CN115970656A - Amino acid covalent grafting cyclodextrin-metal organic framework material and application thereof - Google Patents
Amino acid covalent grafting cyclodextrin-metal organic framework material and application thereof Download PDFInfo
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Abstract
The invention discloses an amino acid covalent grafting cyclodextrin-metal organic framework material and application thereof, wherein the amino acid covalent grafting cyclodextrin-metal organic framework material can efficiently adsorb heavy metal, has high adsorption capacity and good heavy metal removing effect, can be recycled, and has good stability in water through carbonization.
Description
Technical Field
The invention relates to the technical field of adsorption material preparation, and particularly relates to an amino acid covalent grafting cyclodextrin-metal organic framework material and application thereof.
Background
In recent years, metal organic framework materials are porous materials that have been developed more rapidly and have received much attention in recent years. Compared with the traditional porous material, the porous material consisting of the organic ligand and the inorganic metal has the following remarkable characteristics: (1) has a high specific surface area; (2) By changing the types of metal ions and organic ligands, the internal pore structure and surface functional groups can be conveniently and flexibly regulated; (3) The metal ions and organic ligands with high porosity and open framework structure, which are completely exposed on the surface/pore channel, can provide 100% utilization rate. These performance advantages have made such novel porous materials to show great potential for development in the field of adsorption.
At present, methods for removing heavy metals in a system include a chemical precipitation method, an ion exchange method, an adsorption method and a reverse osmosis method, and the methods may cause secondary pollution to the system, have low efficiency or have poor effect on removing low-concentration metal ions. The adsorption method is a simple, economic and environment-friendly treatment method, but the core problem is to find an adsorbent which is suitable for a system and is efficient and environment-friendly.
The cyclodextrin-metal organic framework is derived from cyclodextrin and alkali metal cations, and constitutes a porous renewable and edible green metal organic framework material, and the expanded structure of the cyclodextrin-metal organic framework material shows strong crystallinity, permanent porosity and excellent biocompatibility. Because the expanded porous skeleton can adsorb guest molecules including gas, drugs, metal-based nanoclusters and nanoparticles, the cyclodextrin-metal organic framework has potential application prospects in the fields of template synthesis, adsorption and separation of metal nanoparticles and gel, capture of high-activity intermediates, catalyst carriers, sensing, electric memory, drug delivery, food and the like. However, the cyclodextrin organic framework has low selective adsorption on heavy metals and poor water stability.
Heavy metals in grease are difficult to remove, and the treatment effect is limited by adsorption treatment with activated carbon, clay and the like.
Disclosure of Invention
The invention aims to provide an amino acid covalent grafting cyclodextrin-metal organic framework material and application thereof, which can efficiently adsorb heavy metal, have high adsorption capacity, good heavy metal removal effect, reusability and good stability.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an amino acid covalent grafting cyclodextrin-metal organic framework material is prepared by the following method:
(1) Dissolving amino acid and potassium hydroxide in water, and stirring and incubating at 40-80 deg.C for 20min-2h to obtain a first mixed solution; uniformly mixing the first mixed solution and a cyclodextrin aqueous solution in equal volume to obtain a second mixed solution, wherein the molar ratio of cyclodextrin to potassium hydroxide is 1;
(2) And filtering the second mixed solution (preferably a 0.45-micron membrane), placing the filtrate in an alcohol gas atmosphere or adding an alcohol solution, standing at room temperature until crystals grow out after pretreatment, centrifuging (preferably 10000rpm for 5 min), washing precipitates, and drying (preferably methanol for 3 times, and then drying in vacuum at 60 ℃ for 12 h) to obtain the amino acid covalent grafting cyclodextrin-metal organic framework composite material.
On the basis of inheriting the porous structure of a metal organic framework, functional groups on amino acid are combined and utilized to synthesize an amino acid covalent grafting cyclodextrin-metal organic framework composite material which is applied to repairing heavy metal polluted water; solves the problems of slow synthesis speed of cyclodextrin-metal organic framework, low efficiency of heavy metal adsorption and water instability.
