of passing through the column is time-consuming, and complicated operations such as filtration and centrifugation are required. Therefore, the magnetic metal organic framework composite material synthesized by the method can perfectly solve the problems of the method.
The invention has the beneficial effects that:
(1) the magnetic metal organic framework material is successfully prepared, the synthetic method is simple, the nano composite material is complete in shape and uniform in size, has a good core-shell structure and a large specific surface area, and can be applied to enrichment detection of pollutants in drinking water.
(2) Compared with the traditional nano material, the magnetic metal organic framework material prepared by the invention has better structural stability and chemical stability, the synthetic process is simple and environment-friendly, and the sample can be subjected to rapid enrichment adsorption treatment by a magnetic solid phase extraction technology.
Description of the drawings:
FIG. 1: scanning electron microscope and transmission electron microscope images of magnetic metal organic framework composite material
FIG. 2: elemental composition characterization of magnetic metal organic framework composites
FIG. 3: characterization of crystal structure of magnetic metal-organic framework composite material
FIG. 4: characterization of specific surface area of magnetic metal-organic framework composite materials
Detailed Description
In order that the above features and advantages of the present invention will be readily understood and appreciated, embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
Example 1
A preparation method and application of a magnetic metal organic framework material comprise the following steps:
(1) preparation of ferroferric oxide Fe by means of solvothermal method3O4Magnetic nanoparticles and citric acid functionalization are carried out;
3.24g FeCl was accurately weighed3·6H2Dissolving O in 80mL of glycol, and stirring vigorously for 30min to completely dissolve the O until the O is clear and transparent. Then, adding 4.8g of anhydrous sodium acetate and 0.8g of sodium citrate under the condition of vigorous stirring, fully stirring to obtain an orange solution, then transferring the orange solution into a hydrothermal reaction kettle, reacting for 8 hours at the temperature of 200 ℃, washing a product for five times by using anhydrous ethanol to obtain citric acid functionalized ferroferric oxide Fe3O4Magnetic nanoparticles.
(2) Fe functionalized in citric acid3O4The surface of the magnetic nano-particle is coated with MIL-100(Fe) metal organic framework to obtain Fe3O4@ MIL-100(Fe) composite material and is applied to the enrichment detection of bisphenol A in drinking water.
(1)Fe3O4Preparation of @ MIL-100(Fe) nanomaterial precursor: accurately weigh 0.10g citric acid functionalized Fe3O4Magnetic nanoparticles dispersed in 5mL FeCl at 70 deg.C3·6H2O (0.027g) in ethanol for 15min, then separated magnetically and washed 3 times with ethanol. Secondly, it was dispersed in 30mL of an ethanol solution of trimesic acid (0.021g) at 70 ℃ for 30min, then subjected to magnetic separation and washed with ethanol 3 times to obtain Fe3O4@ MIL-100(Fe) precursor;
(2)Fe3O4preparation of @ MIL-100(Fe) nano material: mixing Fe3O4@ MIL-100(Fe) nanomaterial precursor dispersed in 60mL FeCl3·6H2O (0.27g) and trimesic acid (0.21g) in ethanol solution, then transferring the solution into a hydrothermal reaction kettle, reacting for 24h at 70 ℃, washing the product with absolute ethyl alcohol for three times, and drying in vacuum for 12h to obtain Fe3O4@ MIL-100(Fe) nanomaterial;
(3) and (3) enrichment detection of bisphenol A: using the Fe obtained above3O4The @ MIL-100(Fe) magnetic composite nano material is used as an adsorbent, added into a to-be-detected sample solution containing bisphenol A, vibrated for 60min, subjected to magnetic separation to remove supernatant, added with an eluent to recover the bisphenol A, and subjected to ultraviolet spectrometry.
Example 2
The steps and the method of the preparation method of the magnetic metal organic framework material are basically the same as the steps and the method of the embodiment 1, and the difference is that the applied sample solution to be detected is a sulfonamide veterinary drug.
Example 3
The preparation method and the application of the magnetic metal organic framework material are basically the same as the steps and the method in the embodiment 1, and the difference is that the applied sample solution to be detected is biotoxin.
FIG. 1 is a scanning electron microscope image and a transmission electron microscope image of the magnetic metal organic framework composite material, which show that the prepared framework material has a good core-shell structure, uniform particle size, and a size of about 150nm, and is suitable for being used as an adsorbing material.
Fig. 2 is a representation of the element composition of the magnetic metal organic framework composite material, which shows that the prepared nano material mainly contains three elements of Fe, C and O, does not need excessive organic chemical reagents in the synthesis process, and accords with the green chemical concept.
FIG. 3 is a crystal structure characterization of the magnetic metal organic framework composite material, which shows that the prepared nano material is made of Fe3O4And MIL-100(Fe), and has stable crystal structure and good chemical stability.
