CN113058556A - Magnetic adenine-based biological MOF material capable of adsorbing plasticizer and preparation method and application thereof - Google Patents
Magnetic adenine-based biological MOF material capable of adsorbing plasticizer and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional adsorption materials, and particularly relates to a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer, and a preparation method and application thereof; the preparation method comprises the following steps: (1) mixing Fe3O4The nano particles are placed in alcoholic solution containing surface modifier to prepare surface modified Fe3O4A nanoparticle; (2) surface-modified Fe3O4Synthesizing magnetic adenine-based biological MOF with a core-shell structure by the nanoparticles and adenine at the temperature of 70-120 ℃; (3) the magnetic adenine base biological MOF is modified at 100-200 ℃ under the action of an MOF modifier to prepare the magnetic capable of adsorbing the plasticizerA sexual adenine based biological MOF material. The preparation method is simple in preparation process and environment-friendly, and the prepared MOF material has good stability and can be recycled for a long time; more importantly, the prepared MOF material has higher specific surface area, porosity and magnetism, can enhance the adsorption effect on the plasticizer, and is easy to separate.
Description
Technical Field
The invention belongs to the technical field of functional adsorption materials, relates to a MOF material for adsorbing a plasticizer, and particularly relates to a magnetic adenine-based biological MOF material capable of adsorbing the plasticizer, and a preparation method and application thereof.
Background
Compared with the past in China, the problem of temperature fullness is not the problem to be solved urgently any more, but the quality of life is improved, wherein higher requirements are made on the quality of the oil, and the plasticizer generated in processing, transportation and storage of the oil seriously influences the quality of the oil and is harmful to the health of human bodies.
The existing technology or means for removing the plasticizer in the grease usually needs a large amount of additives, and although the requirement for removing the plasticizer can be met and the national standard is met, the process is complicated, the operation is inconvenient, and some additives even destroy nutrient substances in the grease and are irreparable.
The metal organic framework has very high specific surface area and has great advantages as an adsorbing material. A high-performance grease plasticizer removal material is developed based on the metal organic framework, so that the process in the grease processing process is perfected, the grease quality is ensured, and the method has practical significance for increasing requirements of people in China on the grease quality.
Disclosure of Invention
Aiming at the problems of complicated process and inconvenient operation of the prior process for removing the plasticizer from the grease, the invention aims to provide a magnetic adenine-based biological MOF material and application thereof in plasticizer adsorption; the MOF material provided by the application has an ultrahigh specific surface area and a large adsorption capacity, and can effectively remove a plasticizer in grease; in addition, magnetic particles are introduced into the magnetic adenine-based biological MOF material, so that the problem that the magnetic adenine-based biological MOF material is difficult to separate from the grease after the plasticizer in the grease is adsorbed in the prior art is further solved; the preparation method of the magnetic adenine-based biological MOF material is provided as another object of the invention.
Based on the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer, which is characterized by comprising the following steps:
(1) mixing Fe3O4The nano particles are put in alcoholic solution containing surface modifier for surface modificationUnder the action of the agent, surface modified Fe is prepared3O4A nanoparticle;
(2) surface-modified Fe3O4Synthesizing magnetic adenine-based biological MOF with a core-shell structure by the nanoparticles and adenine at the temperature of 70-120 ℃;
(3) and (3) modifying the magnetic adenine base biological MOF prepared in the step (2) at the temperature of 100-200 ℃ under the action of an MOF modifier to prepare the magnetic adenine base biological MOF material capable of adsorbing the plasticizer.
The invention is prepared by modifying the surface of the treated Fe3O4Preparing biological MOF with a core-shell structure from the nano particles and adenine, and then carrying out modification treatment on the biological MOF to prepare a magnetic adenine-based biological MOF material (modified biological MOF) capable of adsorbing a plasticizer; the invention prepares the biological MOF by simply and effectively utilizing the coordination of metal organic compounds through hydrothermal reaction, and has the advantages of simple and easily controlled preparation process, mild reaction conditions and green and pollution-free reaction process; in addition, the modified biological MOF is prepared by further carrying out structural modification on the prepared biological MOF, so that the adsorption selectivity of a product is improved, and the adsorption efficiency of a plasticizer is improved.