Preferably, in step (1), the amino acid is selected from one or more of L-tyrosine, aspartic acid and cysteine; the molar ratio of the amino acid to the potassium hydroxide is 1-1.
Preferably, in the step (1), the concentration of potassium hydroxide in the first mixed solution is 0.1 to 0.8mol/L.
Preferably, in the step (1), the cyclodextrin concentration of the cyclodextrin aqueous solution is 0.025-0.1mol/L, and the cyclodextrin comprises alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
Preferably, in the step (2), the alcohol in the alcohol gas atmosphere or the alcohol solvent is selected from one or two of methanol and ethanol, and after the filtrate is added to the alcohol solvent to form the second mixed solution-alcohol mixed solution, the volume concentration of the alcohol in the second mixed solution-alcohol mixed solution is 30-40%.
Preferably, in the step (2), the pretreatment is one or a combination of solvent heat treatment, ultrasonic treatment and microwave treatment; the temperature of the solvent heat treatment is 40-60 ℃, and the time is 12-24h; the ultrasonic frequency of the ultrasonic treatment is 30-40kHz, the ultrasonic time is 1-4h, and the temperature is controlled to be 40-60 ℃ during ultrasonic treatment; the microwave power of the microwave treatment is 400-600W, the microwave time is 5-20min, and the temperature is controlled to be 50-90 ℃ during the microwave treatment.
In the step (2), adding a size regulator into the pretreated second mixed solution, wherein the size regulator is selected from one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP) and methanol; wherein the amount of polyethylene glycol is 0.01-0.1 times (preferably 0.03 times) of the amount of cyclodextrin, the amount of polyvinylpyrrolidone is 0.005-0.05 times (preferably 0.01 times) of the amount of cyclodextrin, and the amount of methanol is 15% -50%, preferably 20% of the volume of the second mixed solution.
The application of the amino acid covalent grafting cyclodextrin-metal organic framework material in the preparation of the heavy metal adsorbent is that when the amino acid covalent grafting cyclodextrin-metal organic framework material adsorbs heavy metals in organic liquid, the addition amount is 0.1-2g/L, and the preferable addition amount is 0.5-1g/L. The adsorption is carried out at the temperature of 25 ℃ and the rpm of 300, and the adsorption effect on cadmium, chromium and arsenic is more obvious and more economic. The amino acid covalent grafting cyclodextrin-metal organic framework material is dissolved and disintegrated in water, cannot play a role in adsorbing heavy metals, is stable in an organic system, is particularly suitable for removing the heavy metals in the organic system, is safe, environment-friendly and easy to recover, and is particularly suitable for removing the heavy metals in food oil, such as euphausia superba oil, peanut oil, rapeseed oil, palm oil and the like. The heavy metal ions are cadmium, mercury, chromium, arsenic and lead, but are not limited to the 5 heavy metals.
The amino acid covalent grafting cyclodextrin-metal organic framework derived carbon material is obtained by calcining the amino acid covalent grafting cyclodextrin-metal organic framework material in air or nitrogen for carbonization, and the calcining conditions are as follows: heating to 200-500 deg.C at a rate of 0.5-5 deg.C/min, and calcining for 2-5h. When the temperature rise rate is controlled to be in the range of 0.5-5 ℃/min, the organic gas is slowly released, so that the amino acid covalent grafting cyclodextrin-metal organic framework can be maintained, and a large specific surface area (11.4 m) can be obtained 2 /g) and a large number of nano-pore (2.3 nm) carbon materials, and furthermore, a large retention of oxygen-containing functional groups. According to the invention, the amino acid covalent grafting cyclodextrin-metal organic framework is carbonized, so that the structure of the composite material in water is stable, heavy metals in water can be effectively removed, and the composite material is convenient to recover.