Fig. 4 is a specific surface area test of the magnetic metal organic framework composite material, which shows that the prepared magnetic framework material has a larger specific surface area and is suitable for being used as an adsorption material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a magnetic metal organic framework material comprises the following steps:
(a) preparation of ferroferric oxide Fe by means of solvothermal method3O4Magnetic nanoparticles and citric acid functionalization are carried out;
(b) functionalization of Fe in citric acid3O4The surface of the magnetic nano-particle is coated with MIL-100(Fe) metal organic framework to obtain Fe3O4The @ MIL-100(Fe) composite material is applied to enrichment detection of pollutants in drinking water.
2. The method for preparing a magnetic metal organic framework composite material according to claim 1, wherein the step (a) is to prepare Fe ferroferric oxide by a solvothermal method3O4The magnetic nanoparticles and the citric acid functionalization process are as follows:
3.24g FeCl was accurately weighed3·6H2Dissolving O in 80mL of glycol, and stirring vigorously for 30min to completely dissolve the O until the O is clear and transparent. Then, adding anhydrous sodium acetate and sodium citrate under the condition of vigorous stirring, fully stirring to obtain an orange solution, then transferring the orange solution into a hydrothermal reaction kettle for reaction for 8 hours, washing a product for five times by using anhydrous ethanol to obtain citric acid functionalized ferroferric oxide Fe3O4Magnetic nanoparticles.
3. The method of claim 2, wherein the amount of anhydrous sodium acetate and sodium citrate added in the step is 4.8g and 0.8g, respectively.
4. The method for preparing a magnetic metal organic framework material according to claim 2, wherein the hydrothermal reaction temperature in the step (1) is 200 ℃.
5. The method of claim 1, wherein step (b) is performed with Fe3O4The surface of the magnetic nano-particle is coated with MIL-100(Fe) metal organic framework to obtain Fe3O4The process of the @ MIL-100(Fe) composite material applied to the enrichment detection of pollutants in drinking water is as follows:
(1)Fe3O4preparation of @ MIL-100(Fe) nanomaterial precursor: accurately weigh 0.10g citric acid functionalized Fe3O4Magnetic nanoparticles in 5mL FeCl3·6H2Dispersing in O ethanol solution for 15min, magnetically separating, and washing with ethanol for 3 times; secondly, dispersing the Fe-Fe3O4@ MIL-100(Fe) precursor;
(2)Fe3O4preparation of @ MIL-100(Fe) nano material: mixing Fe3O4@ MIL-100(Fe) nanomaterial precursor dispersed in 60mL FeCl3·6H2Of O and trimesic acidTransferring the solution into an ethanol solution, reacting for 24 hours in a hydrothermal reaction kettle, washing the product with absolute ethyl alcohol for three times, and drying in vacuum for 12 hours to obtain Fe3O4@ MIL-100(Fe) nanomaterial;
(3) enriching and detecting pollutants in drinking water: using the Fe obtained above3O4The @ MIL-100(Fe) magnetic composite nano material is used as an adsorbent, added into a sample solution to be detected containing a target substance, vibrated for 60min, subjected to magnetic separation to remove supernatant, added with an eluant to the obtained mixed material to recover the target substance, and subjected to ultraviolet spectrometry.
6. The method of claim 5, wherein FeCl is added in the step (1)3·6H2The contents of O and trimesic acid are 0.027g and 0.021g respectively.
7. The method for preparing a magnetic metal organic framework material according to claim 5, wherein the temperature for dispersing in the step (1) is 70 ℃.
8. The method of claim 5, wherein FeCl is added in the step (2)3·6H2The contents of O and trimesic acid were 0.27g and 0.21g, respectively.
9. The method according to claim 5, wherein the hydrothermal reaction temperature in step (2) is 70 ℃.
10. The method for preparing a magnetic metal-organic framework material according to claim 5, wherein the eluent used in the step (3) is methanol/acetic acid (v/v,40: 1).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115254071A (en) * | 2022-08-04 | 2022-11-01 | 华侨大学 | Magnetic metal organic framework composite material and preparation method and application thereof |
| CN115805063A (en) * | 2022-11-29 | 2023-03-17 | 浙江大学 | Multifunctional porous core-shell composite nano material and preparation method thereof |
| TWI835609B (en) | 2023-03-24 | 2024-03-11 | 長庚大學 | A modified magnetic iron metal organic framework, its preparation method and an electrochemical sensing set |
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| CN115254071A (en) * | 2022-08-04 | 2022-11-01 | 华侨大学 | Magnetic metal organic framework composite material and preparation method and application thereof |
| CN115805063A (en) * | 2022-11-29 | 2023-03-17 | 浙江大学 | Multifunctional porous core-shell composite nano material and preparation method thereof |
| TWI835609B (en) | 2023-03-24 | 2024-03-11 | 長庚大學 | A modified magnetic iron metal organic framework, its preparation method and an electrochemical sensing set |
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