CN113058556B - Magnetic adenine-based biological MOF material capable of adsorbing plasticizer as well as preparation method and application thereof - Google Patents
Magnetic adenine-based biological MOF material capable of adsorbing plasticizer as well as preparation method and application thereof Download PDFInfo
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- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229930024421 Adenine Natural products 0.000 title claims abstract description 142
- 229960000643 adenine Drugs 0.000 title claims abstract description 142
- 239000000463 material Substances 0.000 title claims abstract description 121
- 239000004014 plasticizer Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 82
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 5
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 46
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 10
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 14
- 230000005389 magnetism Effects 0.000 abstract description 4
- 239000012621 metal-organic framework Substances 0.000 description 154
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 49
- 239000008157 edible vegetable oil Substances 0.000 description 39
- 235000010469 Glycine max Nutrition 0.000 description 37
- 244000068988 Glycine max Species 0.000 description 37
- 239000004519 grease Substances 0.000 description 31
- 230000004048 modification Effects 0.000 description 25
- 238000012986 modification Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 230000008901 benefit Effects 0.000 description 11
- 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 description 10
- 230000008569 process Effects 0.000 description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 229940032296 ferric chloride Drugs 0.000 description 9
- 229910001447 ferric ion Inorganic materials 0.000 description 9
- 229960002089 ferrous chloride Drugs 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 9
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 9
- 238000007885 magnetic separation Methods 0.000 description 8
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- IKTPUTARUKSCDG-UHFFFAOYSA-N 1h-pyrazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1C=NNC=1C(O)=O IKTPUTARUKSCDG-UHFFFAOYSA-N 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
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 Fe 3 O 4 The nano particles are placed in alcoholic solution containing surface modifier to prepare surface modified Fe 3 O 4 A nanoparticle; (2) Surface-modified Fe 3 O 4 Synthesizing 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-based MOF is modified at 100-200 ℃ under the action of an MOF modifier to prepare the magnetic adenine-based MOF material capable of adsorbing the plasticizer. 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. The 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, one of the purposes of the invention is to provide a magnetic adenine-based biological MOF material and the 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 plasticizers 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; a method for preparing 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 Fe 3 O 4 The nano particles are placed in alcoholic solution containing surface modifier, and under the action of the surface modifier, surface modified Fe is prepared 3 O 4 A nanoparticle;
(2) Surface-modified Fe 3 O 4 Synthesizing 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 Fe 3 O 4 Preparing 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 hydrothermal reaction by simply and effectively utilizing coordination of metal organic compounds, 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 modifying the structure of the prepared biological MOF, which is beneficial to improving the adsorption selectivity of the product and improving the adsorption efficiency of the plasticizer.
Further, said Fe 3 O 4 The preparation method comprises the following steps:
mixing ferric salt and ferrous salt, and coprecipitating at 70-100 deg.C to obtain superparamagnetism Fe 3 O 4 And (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 superparamagnetism 3 O 4 The 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 Fe 3 O 4 The nanoparticles are surface modified to facilitate subsequent adenine incorporation in Fe 3 O 4 And 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 structure of the magnetic adenine-based biological MOF is modified by the MOF modifier, so that the porosity of the material is improved, contact points for enrichment and 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 Fe 3 O 4 After 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 Fe 3 O 4 Preparing modified biological MOF by using nano particles as raw materials and utilizing modified Fe 3 O 4 The 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 a 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, so that the material has the advantage of being easy to separate from a 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 Fe 3 O 4 Preparing nano particles:
mixing anhydrous ferric chloride and ferrous sulfate heptahydrate according to the molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Superparamagnetic Fe 3 O 4 Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1) 3 O 4 The nanoparticles were surface modified in 200mL of ethanol solution containing 0.03mmol of thioglycolic acid for 48h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2) 3 O 4 After the nano particles are mixed with adenine, the nano particles grow on the surfaces of the modified nano particles at 70 ℃, and the magnetic adenine-based MOF with a core-shell structure is synthesized.
(4) Preparation of magnetic adenine-based biological MOF material capable of adsorbing plasticizer:
and (4) modifying the magnetic adenine-based MOF synthesized in the step (3) and adipic acid at 100 ℃, namely performing structural modification on the magnetic adenine-based MOF by using the adipic acid to prepare the magnetic adenine-based 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 capable of adsorbing the plasticizer, which is prepared by the method and is used as an adsorbent, continuously adsorbing for 16 hours, and then recovering by adopting magnetic separation; 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 plasticizers comprises the following steps:
(1) Superparamagnetic Fe 3 O 4 Preparing nanoparticles:
mixing ferric chloride hexahydrate and ferrous chloride according to the molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Superparamagnetic Fe 3 O 4 Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1) 3 O 4 And (3) placing the nanoparticles in 200mL of ethanol solution containing 0.3mmol of titanate coupling agent for surface modification for 24h.
(3) Preparation of magnetic adenine-based biological MOFs:
modifying the modified superparamagnetic Fe prepared in the step (2) 3 O 4 After the nano particles are mixed with adenine, the nano particles grow on the surfaces of the modified nano particles at 120 ℃, and the magnetic adenine-based MOF with a core-shell structure is synthesized.
