CN106040182B - A kind of preparation method of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent - Google Patents

A kind of preparation method of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent Download PDF

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CN106040182B
CN106040182B CN201610592278.1A CN201610592278A CN106040182B CN 106040182 B CN106040182 B CN 106040182B CN 201610592278 A CN201610592278 A CN 201610592278A CN 106040182 B CN106040182 B CN 106040182B
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boric acid
phenyl boric
organic framework
preparation
modified carbon
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CN106040182A (en
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刘树成
潘建明
夏大厦
姚俊彤
黄伟
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Jiangsu University
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    • 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
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
    • C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

Abstract

The invention belongs to technical field of environment function material preparation, specifically disclose a kind of preparation method of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent.High internal phase material resistant to high temperature is synthesized first, secondly carbon foam is sintered into tube furnace, and then carbon foam bubble in the solution of zinc ion, then organic ligand (terephthalic acid (TPA)) and ligand fragment (3 is added, 5- dicarboxyl phenyl boric acid) carry out a series of processing after obtain adsorbent, and adsorbent to be used for Selective recognition and the separation of luteolin.The lotion imprinted polymer microballoon of preparation has very strong thermal stability, with efficient absorption luteolin and can have soda acid to control release performance.

Description

A kind of preparation of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent Method
Technical field:
The invention belongs to technical field of environment function material preparation, are related to a kind of phenyl boric acid type metal-organic framework material modification The method of carbon foam adsorbent.
Background technique
Large pore material is because numerous areas is widely paid close attention to and be applied to its significant anti-pressure ability, such as is catalyzed Agent, organizational project, absorption and separation etc.；The conventional method for preparing this large pore material is exactly to pass through polymerization with surfactant Carry out stable High Internal Phase Emulsion to produce, High Internal Phase Emulsion (High Internal Phase Emulsion, HIPE) is also known as height Concentrated emulsions, it is a kind of lotion of the dispersed phase volume fraction greater than 74.05%.
Metal organic frame is that have three by what coordinate bond was self-assembly of by organic ligand and metal ion or cluster Tie up porous material.Since it has huge specific surface area and aperture, metal-organic framework material is applied in recent ten years It is recycled to a large amount of field, such as gas, pharmaceutical carrier, catalysis, the fields such as separation.Nearest functional form metal-organic framework material is inhaled Draw very big concern, goes synthesis metal-organic framework material by introducing functional monomer as organic ligand segment.In this way Strategy the use scope of metal framework material is greatly facilitated.
Luteolin is natural flavonoid compound, has a variety of pharmacological activity, such as antibacterial, anticancer is antiviral, anti-oxidant Etc. abilities.The conventional method that luteolin in purification peanut shell commonly isolates and purifies mainly has macroporous resin adsorption separation Method, acid heavy method, gradient extraction etc..Although these methods respectively there are particular advantages, also respectively there is its limitation, wherein general character is scarce Falling into is poor selectivity, and reuse rate is low, costly.Therefore, it establishes and improves Selective recognition and isolate and purify peanut shell Higher degree, which is obtained, while the new strategy of luteolin, increase product yield in extracting solution has attracted very big concern.
Therefore this work is the method by growth in situ, then grows metal organic frame material in phase template in height Material, and introduce boronic acid monomer in metal-organic framework material and then be used to adsorb the original that luteolin utilizes boron affinity interaction Reason.
Summary of the invention
The present invention prepares boric acid modified type metal-organic framework material modified carbon foamed absorbent using in-situ growth technology (MOF-5-B-CF).High Internal Phase Emulsion material is synthesized first, and a mixed solution is formed by formaldehyde and melamine, is then introduced Triethanolamine, poly- liquid before eventually forming one, poly- liquid and toluene are vigorously stirred before then taking, and are formed High Internal Phase Emulsion, are then used Ethyl alcohol removes impurity, and the High Internal Phase Emulsion material of acquisition is dipped into zinc ion solution, and organic ligand is then added (to benzene two Formic acid) and ligand fragment (3,5- dicarboxyl phenyl boric acid) grow metal organic frame material in high internal phase material at high temperature under high pressure Material.Then it is used to isolate and purify luteolin.