The use method of the amino acid covalent grafting cyclodextrin-metal organic framework derived carbon material comprises the following steps: placing the amino acid covalent grafting cyclodextrin-metal organic framework derived carbon material in a water phase heavy metal solution, and adsorbing at the conditions of 25 ℃, pH3-7 and 300 rpm; the heavy metals in the water phase comprise cadmium, chromium, mercury, arsenic and lead; the addition amount of the amino acid covalent grafting cyclodextrin-metal organic framework derived carbon material in the aqueous phase heavy metal solution is 0.1-2g/L. The addition amount of the amino acid covalent grafting cyclodextrin-metal organic framework derived carbon material in the organic liquid is 0.1-2g/L, preferably 0.5-1g/L, the pH value is 6-7, and the adsorption effect on cadmium, chromium and arsenic is more remarkable and more economical.
The invention has the beneficial effects that: amino acid is derived on the basis of a cyclodextrin-metal organic framework, so that groups on the surface of the cyclodextrin-metal organic framework are enriched, and the cyclodextrin-metal organic framework has high-efficiency adsorption capacity for different heavy metals; the amino acid covalent grafting cyclodextrin-metal organic framework material can effectively adsorb heavy metals in a water phase and a non-water phase, and can be used as an effective application means for adsorbing the heavy metals; the amino acid covalent grafting cyclodextrin-metal organic framework carbon material is economical and easy to obtain, and has high adsorption rate to heavy metals, high adsorption capacity and high repeated utilization rate; the amino acid covalent grafting cyclodextrin-metal organic framework derivative material is an edible green material without toxic action on human bodies, and can be widely applied to the fields of food, medicine, environment and the like.
Drawings
FIG. 1 is an SEM electron micrograph of amino acid covalent grafting cyclodextrin-metal organic framework composite material obtained by the method of example 1 of the invention.
FIG. 2 shows the adsorption efficiency of amino acid covalently grafted cyclodextrin-metal organic framework carbon material on cadmium (II) ions in a series of cadmium solutions according to example 7 of the present invention.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1 preparation of amino acid covalently grafted Cyclodextrin-Metal organic framework Material
Preparation of amino acid covalent grafting cyclodextrin-metal organic framework composite material by solvothermal method
0.72g (4 mmol) of L-tyrosine and 0.45g (8 mmol) of KOH are mixed in 10mL of water solution, and the mixture is incubated and stirred for 60min at 60 ℃ to obtain amino acid mixture. Adding 10mL of water solution dissolved with 1.30g (1 mmol) of gamma-cyclodextrin (gamma-CD) into the amino acid mixed solution, uniformly mixing and passing through a 0.45 mu m filter membrane, placing the filtered mixed solution into a sealed methanol gas environment, heating the methanol environment to 50 ℃, keeping for 24h, evaporating methanol steam into the mixed solution until a large number of colorless transparent crystals are obtained, discarding the supernatant, centrifuging for 5min at 10000rpm, washing the precipitate with 50mL of methanol for three times, and drying the obtained crystals at 60 ℃ in vacuum for 12h to obtain the tyrosine-cyclodextrin-metal organic framework (figure 1), wherein the size is 0.4-01 mu m, and the yield is 88.9%.
Example 2 preparation of amino acid covalently grafted Cyclodextrin-Metal organic framework Material
Microwave method for preparing amino acid covalent grafting cyclodextrin-metal organic framework composite material
0.72g (4 mmol) of L-tyrosine and 0.45g (8 mmol) of KOH are mixed in 10mL of water solution, and the mixture is incubated and stirred for 60min at 60 ℃ to obtain amino acid mixture. Adding 10mL of aqueous solution dissolved with 1.30g (1 mmol) of gamma-cyclodextrin (gamma-CD) into the amino acid mixed solution, uniformly mixing and passing through a 0.45 mu m filter membrane, adding 5mL of methanol into the filtrate, then carrying out microwave treatment for 3min at the temperature of 500W and 80 ℃, taking out the solution, adding 256mg of PEG20000, standing at room temperature for 30min, removing the supernatant, centrifuging for 5min at 10000rpm, washing the precipitate with 50mL of methanol for three times, and carrying out vacuum drying on the obtained crystal for 12h at the temperature of 60 ℃ to obtain the tyrosine-cyclodextrin-metal organic framework, wherein the size is 200 to 800nm, and the yield is 90.2%.