(4) Preparation of magnetic adenine base biological MOF material capable of adsorbing plasticizer:
and (4) modifying the magnetic adenine-based MOF synthesized in the step (3) and rigid di-branched carboxylic acid at 200 ℃, namely, performing structural modification on the magnetic adenine-based MOF by utilizing the rigid di-branched carboxylic acid to prepare the magnetic adenine-based 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 plasticizers comprises the following steps:
(1) Superparamagnetic Fe 3 O 4 Preparing nanoparticles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Superparamagnetic Fe 3 O 4 Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1) 3 O 4 The nanoparticles were surface modified in 200mL of ethanol solution containing 0.08mmol of oleic acid for 24h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2) 3 O 4 And (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 (4) modifying the magnetic adenine-based MOF synthesized in the step (3) and isonicotinic acid at 150 ℃, namely, carrying out structural modification on the magnetic adenine-based MOF by using the isonicotinic acid to prepare the magnetic adenine-based 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 Fe 3 O 4 Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Superparamagnetic Fe 3 O 4 Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1) 3 O 4 The nanoparticles were surface-modified in 200mL of an ethanol solution containing 0.1mmol of a silane coupling agent for 24h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2) 3 O 4 After the nano particles are mixed with adenine, the nano particles grow on the surfaces of the modified nano particles at 100 ℃, and the magnetic adenine-based MOF with a core-shell structure is synthesized.
(4) Preparation of magnetic adenine base biological MOF material capable of adsorbing plasticizer:
and (4) modifying the magnetic adenine-based biological MOF synthesized in the step (3) and the pyrazoledicarboxylic acid at 150 ℃, namely, performing structural modification on the magnetic adenine-based biological MOF by using the pyrazoledicarboxylic 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 DEHP in the soybean edible oil by the prepared biological MOF material is 94%.
Example 5
A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing plasticizers comprises the following steps:
(1) Superparamagnetic Fe 3 O 4 Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Superparamagnetic Fe 3 O 4 Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1) 3 O 4 The nanoparticles were surface modified in 200mL of ethanol solution containing 0.2mmol of thioglycolic acid for 24h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2) 3 O 4 After the nano particles are mixed with adenine, the nano particles grow on the surfaces of the modified nano particles at 100 ℃, and the magnetic adenine-based MOF with a core-shell structure is synthesized.
(4) Preparation of magnetic adenine-based 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-benzenetricarboxylic acid at 150 ℃, namely performing structural modification on the magnetic adenine-based biological MOF by using the 1,3, 5-benzenetricarboxylic 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 DEHP in the soybean edible oil by the prepared biological MOF material is 97%.
Example 6
A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing plasticizers comprises the following steps:
(1) Superparamagnetic Fe 3 O 4 Preparing nanoparticles:
mixing anhydrous ferric chloride and ferrous chloride according to a molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Superparamagnetic Fe 3 O 4 Modification of nanoparticles:
the superparamagnetic Fe prepared in the step (1) 3 O 4 The nanoparticles were surface modified in 200mL of ethanol solution containing 0.2mmol of thioglycolic acid for 24h.
(3) Preparation of magnetic adenine-based biological MOFs:
modifying the modified superparamagnetic Fe prepared in the step (2) 3 O 4 And (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-based 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 DEHP in the soybean edible oil by the prepared biological MOF material is 93%.
Comparative example 1
The plasticizer-adsorbable magnetic adenine-based MOF material of comparative example 1 was prepared according to the method described in example 5, differing from example 5 only in the superparamagnetic Fe of comparative example 1 3 O 4 The 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 Fe 3 O 4 Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to the molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Preparation of magnetic adenine-based biological MOFs:
mixing superparamagnetic Fe 3 O 4 After the nano particles are mixed with adenine, synthesizing the adenine-based MOF with a core-shell structure at 100 ℃. Due to Fe 3 O 4 The nanoparticles are not subjected to surface modification treatment, so that adenine cannot be in Fe 3 O 4 The nanoparticles grew on the surface, so the synthesized adenine-based biological MOF was not magnetic.
(3) Preparation of plasticizer-adsorbable adenine-based biological MOF material:
the synthesized adenine-based biological MOF and 1,3, 5-benzenetricarboxylic acid are modified at the temperature of 150 ℃, namely the 1,3, 5-benzenetricarboxylic acid is used for carrying out structural modification on the adenine-based biological MOF, so that the adenine-based biological MOF material capable of adsorbing the plasticizer is prepared.
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 effect of the adenine-based MOF material capable of adsorbing the plasticizer on the absorption of the plasticizer in the grease, the following method was used 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 comparative example 1 was added as an adsorbent, and the adsorption was continued for 16 hours. Due to Fe 3 O 4 The nanoparticles are not subjected to surface modification treatment, so that the adenine-based MOF material prepared in comparative example 1 cannot be separated magnetically after adsorbing the plasticizer, and therefore, the adenine-based MOF material is separated by adopting other conventional means such as filtration. The content of DEHP in the separated soybean edible oil is detected by using a gas chromatography method, and the removal rate of DEHP in the soybean edible oil is calculated, and the result shows that the removal rate of DEHP in the soybean edible oil by the biological MOF material prepared in the comparative example 1 is 92%.