Invention the technical solution adopted is that:
(1) preparation of carbon foam (CF):
Formalin and melamine are mixed, triethanolamine is added, is vigorously stirred 20- under 500rpm at 50-70 DEG C 40min, poly- liquid before obtaining；
Then to toluene solution is gradually added dropwise in the preceding poly- liquid, 2min is stirred under 1000rpm；Obtained lotion is in 60- Polyase 13-5 hours at 80 DEG C is dried 12-48 hours at 50-70 DEG C of vacuum, and obtained High Internal Phase Emulsion burns kettle with tube furnace respectively 2 hours, it is heated to 400-600 DEG C with 5 DEG C/min, obtains CF-T；
(2) CF-T-B-MOF is prepared:
Zinc nitrate hexahydrate is dissolved in first in the mixed solution of second alcohol and water, the CF-T for adding step (1) preparation is obtained To solution A, 3,5- dicarboxyl phenyl boric acid (BBDC) and terephthalic acid (TPA) (H is then added into solution A again2BDC solution) is obtained Solution B is placed in the reaction kettle of polytetrafluoroethylene (PTFE) by B, is reacted 6-24 hours at 100-200 DEG C, and the product finally obtained is used Ethyl alcohol is washed 3 times, is dried at 50-70 DEG C of vacuum.
In step (1), the formaldehyde, triethanolamine, melamine, the ratio of toluene is 3-4mL:2-3mL:1.5- 2g:6-10mL。
In step (2), the ratio of the CF-T, zinc nitrate hexahydrate, the mixed solution of second alcohol and water are 50-100mg: 0.1-0.2g:5-15mL。
In the mixed solution of the second alcohol and water, the volume ratio of second alcohol and water is 1:1.
In step (2), 3, the 5- dicarboxyl phenyl boric acid (BBDC), terephthalic acid (TPA) (H2BDC ratio) is 40- 50mg:40-50mg。
The 3,5- dicarboxyl phenyl boric acid (BBDC): the amount ratio of CF-T is 40-50mg:50-100mg.
Phenyl boric acid type metal-organic framework material modified carbon foamed absorbent prepared by the present invention is for isolating and purifying sweet-scented osmanthus Careless element.
Technological merit of the invention:
The product is by preparing boric acid modified type metal-organic framework material modified carbon foamed absorbent, first in MOF-5 Middle introducing boric acid function monomer, and growth in situ goes out metal-organic framework material on large pore material, material has high temperature resistant, tool There is excellent chemical property, furthermore also there is material pH response function can simplify adsorption/desorption operation.
Detailed description of the invention
Fig. 1 is the SEM figure that the high internal phase material of kettle is burnt in different temperatures, wherein A1, A2 are not through burning kettle, B1, B2 For the SEM figure of the high internal phase material of 400 DEG C of burning kettles, C1, C2 are the SEM figure of the high internal phase material of 500 DEG C of burning kettles, D1, D2 600 The SEM figure of the high internal phase material of DEG C burning kettle.
Fig. 2 growth in situ metal on high internal phase material (500 DEG C) for the polymerization time in embodiment 1 by 6 hours Organic framework materials (A1-A2), by the polymerization time of 12 hours, growth in situ metal has on high internal phase material (500 DEG C) Machine frame frame material (B1-B2), by the polymerization time of 24 hours, growth in situ metal is organic on high internal phase material (500 DEG C) The SEM of frame material (C1-C2) schemes.
Fig. 3 is high internal phase material (a) in embodiment 1, the high internal phase material (b) of kettle is burnt at 500 DEG C, by 24 hours Polymerization time growth in situ metal-organic framework material (c) on high internal phase material (500 DEG C) Raman figure.
Fig. 4 is high internal phase material (a) in embodiment 1, the high internal phase material (b) of kettle is burnt at 500 DEG C, by 24 hours Polymerization time growth in situ metal-organic framework material (c) on high internal phase material (500 DEG C) X-ray diffraction spectrogram.
Fig. 5 is high internal phase material (a) in embodiment 1, the high internal phase material (b) of kettle is burnt at 500 DEG C, by 24 hours Polymerization time growth in situ metal-organic framework material (c) on high internal phase material (500 DEG C) x-ray photoelectron spectroscopy Figure.
Fig. 6 is the curve of adsorption kinetics figure of 1 products therefrom of embodiment.
Fig. 7 is the adsorption isothermal curve figure of 1 products therefrom of embodiment.
Fig. 8 is the competitor adsorption curve figure of 1 products therefrom of embodiment.
Specific embodiment