Example 3 preparation of amino acid covalently grafted Cyclodextrin-Metal organic framework Material
Preparation of amino acid covalent grafting cyclodextrin-metal organic framework composite material by ultrasonic method
0.72g (4 mmol) of L-tyrosine and 0.45g (8 mmol) of KOH are mixed in 10mL of water solution, and the mixture is incubated and stirred for 60min at 60 ℃ to obtain amino acid mixture. Adding 10mL of aqueous solution dissolved with 1.30g (1 mmol) of gamma-cyclodextrin (gamma-CD) into the amino acid mixed solution, uniformly mixing and passing through a 0.45 mu m filter membrane, adding 5mL of methanol into the filtrate, carrying out ultrasonic treatment for 1h at 40kHz and 50 ℃, taking out the solution, adding 500mg of PVP-30, standing at room temperature for 30min, discarding the supernatant, centrifuging at 10000rpm for 5min, washing the precipitate with 50mL of methanol for three times, and carrying out vacuum drying on the obtained crystal for 12h at 60 ℃ to obtain the tyrosine-cyclodextrin-metal organic framework, wherein the size is 200 to 800nm, and the yield is 80.4%.
Example 4 amino acid covalently grafted Cyclodextrin-Metal organic framework carbon Material
Placing the amino acid covalent grafting cyclodextrin-metal organic framework material dried in the embodiment 2 into a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, firing for 4h, taking out after cooling to room temperature, carrying out the whole heating and cooling process under the protection of nitrogen, and cooling to obtain the tyrosine covalent grafting cyclodextrin-metal organic framework carbon material.
Example 5 amino acid covalently grafted Cyclodextrin-Metal organic framework carbon Material
Placing the amino acid covalent grafting cyclodextrin-metal organic framework material dried in the embodiment 2 into a tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, firing for 2h, taking out after cooling to room temperature, carrying out the whole heating and cooling process under the protection of nitrogen, and cooling to obtain the tyrosine covalent grafting cyclodextrin-metal organic framework carbon material.
Example 6 adsorption of organic arsenic from Antarctic krill oil by amino acid covalently grafted Cyclodextrin-Metal organic framework Material
10mL of antarctic krill oil (purchased from Sichuan corporation) was dispersed in 20mL petroleum ether, and 10mg of the amino acid covalently grafted cyclodextrin-metal organic framework material prepared in example 2 was added. Adsorbing for 1h at 25 ℃ and 300rpm, filtering, taking supernatant, digesting by sulfuric acid and nitric acid according to national standard, measuring the content of arsenic after treatment by inductively coupled plasma atomic emission spectrometry, and calculating the removal rate of arsenic to be 89%.
Example 7 adsorption of cadmium ions by amino acid covalently grafted Cyclodextrin-Metal organic framework carbon Material
The amino acid covalent grafting cyclodextrin-metal organic framework carbon material prepared in example 5 is used as an adsorbent, 10mg of the carbon material is taken and 10mL of 5, 10, 20, 30, 40, 50, 60, 80, 100, 200 and 500mg/L aqueous solution of cadmium (II) ions are sequentially added, and each group of three parallel samples and one control sample (the control sample is not added with the carbon material). Magnetically stirring at 25 deg.C and 300rpm for 1 hr, filtering, collecting supernatant, and measuring cadmium content by inductively coupled plasma atomic emission spectrometry (see FIG. 2). The result shows that the amino acid covalent grafting cyclodextrin-metal organic framework carbon material has specific adsorption effect on cadmium (II) ions in water, and the removal rate is nearly 99%.
