CN108467490B - Functionalized metal organic framework porous material and preparation method and application thereof - Google Patents

Functionalized metal organic framework porous material and preparation method and application thereof Download PDF

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CN108467490B
CN108467490B CN201810271431.XA CN201810271431A CN108467490B CN 108467490 B CN108467490 B CN 108467490B CN 201810271431 A CN201810271431 A CN 201810271431A CN 108467490 B CN108467490 B CN 108467490B
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organic framework
porous material
functionalized metal
graphene oxide
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CN108467490A (en
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徐东辉
刘广洋
李凌云
黄晓东
张若楠
林桓
许晓敏
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Institute of Vegetables and Flowers Chinese Academy of Agricultural Sciences
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Abstract

The invention provides a functionalized metal organic framework porous material, a preparation method and application thereof. The functionalized metal organic framework porous material consists of a carrier and a metal organic framework loaded on the carrier; the carrier is magnetic graphene oxide/chitosan composite nanoparticles; the ligand of the metal organic framework is amino terephthalic acid. The material is a composite material formed by connecting MOFs, magnetic graphene oxide and chitosan, integrates the excellent characteristics of the three materials, has the advantages of high selectivity, high flux, rapid enrichment and separation and the like, is widely applied to the field of compound adsorption and separation, and adopts a self-assembly technology and a one-pot synthesis method, so that the process is simple, the preparation efficiency is high, and the yield is high.

Description

Functionalized metal organic framework porous material and preparation method and application thereof
Technical Field
The invention relates to the technical field of new materials, in particular to a functionalized metal organic framework porous material and a preparation method and application thereof.
Background
Metal-organic frameworks (MOFs) are a class of organic-inorganic hybrid materials with topological structures, which are synthesized from Metal ions or Metal clusters and organic ligands by self-assembly. The material has the advantages of high porosity, large specific surface area, adjustability of the pore size of the framework, cuttability and diversity of the structure and the like, and has wide application in the fields of compound adsorption and separation, sensors, drug slow release, luminescence, catalysis and the like. Although the structure and function of the metal center and the organic ligand, which can change the MOFs, are diversified, the single MOFs are deficient in the properties such as selectivity, mechanical strength and recycling.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a functionalized metal organic framework porous material, which is a composite material formed by connecting MOFs, magnetic graphene oxide and chitosan, integrates the excellent characteristics of the three materials, has the advantages of high selectivity, high flux, rapid enrichment and separation and the like, and is widely applied to the field of compound adsorption and separation.
The second purpose of the invention is to provide the application of the functionalized metal organic framework porous material, which has the characteristics of the traditional MOFs, so that the functionalized metal organic framework porous material also has wide application in the fields of compound adsorption and separation, sensors, drug slow release, luminescence, catalysis and the like, and has the advantages of high selectivity, rapid enrichment and separation and the like, so that the functionalized metal organic framework porous material has outstanding advantages in the aspects of adsorption or separation of nitrogen-containing heterocyclic compounds, and can be particularly used for removing nitrogen-containing heterocyclic bactericides in sewage.
The third purpose of the invention is to provide a preparation method of the functionalized metal organic framework porous material, which adopts a self-assembly technology and a one-pot synthesis method, so that the preparation method has the advantages of simple process, high preparation efficiency and high yield.
In order to achieve the above purpose, the invention provides the following technical scheme:
the functionalized metal organic framework porous material consists of a carrier and a metal organic framework loaded on the carrier;
the carrier is magnetic graphene oxide/chitosan composite nanoparticles;
the ligand of the metal organic framework is amino terephthalic acid.