Further, said Fe3O4The preparation method comprises the following steps:
mixing ferric iron salt and ferrous iron salt, and coprecipitating at 70-100 deg.C to obtain superparamagnetism Fe3O4And (3) nanoparticles.
Further, the ferric salt is anhydrous ferric chloride and/or ferric chloride hexahydrate; the ferrous iron is ferrous sulfate heptahydrate and/or ferrous chloride.
The invention uses Fe with superparamagnetism3O4The nano particles are used as raw materials, so that the finally prepared modified biological MOF has magnetism, has the advantage of easy separation from a solution, and achieves the purposes of quickly adsorbing and separating the plasticizer in the grease.
Furthermore, the concentration of the surface modifier in the alcoholic solution is 0.03-0.3 mmol/L.
Further, the surface modifier in the step (1) is at least one of titanate coupling agent, silane coupling agent, oleic acid and thioglycolic acid.
The invention uses surface modifier to react Fe3O4The nanoparticles are surface modified to facilitate subsequent adenine incorporation in Fe3O4And carrying out grafting growth on the surfaces of the nano particles to form the macromolecular bio-based MOF material.
Further, the MOF modifier in the step (3) is a carboxylic acid modifier.
Further, the MOF modifier is at least one of adipic acid, 1,3, 5-benzenetricarboxylic acid, rigid di-branched carboxylic acid, isonicotinic acid, pyrazole carboxylic acid, pyrazole dicarboxylic acid and 4, 4' -dicarboxydiphenyl ether.
According to the invention, the magnetic adenine-based biological MOF is subjected to structural modification through the MOF modifier, so that the porosity of the material is improved, contact points for enrichment adsorption are increased, and the adsorption effect of the material to be adsorbed is enhanced.
In a second aspect, the invention provides a plasticizer-adsorbable magnetic adenine-based biological MOF material prepared by the above method.
By the invention using modified Fe3O4After the nanoparticles and adenine synthesize the biological MOF, further modifying to prepare a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer, and preparing the modified biological MOF by coordinating improved metal ions with an organism and modifying, wherein the prepared modified biological MOF has higher firmness, thermal stability and mechanical stability and can be repeatedly utilized for a long time; in addition, the prepared modified biological MOF is in a porous structure and has higher specific surface area and porosity, so that contact points for enrichment and adsorption are increased, and the adsorption effect on the plasticizer is enhanced.
In addition, the invention uses modified Fe3O4Preparing modified biological MOF by using nano particles as raw materials and utilizing modified Fe3O4The modified biological MOF prepared by the method has the advantage of easy separation from a solution due to the superparamagnetism of the nano particles, and the effects of quickly adsorbing and separating the plasticizer in the grease are realized.
In a third aspect, the invention provides an application of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer in removal of the grease plasticizer.
Furthermore, the removal rate of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer to the plasticizer in the grease is 92-97%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for preparing the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer, provided by the invention, has the advantages of simple preparation process, mild reaction process, greenness and no pollution; and the preparation raw materials are easy to obtain and the cost is low.
(2) The invention provides a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer, which has the advantages of stable structure and reutilization; in addition, the material is of a porous structure, has higher specific surface area and porosity, increases contact points for enrichment adsorption, and has the advantages of high adsorption efficiency and large adsorption capacity; in addition, the material has superparamagnetism, thereby having the advantage of easy separation from the solution.
(3) The magnetic adenine-based biological MOF material capable of adsorbing the plasticizer, which is prepared by the invention, has the characteristics of no corrosivity, harmlessness, no toxicity, no odor, no pollution, no flammability and no explosion; in addition, the material also has degradability and is environment-friendly.