Comparative example 1 adsorption of cadmium ions in Water by Cyclodextrin Metal-organic framework carbon Material
Weighing 0.45g (8 mmol) of KOH and 1.30g (1 mmol) of gamma-cyclodextrin, dissolving in 20mL of aqueous solution, uniformly mixing, filtering with a 0.45 mu m filter membrane, placing the filtered mixed solution in a sealed methanol environment, heating the methanol environment to 50 ℃, keeping for 24h, evaporating methanol steam to the mixed solution until a large amount of colorless transparent crystals are obtained, discarding the supernatant, centrifuging at 10000rpm for 5min, washing the precipitate with 50mL of methanol for three times, and vacuum drying the obtained crystals at 60 ℃ for 12h to obtain the cyclodextrin-metal organic framework material with the size of 0.4-01 mu m and the yield of 89.5%.
And placing the obtained cyclodextrin-metal organic framework material in a tubular furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, firing for 2h, taking out after cooling to room temperature, carrying out the whole heating and cooling process under the protection of nitrogen, and cooling to obtain the cyclodextrin-metal organic framework carbon material.
11 kinds of cadmium (II) ion solutions having different concentrations were adsorbed by the same method as in example 7, and the amount of the adsorbent added was 1mg/mL. The reaction time is 1h, the reaction temperature is 25 ℃, and the stirring speed is 300rpm. And after adsorption is finished, filtering, taking supernatant, measuring the content of the treated cadmium through inductive coupling plasma atomic emission spectrometry, and calculating to obtain the cyclodextrin-metal organic framework carbon material with the adsorption rate of the cadmium (II) ions reaching 88.7%.
Comparative example 2 adsorption of organic arsenic in Antarctic krill oil by Cyclodextrin Metal organic framework Material
Using the cyclodextrin-metal organic framework material prepared in comparative example 1, 10mL of Antarctic krill oil (purchased from Sichuan corporation, sichuan corporation) was dispersed in 20mL of petroleum ether in the same manner as in example 6, and 10mg of the cyclodextrin-metal organic framework material was added. Adsorbing for 1h at 25 ℃ and 300rpm, filtering, taking supernatant, digesting by sulfuric acid and nitric acid according to national standard, measuring the content of arsenic after treatment by inductively coupled plasma atomic emission spectrometry, and calculating the removal rate of arsenic to reach 74.7%.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. An amino acid covalent grafting cyclodextrin-metal organic framework material for removing heavy metal in organic liquid is characterized by being prepared by the following steps:
(1) Dissolving amino acid and potassium hydroxide in water, and stirring and incubating at 40-80 deg.C for 20min-2h to obtain a first mixed solution; uniformly mixing the first mixed solution and the cyclodextrin aqueous solution in equal volume to obtain a second mixed solution;
(2) And filtering the second mixed solution, placing the filtrate in an alcohol gas atmosphere or adding an alcohol solvent, pretreating, standing at room temperature until crystals grow out, centrifuging, washing precipitates, and drying to obtain the amino acid covalent grafting cyclodextrin-metal organic framework composite material.
2. The amino acid covalently grafted cyclodextrin-metal-organic framework material of claim 1, wherein in step (1), the amino acid is selected from one or more of L-tyrosine, aspartic acid, cysteine; the molar ratio of the amino acid to the potassium hydroxide is 1-1.
3. The amino acid covalently grafted cyclodextrin-metal-organic framework material of claim 1, wherein in step (1), the concentration of potassium hydroxide in the first mixture is 0.1-0.8mol/L.
4. The amino acid covalently grafted cyclodextrin-metal-organic framework material of claim 1, wherein in step (1), the cyclodextrin concentration of the aqueous cyclodextrin solution is 0.025-0.1mol/L, and the cyclodextrin comprises α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin.