The porous material provided by the invention takes the magnetic graphene oxide/chitosan composite nanoparticles as the carrier (or support) of the MOFs, so that the overall mechanical strength of the material is improved, and the binding sites and pore channels of the MOFs can be exposed outside, so that the performances of high flux, high adsorption force and the like of the MOFs are fully reserved. Meanwhile, both chitosan and amino terephthalic acid are rich in amino, so that the nitrogen-containing heterocyclic compound can be adsorbed with high selectivity. The magnetic graphene oxide is a nano-sheet material, contains oxygen-containing groups such as carboxyl, hydroxyl, epoxy and the like in the structure, has an ultra-large specific surface area, can quickly enrich a target object through acting forces such as hydrogen bonds and the like, and can be separated through magnetic adsorption due to superparamagnetism, so that the porous material is recycled.
As a functionalized metal organic framework porous material with more excellent performance, the crystal structure parameters are as follows:
diffraction peaks at 30.30 ° ± 0.5 °, 35.87 ° ± 0.5 °, 43.21 ° ± 0.5 °, 53.69 ° ± 0.5 °, 57.43 ° ± 0.5 ° and 62.97 ° ± 0.5 ° at 2 θ respectively correspond to Fe3O4(220), (311), (400), (422), (511) and (440); the (002) diffraction peak at 13.5 ° ± 0.3 ° 2 θ is a graphene characteristic peak;
or preferably, the central ion of the metal-organic framework is Zn2+。
Or preferably, the average pore diameter of the functionalized metal organic framework porous material is 7-10 nm, preferably 8.5-10 nm; the specific surface area is 100-130 m2Per g, preferably 115.5126-130 m2/g。
Or preferably, in the magnetic graphene oxide/chitosan composite nanoparticle, graphene oxide is electrostatically bonded to chitosan. The preparation method of the electrostatic combined magnetic graphene oxide/chitosan composite nano particle is simple, and the product purity is high. The electrostatic bonding in the present invention refers to electrostatic adsorption of carboxyl groups in Graphene Oxide (GO) and amino groups in chitosan.
In the traditional technology, the graphene oxide and the chitosan composite nanoparticles are coupled together through chemical groups such as amido bonds, the preparation method of the product is complex, the cost is high, and in addition, the number of byproducts is large in the preparation process, so the product purity is low, and the adsorption performance of the porous material is further reduced.
The invention provides a method for preparing the functionalized metal organic framework porous material, which comprises the following steps:
mixing magnetic graphene oxide/chitosan composite nanoparticles with a metal ion solution in an organic solvent, then adding a solution of amino terephthalic acid, carrying out continuous self-assembly, then adding a phase transfer catalyst for reaction, and then carrying out magnetic adsorption separation to obtain a target product;
wherein, the magnetic graphene oxide/chitosan composite nanoparticle: metal ions: the mass ratio of the amino terephthalic acid is as follows:
0.2-0.4: 0.24-0.32: 0.46, preferably 0.2 to 0.3: 0.3-0.32: 0.46.
as described in the above steps, the whole reaction is continuously carried out in one container, namely the characteristic of one-pot synthesis, and the self-assembly technology is adopted, so that the process is simple, the preparation efficiency is high, and the yield is high.
In addition, compared with the traditional MOFs modification method, the MOFs is not compounded with the magnetic graphene oxide/chitosan composite nanoparticles after being synthesized, but the MOFs and the magnetic graphene oxide/chitosan composite nanoparticles are simultaneously compounded, so that the purpose of avoiding the binding sites and the pore channels of the MOFs from being shielded by the magnetic graphene oxide/chitosan composite nanoparticles is realized, and the problems of low mechanical strength and easiness in collapse of the MOFs without a carrier support inside are also avoided.
The above preparation method can be further improved, specifically as follows.
Preferably, the metal ion is aluminum ion, iron ion or cobalt ion, with Zn being preferred2+。
Zn2+Can be added in any soluble zinc salt, such as zinc nitrate, zinc sulfate or zinc chloride, etc.
Preferably, the organic solvent is DMF.
Preferably, the reaction temperature of the continuous self-assembly is 15-35 ℃, and the reaction time is preferably 3-6 h.
Preferably, the mixing time of the magnetic graphene oxide/chitosan composite nanoparticles and the metal ion solution is more than 1h, and stirring is performed in the mixing process.