Recognition performance evaluation carries out by the following method in the specific embodiment of the invention: complete using Staticadsorption experiment At.The certain density LTL solution of 10ml is added in centrifuge tube, a certain amount of phenyl boric acid type metal-organic framework material is added Modified carbon foamed absorbent is placed in 25 DEG C of constant temperature waters and stands several hours, and LTL content is divided light with UV, visible light after absorption Degree meter measurement, and adsorption capacity is calculated according to result；After saturation absorption, metal-organic framework material modified carbon foamed absorbent It is collected with high speed centrifugation, selects several structures and kin hydroxy kind compound, as competitive Adsorption object, it is poly- to participate in research Close the recognition performance of object.
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1:
(1) preparation of carbon foam (CF)
3mL formalin and the mixing of 1.5mL melamine, then add 2g triethanolamine, then under 50 degree 20min is vigorously stirred under 500rpm, poly- liquid before then obtaining.Then 6mL toluene solution is gradually added dropwise in poly- liquid before, then exists 2min is stirred under 1000rpm.Then the lotion obtained polyase 13 hour under 60 degree.Then it is dried 12 hours under 50 degree of vacuum. Obtained 50mg High Internal Phase Emulsion is burnt kettle 2 hours with tube furnace respectively, is heated to 400,500,600 degree with 5 DEG C/min, is obtained CF-400,CF-500,CF-600。
(2) CF-500-B-MOF is prepared
First the CF-500 of 50mg is put into and to be made of in the zinc nitrate hexahydrate solution of 0.1g the second alcohol and water of 5mL Mixed solution (v:v, 1:1) stirs 6 hours in the reaction kettle of polytetrafluoroethylene (PTFE).Then the 3,5- dicarboxyl benzene of 40mg is added Terephthalic acid (TPA) (the H of boric acid (BBDC) and 40mg2BDC it) is reacted 6 hours under 100 degree.The product finally obtained washes 3 with ethyl alcohol Time, then 50 degree of vacuum lower drying again.
Embodiment 2:
(1) preparation of carbon foam (CF)
4mL formalin and the mixing of 2mL melamine, then add 3g triethanolamine, then the 500rpm under 70 degree Under be vigorously stirred 40min, then obtain before poly- liquid.Then 10mL toluene solution is gradually added dropwise in poly- liquid before, then in 1000rpm Lower stirring 2min.Then the lotion obtained polymerize 5 hours under 80 degree.Then it is dried 48 hours under 70 degree of vacuum.It obtains 50mg High Internal Phase Emulsion is burnt kettle 2 hours with tube furnace respectively, is heated to 400,500,600 degree with 5 DEG C/min, is obtained CF-400, CF-500,CF-600。
(2) CF-500-B-MOF is prepared
The CF-500 of 100mg is put into the zinc nitrate hexahydrate solution of 0.2g first and is made of the second alcohol and water of 15mL Mixed solution (v:v, 1:1) stir 24 hours in the reaction kettle of polytetrafluoroethylene (PTFE).Then the 3,5- dicarboxyl of 50mg is added Terephthalic acid (TPA) (the H of base phenyl boric acid (BBDC) and 50mg2BDC it) is reacted 24 hours under 200 degree.The product second finally obtained Alcohol is washed 3 times, then 70 degree of vacuum lower drying again.
Embodiment 3:
(1) preparation of carbon foam (CF)
3.5mL formalin and the mixing of 2mL melamine, then add 2.5g triethanolamine, then under 60 degree 30min is vigorously stirred under 500rpm, poly- liquid before then obtaining.Then 8mL toluene solution is gradually added dropwise in poly- liquid before, then exists 2min is stirred under 1000rpm.Then the lotion obtained polymerize 4 hours under 70 degree.Then it is dried 24 hours under 60 degree of vacuum. Obtained 50mg High Internal Phase Emulsion is burnt kettle 2 hours with tube furnace respectively, is heated to 400,500,600 degree with 5 DEG C/min, is obtained CF-400,CF-500,CF-600。
(2) CF-500-B-MOF is prepared
The CF-500 of 75mg is put into the zinc nitrate hexahydrate solution of 0.15g first and is made of the second alcohol and water of 10mL Mixed solution (v:v, 1:1) stir 12 hours in the reaction kettle of polytetrafluoroethylene (PTFE).Then the 3,5- dicarboxyl of 45mg is added Terephthalic acid (TPA) (the H of base phenyl boric acid (BBDC) and 45mg2BDC it) is reacted 12 hours under 120 degree, the product second finally obtained Alcohol is washed 3 times, then 60 degree of vacuum lower drying again.
Fig. 1 is the SEM figure that the high internal phase material of kettle is burnt in different temperatures, wherein A1, A2 are not through burning kettle, B1, B2 For the SEM figure of the high internal phase material of 400 DEG C of burning kettles, C1, C2 are the SEM figure of the high internal phase material of 500 DEG C of burning kettles, D1, D2 600 The SEM figure of the high internal phase material of DEG C burning kettle.It can be concluded that, as temperature increases, high internal phase material is deformed more severe from figure, It was found that porous structure that high internal phase material at 500 DEG C has had and excellent rigidity.
Fig. 2 growth in situ metal on high internal phase material (500 DEG C) for the polymerization time in embodiment 1 by 6 hours Organic framework materials (A1-A2), by the polymerization time of 12 hours, growth in situ metal has on high internal phase material (500 DEG C) Machine frame frame material (B1-B2), by the polymerization time of 24 hours, growth in situ metal is organic on high internal phase material (500 DEG C) The SEM of frame material (C1-C2) schemes.