5. The amino acid-covalently grafted cyclodextrin-metal organic framework material of claim 1, wherein in step (2), the alcohol in the alcohol gas atmosphere or alcohol solvent is selected from one or two of methanol and ethanol, and after the filtrate is added to the alcohol solvent to form a second mixture-alcohol mixture, the volume concentration of the alcohol in the second mixture-alcohol mixture is 30-40%.
6. The amino acid covalent grafting cyclodextrin-metal organic framework material of claim 1, wherein in the step (2), the pretreatment is selected from one or more of solvent heat treatment, ultrasonic treatment and microwave treatment; the temperature of the solvent heat treatment is 40-60 ℃, and the time is 12-24h; the ultrasonic frequency of the ultrasonic treatment is 30-40kHz, the ultrasonic time is 1-4h, and the temperature is controlled to be 40-60 ℃ during ultrasonic treatment; the microwave power of the microwave treatment is 400-600W, the microwave time is 5-20min, and the temperature is controlled to be 50-90 ℃ during the microwave treatment.
7. The amino acid covalent grafting cyclodextrin-metal organic framework material of claim 1, wherein in step (2), a size regulator is added to the pretreated second mixed solution, and the size regulator is selected from one or more of polyethylene glycol, polyvinylpyrrolidone and methanol; wherein the dosage of the polyethylene glycol is 0.01 to 0.1 time of the dosage of the cyclodextrin substance, the dosage of the polyvinylpyrrolidone is 0.005 to 0.05 time of the dosage of the cyclodextrin substance, and the dosage of the methanol is 15 to 50 percent of the volume of the second mixed solution.
8. The use of the amino acid covalently grafted cyclodextrin-metal organic framework material of claim 1 in the preparation of heavy metal adsorbents, wherein the amino acid covalently grafted cyclodextrin-metal organic framework material is added in an amount of 0.1 to 2g/L when adsorbing heavy metals in organic liquids.
9. An amino acid covalent grafting cyclodextrin-metal organic framework derived carbon material, which is characterized in that the amino acid covalent grafting cyclodextrin-metal organic framework material of claim 1 is calcined in air or nitrogen for carbonization to obtain the amino acid covalent grafting cyclodextrin-metal organic framework derived carbon material, wherein the calcining conditions are as follows: heating to 200-500 deg.C at a rate of 0.5-5 deg.C/min, and calcining for 2-5h.
10. The use of the carbon material derived from the amino acid-covalently grafted cyclodextrin-metal organic framework in the preparation of a heavy metal adsorbent according to claim 9, wherein the amino acid-covalently grafted cyclodextrin-metal organic framework carbon material is added in an amount of 0.1 to 2g/L in an aqueous solution and in an amount of 0.1 to 2g/L in an organic liquid when adsorbing heavy metals.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117085638A (en) * | 2023-09-14 | 2023-11-21 | 山东环瑞生态科技有限公司 | Efficient defluorination medicament suitable for lithium battery wastewater and application thereof |
| CN117299087A (en) * | 2023-11-29 | 2023-12-29 | 陕西天谷药业有限公司 | Adsorbent for removing heavy metals in traditional Chinese medicinal materials and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117085638A (en) * | 2023-09-14 | 2023-11-21 | 山东环瑞生态科技有限公司 | Efficient defluorination medicament suitable for lithium battery wastewater and application thereof |
| CN117085638B (en) * | 2023-09-14 | 2024-03-19 | 山东环瑞生态科技有限公司 | Efficient defluorination medicament suitable for lithium battery wastewater and application thereof |
| CN117299087A (en) * | 2023-11-29 | 2023-12-29 | 陕西天谷药业有限公司 | Adsorbent for removing heavy metals in traditional Chinese medicinal materials and preparation method thereof |
| CN117299087B (en) * | 2023-11-29 | 2024-03-01 | 陕西天谷药业有限公司 | Adsorbent for removing heavy metals in traditional Chinese medicinal materials and preparation method thereof |
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