(4) The magnetic adenine-based biological MOF material capable of adsorbing the plasticizer is used for adsorbing and removing the plasticizer in the grease, and has the advantages of large adsorption quantity, high removal efficiency and easiness in separation from the grease; when the plasticizer is added into the edible oil in an adding amount of 2%, the removal rate of the plasticizer in the edible oil reaches over 90%.
(5) The magnetic adenine-based biological MOF material is reasonably applied to the processing process of the grease, so that the quality and safety of the grease can be improved, and the requirement of consumers on the quality of the grease is met.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
Example 1
A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer comprises the following steps:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing anhydrous ferric chloride and ferrous sulfate heptahydrate according to the molar ratio of iron ions of 1:1, and coprecipitating at 70 ℃ to obtain Fe with superparamagnetism3O4And (3) nanoparticles.
(2) Superparamagnetic Fe3O4Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1)3O4The nanoparticles were surface modified in 200mL of ethanol solution containing 0.03mmol of thioglycolic acid for 48 h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2)3O4And (3) mixing the nanoparticles with adenine, and growing on the surface of the modified nanoparticles at 70 ℃ to synthesize the magnetic adenine-based biological MOF with the core-shell structure.
(4) Preparation of magnetic adenine base biological MOF material capable of adsorbing plasticizer:
and (3) modifying the magnetic adenine-based biological MOF synthesized in the step (3) with adipic acid at 100 ℃, namely performing structural modification on the magnetic adenine-based biological MOF by using the adipic acid to prepare the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer.
The magnetic adenine-based biological MOF material capable of adsorbing the plasticizer is prepared by the method.
In order to investigate the adsorption effect of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer on the plasticizer in the grease, the following method is adopted for experimental analysis.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, simultaneously adding 2% of the magnetic adenine-based biological MOF material which is prepared by the method and can absorb the plasticizer, serving as an adsorbent, continuously adsorbing for 16h, and then performing magnetic separation and recovery; the content of DEHP in the soybean edible oil is detected by using a gas chromatography, and the removal rate of the DEHP is calculated, so that the result shows that the removal rate of the biological MOF material prepared by the method for the DEHP in the soybean edible oil is 92%.
Example 2
A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer comprises the following steps:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing ferric chloride hexahydrate and ferrous chloride according to the molar ratio of ferric ions of 1:1, and coprecipitating at 100 ℃ to obtain superparamagnetic Fe3O4And (3) nanoparticles.
(2) Superparamagnetic Fe3O4Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1)3O4The nanoparticles were surface modified in 200mL of ethanol solution containing 0.3mmol of titanate coupling agent for 24 h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2)3O4And (3) after the nano particles are mixed with adenine, growing on the surfaces of the modified nano particles at 120 ℃ to synthesize the magnetic adenine-based biological MOF with the core-shell structure.
(4) Preparation of magnetic adenine base biological MOF material capable of adsorbing plasticizer:
and (3) modifying the magnetic adenine-based biological MOF synthesized in the step (3) and rigid di-branched carboxylic acid at 200 ℃, namely performing structural modification on the magnetic adenine-based biological MOF by using the rigid di-branched carboxylic acid to prepare the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer.
The magnetic adenine-based biological MOF material capable of adsorbing the plasticizer is prepared by the method.
In order to investigate the adsorption effect of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer on the plasticizer in the grease, the following method is adopted for experimental analysis.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, simultaneously adding 2% of the magnetic adenine-based biological MOF material which is prepared by the method and can absorb the plasticizer, serving as an adsorbent, continuously adsorbing for 16h, and then performing magnetic separation and recovery; the content of DEHP in the soybean edible oil is detected by using a gas chromatography, and the removal rate is calculated, and the result shows that the removal rate of the prepared biological MOF material to the DEHP in the soybean edible oil is 93%.
Example 3
A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer comprises the following steps:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1:1, and coprecipitating at 80 ℃ to obtain Fe with superparamagnetism3O4And (3) nanoparticles.