Fig. 3 is high internal phase material (a) in embodiment 1, the high internal phase material (b) of kettle is burnt at 500 DEG C, by 24 hours Polymerization time growth in situ metal-organic framework material (c) on high internal phase material (500 DEG C) Raman figure, can from c figure To obtain in 1489cm-1There is the peak of boric acid, illustrates phase material in the metallo organic metal frame material load height of borate type modification Expect successfully.
Fig. 4 is high internal phase material (a) in embodiment 1, the high internal phase material (b) of kettle is burnt at 500 DEG C, by 24 hours Polymerization time growth in situ metal-organic framework material (c) on high internal phase material (500 DEG C) X-ray diffraction spectrogram, according to Secondary sequence from top to bottom, from c figure it can be concluded that, by borate type metal-organic framework material load after, height in phase material The peak of material cannot not become sharply, illustrate to load successfully.
Fig. 5 is high internal phase material (a) in embodiment 1, the high internal phase material (b) of kettle is burnt at 500 DEG C, by 24 hours Polymerization time growth in situ metal-organic framework material (c) on high internal phase material (500 DEG C) x-ray photoelectron spectroscopy Figure.It can be concluded that there is the peak value of boric acid in 189cm-1 from c figure, illustrate that borate type modified metal organic framework materials load Success.
Test example 1:
Taking 10ml initial concentration is respectively that the LTL solution of 10mg/l, 15mg/l, 20mg/l, 25mg/l, 30mg/l are added to In centrifuge tube, the phenyl boric acid type metal-organic framework material modified carbon foamed absorbent (CF- that is separately added into 10mg embodiment 1 500-B-MOF), test fluid is placed on 25 DEG C, 35 DEG C, after standing 6h in 45 DEG C of water-bath, supernatant liquor supercentrifuge point From collection, unadsorbed LTL molecular concentration is measured with ultraviolet-uisible spectrophotometer, and calculates adsorption capacity according to result.
As a result, when initial concentration is 25mg/L, phenyl boric acid type metal-organic framework material is repaired as can be drawn from Figure 6 The absorption of decorations carbon foam adsorbent (CF-500-B-MOF) tends to balance.
Test example 2:
Taking 10mL initial concentration is that luteolin (LTL) solution of 20mg/L is added in centrifuge tube, is separately added into 10mg Phenyl boric acid type metal-organic framework material modified carbon foamed absorbent (CF-500-B-MOF) in embodiment 1, puts test fluid In 25 DEG C of water bath chader, taken out when 5min, 15min, 30min, 60min, 120min and 180min respectively； By being centrifuged phenyl boric acid type metal-organic framework material modified carbon foamed absorbent (CF-500-B-MOF) and luteolin (LTL) solution separates, and reuses the micropore nitrocellulose filter that aperture is 0.45mm and is filtered what removal suspended to solution Particle.LC concentration in filtrate is calculated measurement by ultraviolet specrophotometer under the wavelength of 349nm, and calculates suction according to result Attached capacity；
As can be drawn from Figure 7 as a result, the adsorption process of MIPFs can be divided into fast phase (preceding 60min) and slow rank Section, and MIPFs reaches the 96.28% of balancing capacity in the adsorption capacity of fast phase, is slowly increase until balance later, it was demonstrated that Influence of the binding site to absorption on macropore carbon structure, phenyl boric acid type metal-organic framework material modified carbon foamed absorbent (CF-500-B-MOF) be conducive to separate luteolin.
Test example 3: select catechol, p-nitrophenol, resorcinol, Quercetin, luteolin for competitive Adsorption Hydroxy kind compound, is respectively configured the aqueous solution of above four kinds of hydroxy kind compounds, and the concentration of every kind of competitive adsorbate is all 20mg/l takes the configured solution of 10ml to be added in centrifuge tube, and the phenyl boric acid type metal being separately added into 10mg embodiment 1 has Machine frame frame material modified carbon foamed absorbent (CF-500-B-MOF) is placed on test fluid in 25 DEG C of water-bath and stands respectively 6.0h, after the completion of time of repose, supernatant liquor is collected with being centrifuged at a high speed, unadsorbed various competitive Adsorption hydroxy kind chemical combination Object concentration is measured with efficient liquid phase (HPLC).
Result as can be drawn from Figure 8, (CF-500-B-MOF) is to catechol, p-nitrophenol, resorcinol, quercitrin Plain, luteolin adsorption capacity is respectively 9.04mg/g, 4.15mg/g, 3.28mg/g, 14.58mg/g；26.52mg/g.Table Bright CF-500-B-MOF has significant specific recognition ability to LTL, and adsorption capacity is higher than other hydroxyl class compounds.