Preferably, the phase transfer catalyst is triethylamine.
Preferably, the magnetic adsorption separation further comprises: washing with DMF and absolute ethanol alternately for several times.
Preferably, spray drying or oven drying is also performed after the washing.
Preferably, the magnetic graphene oxide/chitosan composite nanoparticle is prepared by the following method:
mixing the graphene oxide water dispersion liquid with the chitosan solution in an inert gas atmosphere to perform electrostatic self-assembly reaction, and then adding Fe into the mixture3+And Fe2+Reacting the solution at 60-90 ℃, adding inorganic base, continuing to react, and performing magnetic adsorption separation to obtain a target product;
wherein, the graphene oxide: and (3) chitosan: fe3+：Fe2+The mass ratio of (A) to (B) is 0.2 to 0.6:0.15 to 0.2:0.3 to 0.35:0.14 to 0.28, preferably 0.2 to 0.6:0.15 to 0.2:0.33:0.14 to 0.28.
The preparation method of the electrostatic combined magnetic graphene oxide/chitosan composite nano particle is simple, and the product purity is high. In addition, the means of finally modifying the magnetism is beneficial to controlling the particle size and the particle size uniformity of the nano particles.
In the preparation process of the magnetic graphene oxide/chitosan composite nanoparticles, reaction parameters can be optimized to improve the magnetism and the bonding strength of the particles, which is specifically as follows.
Preferably, the inorganic base is ammonia water, preferably 25-28% of ammonia water by mass fraction, and the addition amount of the ammonia water is preferably as follows: 0.3-0.35 g Fe each3+Adding 10-15 mL of ammonia water.
Preferably, the reaction time of the electrostatic self-assembly is 0.5h or more.
Preferably, the reaction time after the addition of the inorganic base is 1 hour or more.
Preferably, in the aqueous dispersion of graphene oxide, the concentration of graphene oxide is 0.8-2.4 mg/mL.
As described above, the porous material provided by the invention mainly utilizes amino groups and hydrogen bonds to adsorb compounds, so that the porous material has high selective adsorption on nitrogen-containing heterocyclic compounds, and therefore, the porous material provided by the invention is mainly used for adsorbing or separating nitrogen-containing heterocyclic compounds, preferably adsorbing or separating nitrogen-containing heterocyclic bactericides, preferably adsorbing or separating epoxiconazole, fenbuconazole, pyraclostrobin, difenoconazole and thiabendazole, and more preferably adsorbing pyraclostrobin.
In summary, compared with the prior art, the invention achieves the following technical effects:
(1) the porous material combines MOFs, magnetic graphene oxide and chitosan together, has the advantages of high selectivity, rapid enrichment and separation and the like besides the traditional performances of high flux, high porosity and the like of the MOFs, and can be used for specific enrichment and removal of nitrogen-containing heterocyclic bactericide in sewage;
(2) the preparation method of the porous material provided by the invention utilizes self-assembly and one-pot synthesis technology, and has the advantages of simple flow, high efficiency, high yield and the like; meanwhile, the mechanical strength and the adsorption capacity of the porous material are increased;
(3) the preparation method of the magnetic graphene oxide/chitosan composite nanoparticles provided by the invention utilizes an electrostatic self-assembly technology, and has the advantages of simple process, high efficiency, high yield and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a TEM image of magnetic graphene oxide-chitosan nanoparticles provided in example 1 of the present invention;
FIG. 2 is an SEM image of M-GO-Chit-MOFs provided in embodiment 1 of the present invention;
FIG. 3 is an SEM image of a zinc-based-amino terephthalic acid metal organic framework provided in example 1 of the present invention;
FIG. 4 is an infrared spectrum of M-GO-Chit-MOFs provided in embodiment 1 of the present invention;