(2) Superparamagnetic Fe3O4Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1)3O4The nanoparticles were surface modified in 200mL of ethanol solution containing 0.08mmol of oleic acid for 24 h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2)3O4And (3) after the nano particles are mixed with adenine, growing on the surfaces of the modified nano particles at the temperature of 100 ℃ to synthesize the magnetic adenine-based biological MOF with the core-shell structure.
(4) Preparation of magnetic adenine base biological MOF material capable of adsorbing plasticizer:
and (3) modifying the magnetic adenine-based biological MOF synthesized in the step (3) and isonicotinic acid at 150 ℃, namely, carrying out structural modification on the magnetic adenine-based biological MOF by using the isonicotinic acid to prepare the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer.
The magnetic adenine-based biological MOF material capable of adsorbing the plasticizer is prepared by the method.
In order to investigate the adsorption effect of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer on the plasticizer in the grease, the following method is adopted for experimental analysis.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, simultaneously adding 2% of the magnetic adenine-based biological MOF material which is prepared by the method and can absorb the plasticizer, serving as an adsorbent, continuously adsorbing for 16h, and then performing magnetic separation and recovery; the content of DEHP in the soybean edible oil is detected by utilizing a gas chromatography, and the removal rate is calculated, and the result shows that the removal rate of the prepared biological MOF material to the DEHP in the soybean edible oil is 95%.
Example 4
A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer comprises the following steps:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1:1, and coprecipitating at 80 ℃ to obtain Fe with superparamagnetism3O4And (3) nanoparticles.
(2) Superparamagnetic Fe3O4Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1)3O4The nanoparticles were surface-modified in 200mL of an ethanol solution containing 0.1mmol of a silane coupling agent for 24 h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2)3O4Mixing the nano-particles with adenine, growing on the surface of the modified nano-particles at 100 ℃ to synthesize the magnetic gland with the core-shell structureA purine-based biological MOF.
(4) Preparation of magnetic adenine base biological MOF material capable of adsorbing plasticizer:
and (3) modifying the magnetic adenine-based biological MOF synthesized in the step (3) and pyrazole dicarboxylic acid at 150 ℃, namely performing structural modification on the magnetic adenine-based biological MOF by utilizing the pyrazole dicarboxylic acid to prepare the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer.
The magnetic adenine-based biological MOF material capable of adsorbing the plasticizer is prepared by the method.
In order to investigate the adsorption effect of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer on the plasticizer in the grease, the following method is adopted for experimental analysis.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, simultaneously adding 2% of the magnetic adenine-based biological MOF material which is prepared by the method and can absorb the plasticizer, serving as an adsorbent, continuously adsorbing for 16h, and then performing magnetic separation and recovery; the content of DEHP in the soybean edible oil is detected by using a gas chromatography, and the removal rate is calculated, and the result shows that the removal rate of the prepared biological MOF material to the DEHP in the soybean edible oil is 94%.
Example 5
A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer comprises the following steps:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1:1, and coprecipitating at 80 ℃ to obtain Fe with superparamagnetism3O4And (3) nanoparticles.
(2) Superparamagnetic Fe3O4Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1)3O4The nanoparticles were surface modified in 200mL of ethanol solution containing 0.2mmol of thioglycolic acid for 24 h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2)3O4And (3) after the nano particles are mixed with adenine, growing on the surfaces of the modified nano particles at the temperature of 100 ℃ to synthesize the magnetic adenine-based biological MOF with the core-shell structure.
(4) Preparation of magnetic adenine base biological MOF material capable of adsorbing plasticizer:
and (3) modifying the magnetic adenine-based biological MOF synthesized in the step (3) and 1,3, 5-pyromellitic tricarboxylic acid at 150 ℃, namely performing structural modification on the magnetic adenine-based biological MOF by using the 1,3, 5-pyromellitic tricarboxylic acid to prepare the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer.