Claims (4)

1. a kind of preparation method of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent, which is characterized in that including Following steps:
(1) preparation of carbon foam CF:
Formalin and melamine are mixed, triethanolamine is added, is vigorously stirred 20- under 500rpm at 50-70 DEG C 40min, poly- liquid before obtaining；
Then to toluene solution is gradually added dropwise in the preceding poly- liquid, 2min is stirred under 1000rpm；Obtained lotion is at 60-80 DEG C It is dried 12-48 hours at lower polyase 13-5 hours, 50-70 DEG C of vacuum, it is small that obtained High Internal Phase Emulsion burns kettle 2 with tube furnace respectively When, it is heated to 400-600 DEG C with 5 DEG C/min, obtains CF-T；
The formaldehyde, triethanolamine, melamine, the ratio of toluene are 3-4mL:2-3mL:1.5-2g:6-10mL
(2) CF-T-B-MOF is prepared:
Zinc nitrate hexahydrate is dissolved in first in the mixed solution of second alcohol and water, add step (1) preparation CF-T obtain it is molten Then 3,5- dicarboxyl phenyl boric acid BBDC and terephthalic acid (TPA) H is added in liquid A into solution A again2BDC obtains solution B, by solution B It being placed in the reaction kettle of polytetrafluoroethylene (PTFE), is reacted 6-24 hours at 100-200 DEG C, the product finally obtained is washed 3 times with ethyl alcohol, It is dried at 50-70 DEG C of vacuum；
CF-T, zinc nitrate hexahydrate, the ratio of the mixed solution of second alcohol and water are 50-100mg:0.1-0.2g:5-15mL；
3,5- dicarboxyl the phenyl boric acid BBDC, terephthalic acid (TPA) H2The ratio of BDC is 40-50mg:40-50mg；
The amount ratio of the 3,5- dicarboxyl phenyl boric acid BBDC:CF-T is 40-50mg:50-100mg.
2. a kind of preparation side of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent according to claim 1 Method, which is characterized in that in the mixed solution of the second alcohol and water, the volume ratio of second alcohol and water is 1:1.
3. a kind of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent, which is characterized in that the phenyl boric acid type gold Belonging to organic framework materials modified carbon foamed absorbent is had by the phenyl boric acid type metal as described in any one of claim 1~2 Obtained by the preparation method of machine frame frame material modified carbon foamed absorbent.
4. a kind of application of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent as claimed in claim 3, It is characterized in that, is used for the phenyl boric acid type metal-organic framework material modified carbon foamed absorbent to isolate and purify luteolin.
CN201610592278.1A 2016-07-25 2016-07-25 A kind of preparation method of phenyl boric acid type metal-organic framework material modified carbon foamed absorbent Expired - Fee Related CN106040182B (en)

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CN110849854B (en) * 2019-11-27 2022-05-24 曲阜师范大学 Method for determining Hg2+ and CH3Hg + contents by adopting BA-Eu-MOF composite material
CN111424429B (en) * 2020-04-30 2022-09-23 山东交通学院 Metal sulfide porous framework material, and preparation method and application thereof

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