From the test results of comparative example 1, fe 3 O 4 The nanoparticles are not surface modified so that the final green body is producedThe biological MOF material has no magnetism, and after the biological MOF material adsorbs the plasticizer, the plasticizer needs to be separated from the grease by adopting a relatively complex process, but cannot be separated by adopting a relatively simple magnetic separation process. This indicates that the present invention is directed to Fe 3 O 4 The 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 MOF material in comparative example 2 is as follows:
(1) Superparamagnetic Fe 3 O 4 Preparing nanoparticles:
mixing anhydrous ferric chloride and ferrous chloride according to a molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Superparamagnetic Fe 3 O 4 Modification of the nanoparticles:
the superparamagnetic Fe prepared in the step (1) 3 O 4 The nanoparticles were surface modified in 200mL of ethanol solution containing 0.2mmol of thioglycolic acid for 24h.
(3) Preparation of magnetic adenine-based biological MOF:
modifying the modified superparamagnetic Fe prepared in the step (2) 3 O 4 After the nano particles are mixed with adenine, the nano particles grow on the surfaces of the modified nano particles at 100 ℃, and the magnetic adenine-based MOF with a core-shell structure is synthesized.
The magnetic adenine-based biofmof material of this comparative example 2 was prepared by the above method.
In order to explore 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 is subjected to structural modification, i.e. the MOF material reacts with carboxylic acid to form a large number of amide bonds, which enhances 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 3 3 O 4 The 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 Fe 3 O 4 Preparing nano particles:
mixing anhydrous ferric chloride and ferrous chloride according to a molar ratio of ferric ions of 1 3 O 4 And (3) nanoparticles.
(2) Preparation of magnetic adenine-based biological MOF:
mixing superparamagnetic Fe 3 O 4 After the nano particles are mixed with adenine, the surface of the modified nano particles grows at the temperature of 100 ℃, and the adenine-based biological MOF with the core-shell structure is synthesized. Due to Fe 3 O 4 The nanoparticles are not subjected to surface modification treatment, so that adenine cannot be in Fe 3 O 4 The nanoparticles grow on the surface, and the finally formed adenine-based biological MOF does not have magnetism.
The adenine-based MOF material of this comparative example 3 was prepared by the above method.
In order to investigate the effect of the adenine-based MOF material of comparative example 3 on the adsorption of plasticizers in oils, experimental analysis was performed using the following method.
Taking 10g of commercially available refined soybean edible oil, adding di (2-ethylhexyl) phthalate (DEHP) into the soybean edible oil, and simultaneously adding 2% of the adenine-based biological MOF material capable of adsorbing the plasticizer, which is prepared by the method and is used as an adsorbent, and after continuously adsorbing for 16 hours, separating by adopting other methods such as filtration and the like because the adenine-based biological MOF material cannot be separated magnetically after adsorbing the plasticizer.
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 the prepared biological MOF material 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 added 3 O 4 The 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 (5)
1. A preparation method of a magnetic adenine-based biological MOF material capable of adsorbing a plasticizer is characterized by comprising the following steps of:
(1) Mixing Fe 3 O 4 The nanoparticles are placed in an alcoholic solution containing a surface modifier inUnder the action of the surface modifier, surface modified Fe is prepared 3 O 4 The surface modifier is at least one of oleic acid and thioglycolic acid;
(2) Surface-modified Fe 3 O 4 Synthesizing magnetic adenine-based biological MOF with a core-shell structure by the nanoparticles and adenine at the temperature of 70-120 ℃;
(3) Modifying the magnetic adenine base biological MOF prepared in the step (2) at 100-200 ℃ under the action of an MOF modifier to prepare the magnetic adenine base biological MOF material capable of adsorbing the plasticizer, wherein the MOF modifier is at least one of isonicotinic acid and 1,3, 5-pyromellitic tricarboxylic acid.
2. The preparation method of the magnetic adenine-based biological MOF material capable of adsorbing the plasticizer according to claim 1, characterized in that the Fe 3 O 4 The nano-particles are prepared by the following steps:
mixing ferric iron salt and ferrous iron salt, and coprecipitating at 70-100 deg.C to obtain superparamagnetism Fe 3 O 4 And (3) nanoparticles.
3. A magnetic adenine-based MOF material capable of adsorbing a plasticizer made by the method of any one of claims 1-2.
4. Use of a magnetic adenine-based biofmof material capable of adsorbing plasticizers according to claim 3 for the removal of lipidic plasticizers.
5. The use of claim 4, 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 95-97%.
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| CN110922606A (en) * | 2019-12-23 | 2020-03-27 | 北京工业大学 | Microporous Cu-MOF metal organic framework material constructed by adenine and auxiliary ligand, preparation and application |
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