The magnetic adenine-based biological MOF material capable of adsorbing the plasticizer is prepared by the method.
In order to investigate the adsorption effect of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer on the plasticizer in the grease, the following method is adopted for experimental analysis.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, simultaneously adding 2% of the magnetic adenine-based biological MOF material which is prepared by the method and can absorb the plasticizer, serving as an adsorbent, continuously adsorbing for 16h, and then performing magnetic separation and recovery; the content of DEHP in the soybean edible oil is detected by utilizing a gas chromatography, and the removal rate is calculated, and the result shows that the removal rate of the prepared biological MOF material to the DEHP in the soybean edible oil is 97%.
Example 6
A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer comprises the following steps:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1:1, and coprecipitating at 80 ℃ to obtain Fe with superparamagnetism3O4And (3) nanoparticles.
(2) Superparamagnetic Fe3O4Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1)3O4The nanoparticles were surface modified in 200mL of ethanol solution containing 0.2mmol of thioglycolic acid for 24 h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2)3O4And (3) after the nano particles are mixed with adenine, growing on the surfaces of the modified nano particles at the temperature of 100 ℃ to synthesize the magnetic adenine-based biological MOF with the core-shell structure.
(4) Preparation of magnetic adenine base biological MOF material capable of adsorbing plasticizer:
and (3) modifying the magnetic adenine base biological MOF synthesized in the step (3) and pyrazolecarboxylic acid at 150 ℃, namely, performing structural modification on the magnetic adenine base biological MOF by using the pyrazolecarboxylic acid to prepare the magnetic adenine base biological MOF material capable of adsorbing the plasticizer.
The magnetic adenine-based biological MOF material capable of adsorbing the plasticizer is prepared by the method.
In order to investigate the adsorption effect of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer on the plasticizer in the grease, the following method is adopted for experimental analysis.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, simultaneously adding 2% of the magnetic adenine-based biological MOF material which is prepared by the method and can absorb the plasticizer, serving as an adsorbent, continuously adsorbing for 16h, and then performing magnetic separation and recovery; the content of DEHP in the soybean edible oil is detected by using a gas chromatography, and the removal rate is calculated, and the result shows that the removal rate of the prepared biological MOF material to the DEHP in the soybean edible oil is 93%.
Comparative example 1
The plasticizer-adsorbable magnetic adenine-based bio-MOF material of this comparative example 1 was prepared by referring to the method described in example 5, differing from example 5 only in superparamagnetic Fe of this comparative example 13O4The nanoparticles are not modified.
The specific process for preparing the magnetic adenine-based biological MOF material in the comparative example 1 is as follows:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1:1, and coprecipitating at 80 ℃ to obtain Fe with superparamagnetism3O4And (3) nanoparticles.
(2) Preparation of magnetic adenine-based biological MOF:
mixing superparamagnetic Fe3O4After the nanoparticles are mixed with adenine, the adenine-based biological MOF with a core-shell structure is synthesized at 100 ℃. Due to Fe3O4The nanoparticles are not subjected to surface modification treatment, so that adenine cannot be in Fe3O4The nanoparticles grow on the surface, so the synthetic adenine-based biological MOFs are not magnetic.
(3) Preparation of plasticizer-adsorbable adenine-based biological MOF material:
and modifying the synthesized adenine-based biological MOF and 1,3, 5-pyromellitic tricarboxylic acid at 150 ℃, namely performing structural modification on the adenine-based biological MOF by using the 1,3, 5-pyromellitic tricarboxylic acid to prepare the plasticizer-absorbable adenine-based biological MOF material.
The adenine-based bio-MOF material of this comparative example 1, which can adsorb a plasticizer, was prepared by the above method.
In order to investigate the adsorption effect of the adenine-based biological MOF material capable of adsorbing the plasticizer on the plasticizer in the grease, the following method is adopted for experimental analysis.