FIG. 5 is an XRD diffraction pattern of M-GO-Chit-MOFs provided in example 1 of the present invention;
FIG. 6 is a hysteresis loop curve of M-GO-Chit-MOFs provided in embodiment 1 of the present invention;
FIG. 7 is an adsorption curve of M-GO-Chit-MOFs to fungicides provided in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Firstly, preparing 2D magnetic graphene oxide-chitosan nanoparticles:
uniformly mixing oxidized graphene and a certain volume of high-purity water, placing the mixture into a 500mL three-necked bottle, adding a chitosan solution under mechanical stirring, and carrying out electrostatic self-assembly for 0.5 h. Then FeCl is added respectively3·6H2O and FeCl2·4H2And O, continuously stirring for 1h at the temperature of 60 ℃, then adding a certain volume of ammonia water (the mass fraction is 28%), continuously reacting for 1h, and protecting by using nitrogen in the whole experiment process. And magnetic adsorption separation, solvent washing and vacuum drying are carried out to obtain the magnetic graphene oxide-chitosan nanoparticles. The specific washing process is as follows: 1) suspending the precipitate obtained by magnetic separation in anhydrous ethanol, oscillating and vortexing for 2min, and removing the upper solution after magnetic adsorption; 2) suspending the precipitate obtained by magnetic separation in ultrapure water, oscillating and vortexing for 2min, and washing away water-soluble substances and unreacted ammonia water; 3) repeating the steps 1) and 2) alternately for 3 times; the volume ratio of the absolute ethyl alcohol to the ultrapure water used in each washing is 15mL:30-50 mL.
Wherein, the graphene oxide: and (3) chitosan: high purity water: FeCl3·6H2O：FeCl2·4H2O: 0.4g of ammonia water, 0.15g of ammonia water, 250mL of ammonia water, 1.6g of ammonia water, 0.8g of ammonia water, and 13mL of ammonia water.
Secondly, self-assembly of the functionalized metal organic framework porous structure material:
suspending magnetic graphene oxide-chitosan nanoparticles in 20mL DMF, and adding Zn dissolved in the DMF2+The solution was stirred and adsorbed for 1 h. Dropwise addition of NH under mechanical stirring2-H2BDC solution 10mL, room temperature continued self-assembly for 6h, added triethylamine (1.0-2.4mL) and continued the reaction for 3 h. And (3) obtaining the functional metal organic framework porous structure material (M-GO-Chit-MOFs) after magnetic adsorption separation, alternate washing with DMF and absolute ethyl alcohol for 3 times and vacuum drying.
Wherein, the magnetic graphene oxide-chitosan nanoparticle: zn2+：NH2-H2BDC is 0.3 g: 280 mg: 460 mg.
Thirdly, characterizing the product
The TEM image of the magnetic graphene oxide-chitosan nanoparticles prepared in the first step is shown in FIG. 1, and Fe can be found3O4The nano particles are uniformly deposited on the surface of the graphene nano sheet, the particle size is about 300nm, and the graphene nano sheet has an obvious 2D layered structure.
The SEM image of the M-GO-Chit-MOFs prepared in the second step is shown in figure 2, and the M-GO-Chit-MOFs can be found to be in a loose, porous and highly cross-linked three-dimensional space structure. For comparison, the present invention also provides an SEM image of a zinc-based-amino terephthalic acid metal organic framework, as shown in fig. 3.
The infrared spectrum of the M-GO-Chit-MOFs prepared in the second step is shown in FIG. 4, and is compared with a zinc-based-amino terephthalic acid metal-organic framework. 578cm in the figure-1The absorption peak is the characteristic absorption peak of Fe-O, and is 1064cm-1And 2921cm-1Respectively shows C-O-C and-CH of chitosan2Characteristic absorption peak of (B), indicating Fe3O4The nanoparticles and chitosan molecules have been attached to the graphene oxide surface. In addition, 1382cm-1A strong vibration peak appears, and the peak is NH2-H2Stretching vibration peak of-COOH in BTC, 1652cm-1Has a vibration peak of NH2-H2Of BTC-CCharacteristic peaks, the above analysis shows that the functionalized metal organic framework porous structure material is successfully prepared.