10g of commercially available refined soybean edible oil was taken, di (2-ethylhexyl) phthalate (DEHP) was added to the soybean edible oil, and at the same time, 2% by weight of the oil of the plasticizer-adsorbable adenine-based bio-MOF material prepared in this example 1 was added as an adsorbent, and the adsorption was continued for 16 hours. Due to Fe3O4The nanoparticles are not subjected to surface modification treatment, so that the adenine-based biological MOF material prepared in comparative example 1 cannot be separated magnetically after adsorbing the plasticizer, and therefore, the material can be separated by adopting other conventional means such as filtration. Subjecting the separated soybean edible oil to gas chromatographyThe content of DEHP in the soybean edible oil is detected, and the removal rate of the DEHP in the soybean edible oil is calculated, and the result shows that the removal rate of the biological MOF material prepared in the comparative example 1 on the DEHP in the soybean edible oil is 92%.
From the test results of comparative example 1, Fe3O4The nano particles are not subjected to surface modification treatment, so that the finally prepared biological MOF material has no magnetism, and after the biological MOF material adsorbs the plasticizer, the plasticizer is separated from the grease by adopting a relatively complex process, but a relatively simple magnetic separation process cannot be adopted. This indicates that the present invention is directed to Fe3O4The nanoparticles are subjected to surface modification treatment, so that the subsequent separation process of the biological MOF material and grease is facilitated to be simplified.
Comparative example 2
Referring to the method described in example 5, the biological MOF material of comparative example 2 was prepared, differing from example 5 only in that the biological MOF material of comparative example 2 was not subjected to a structural modification treatment.
The specific process for preparing the magnetic adenine-based biological MOF material in the comparative example 2 is as follows:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1:1, and coprecipitating at 80 ℃ to obtain Fe with superparamagnetism3O4And (3) nanoparticles.
(2) Superparamagnetic Fe3O4Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1)3O4The nanoparticles were surface modified in 200mL of ethanol solution containing 0.2mmol of thioglycolic acid for 24 h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2)3O4And (3) after the nano particles are mixed with adenine, growing on the surfaces of the modified nano particles at the temperature of 100 ℃ to synthesize the magnetic adenine-based biological MOF with the core-shell structure.
The magnetic adenine-based biofmof material of this comparative example 2 was prepared by the above method.
In order to investigate the adsorption effect of the magnetic adenine-based biological MOF material on the plasticizer in the grease, the following method is adopted for experimental analysis.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, simultaneously adding 2% of magnetic adenine-based biological MOF material prepared in the comparative example 2 in the oil weight as an adsorbent, continuously adsorbing for 16h, and then recovering by magnetic separation; the content of DEHP in the soybean edible oil is detected by using a gas chromatography, and the removal rate is calculated, and the result shows that the removal rate of the biological MOF material prepared in the comparative example 2 on the DEHP in the soybean edible oil is 80%.
As can be seen from the comparison of the results of the comparative example 2 and the example 5, the adsorption rate of the biological MOF material in the example 5 to the plasticizer in the grease is obviously higher than that of the comparative example 2; the difference between the two MOF materials is that the MOF material in example 5 was subjected to structural modification, i.e. the MOF material reacted with carboxylic acid to form a large number of amide bonds, enhancing the adsorption of the plasticizer.
Comparative example 3
The preparation of the biological MOF material of comparative example 3, with reference to the process described in example 5, differs from example 5 only in the superparamagnetic Fe of comparative example 33O4The nanoparticles are not modified and the biological MOF material is not structurally modified.
The specific process for preparing the magnetic adenine-based biological MOF material in the comparative example 3 is as follows:
(1) superparamagnetic Fe3O4Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1:1, and coprecipitating at 80 ℃ to obtain Fe with superparamagnetism3O4And (3) nanoparticles.
(2) Preparation of magnetic adenine-based biological MOF:
mixing superparamagnetic Fe3O4Mixing the nanoparticles with adenine, and heating at 100 deg.C to obtain modified nanoparticlesThe surface grows to synthesize adenine base biological MOF with a nucleocapsid structure. Due to Fe3O4The nanoparticles are not subjected to surface modification treatment, so that adenine cannot be in Fe3O4The nanoparticles grow on the surface, and finally, the formed adenine-based biological MOF has no magnetism.
The adenine-based MOF material of this comparative example 3 was prepared by the above method.
In order to investigate the adsorption effect of the adenine-based biological MOF material of comparative example 3 on the plasticizer in the oil, experimental analysis was performed by using the following method.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, simultaneously adding 2% of the adenine-based biological MOF material which is prepared by the method and can absorb the plasticizer, and using the adenine-based biological MOF material as an adsorbent, after continuously adsorbing for 16h, because the adenine-based biological MOF material cannot be separated magnetically after adsorbing the plasticizer, the separation is carried out by adopting other conventional means such as filtration and the like.
The content of DEHP in the separated soybean edible oil is detected by using a gas chromatography, and the removal rate is calculated, and the result shows that the removal rate of the DEHP in the soybean edible oil by using the biological MOF material prepared by the invention is 80%.
In conclusion, in the process of preparing the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer, the superparamagnetic Fe is added3O4The surface modification treatment is carried out on the nano particles, and the structure modification treatment is carried out on the biological MOF material, so that the effect of the magnetic adenine base biological MOF material capable of adsorbing the plasticizer on the adsorption and removal of the plasticizer in the grease is obviously improved, and the magnetic adenine base biological MOF material has the advantages of high adsorption efficiency and simple separation process.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer is characterized by comprising the following steps:
(1) mixing Fe3O4The nano particles are placed in an alcoholic solution containing a surface modifier, and under the action of the surface modifier, surface modified Fe is prepared3O4A nanoparticle;
(2) surface-modified Fe3O4Synthesizing magnetic adenine-based biological MOF with a core-shell structure by the nanoparticles and adenine at the temperature of 70-120 ℃;
(3) and (3) modifying the magnetic adenine base biological MOF prepared in the step (2) at the temperature of 100-200 ℃ under the action of an MOF modifier to prepare the magnetic adenine base biological MOF material capable of adsorbing the plasticizer.
2. The method for preparing the plasticizer-adsorbable magnetic adenine-based biological MOF material of claim 1, wherein the Fe is3O4The preparation method comprises the following steps:
mixing ferric iron salt and ferrous iron salt, and coprecipitating at 70-100 deg.C to obtain superparamagnetism Fe3O4And (3) nanoparticles.
3. The method for preparing the plasticizer adsorbable magnetic adenine-based biological MOF material of claim 1, wherein the concentration of the surface modifier in the alcoholic solution is 0.03-0.3 mmol/L.
4. The method for preparing the plasticizer-adsorbable magnetic adenine-based biological MOF material according to claim 3, wherein the surface modifier in the step (1) is at least one of titanate coupling agent, silane coupling agent, oleic acid and thioglycolic acid.
5. The method for preparing the plasticizer adsorbable magnetic adenine-based biological MOF material of claim 1, wherein in the step (3), the MOF modifier is a carboxylic acid modifier.
6. The method for preparing the plasticizer-adsorbable magnetic adenine-based biological MOF material of claim 5, wherein the MOF modifier is at least one of adipic acid, 1,3, 5-benzenetricarboxylic acid, rigid di-branched carboxylic acid, isonicotinic acid, pyrazolecarboxylic acid, pyrazoledicarboxylic acid, and 4, 4' -dicarboxydiphenyl ether.
7. A plasticizer-adsorbable magnetic adenine-based biological MOF material prepared by the method of any one of claims 1 to 6.
8. The use of the plasticizer adsorbable magnetic adenine-based MOF material of claim 7 in the removal of lipid plasticizers.
9. The use of claim 8, wherein the removal rate of the plasticizer from the oil and fat by the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer is 92-97%.
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