The XRD diffraction pattern of the M-GO-Chit-MOFs prepared in the second step is shown in figure 5, and is compared with that of ferroferric oxide particles, graphene oxide and a zinc-based-amino terephthalic acid metal organic framework. The XRD spectrum of the ferroferric oxide nano-particles contains 6 characteristic diffraction peaks which are matched with Fe in an X-ray diffraction database3O4The data of the standard card (JCPDS card, 19-629) are consistent, and the six characteristic peaks also exist in the diffraction pattern of the functionalized metal organic framework material, which indicates that Fe is in the coating process3O4The crystal structure of the spinel is still maintained. The characteristic peak of the graphene oxide is a diffraction peak at a 2 theta (13.5 degrees), a series of characteristic diffraction peaks appear in a spectrum of the zinc-based metal organic framework material within a range of 10 degrees to 30 degrees, the two characteristic peaks are found in the diffraction spectrum of the functionalized metal organic framework material, and the peak intensity is weakened.
The XRD diffraction pattern data of the M-GO-Chit-MOFs are as follows:
diffraction peaks at 2 θ of 30.30 °, 35.87 °, 43.21 °, 53.69 °, 57.43 ° and 62.97 ° respectively correspond to Fe3O4(220), (311), (400), (422), (511) and (440); the (002) diffraction peak at 13.5 ° 2 θ is a characteristic graphene peak.
The hysteresis loop curve of the M-GO-Chit-MOFs prepared in the second step is shown in FIG. 6, and is compared with ferroferric oxide particles and magnetic graphene oxide-chitosan nanoparticles (i.e. the magnetic composite nanoparticles in the figure). It can be found that the iron tetroxide nanoparticles have higher magnetic saturation intensity, which is 68.3emu/g, and when the graphene oxide-chitosan and zinc-based-metal organic framework materials are modified in sequence, the magnetic saturation intensity is gradually reduced, and the magnetic response is reduced along with the reduction. The residual magnetization and residual coercive force of the three magnetic materials are close to 0, which shows that the three magnetic materials have superparamagnetism.
In the presence of an applied magnetic field, only about 20 seconds is needed for the magnetic MOF to aggregate and separate out of the solution quickly. When the applied magnetic field disappears, the magnetic MOF can be uniformly dispersed in the solution. Fe3O4 as a magnetic core and a carrier can endow the MOF with good superparamagnetism, so that the steps of centrifugal separation and the like can be avoided, the time and the cost are greatly saved, and the fast and efficient adsorption and removal of pesticide pollutants are realized.
According to a BET test, the average porosity of M-GO-Chit-MOFs is 8.57509nm, and the specific surface area is 115.5126M2/g。
Adsorption test of M-GO-chip-MOFs
Adding metal organic frameworks (M-GO-Chit-MOFs) into aqueous solutions of azacyclo-bactericide pesticides (five bactericides, namely epoxiconazole, fenbuconazole, pyraclostrobin, difenoconazole and thiabendazole), adsorbing for 0.5h, and performing magnetic separation to obtain supernatants;
monitoring the supernatant after adsorption by using HPLC-MS/MS;
calculating the adsorption capacity of the metal organic framework structure compound to 5 nitrogen heterocyclic bactericide pesticides, and constructing a static adsorption curve;
the different predetermined concentrations include 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, 5mg/L, 10mg/mL, and 20 mg/L.
The adsorption capacity of the metal organic framework structure compound to 5 nitrogen heterocyclic ring bactericide pesticides comprises the following steps:
the calculation is made according to the following formula: q ═ C0-C)V/M；
In the formula, Q is the adsorption capacity mu g/mg of the metal organic framework structure compound to the nitrogen heterocyclic bactericide pesticide in balance; c0The initial concentration of the nitrogen heterocyclic bactericide pesticide is mg/L; c is the concentration mg/L of the azacyclo-bactericide pesticide in the supernatant liquid during the balance; v is the volume mL of the aqueous solution of the azacyclo-bactericide pesticide; m is the mass mg of the metal-organic framework structure compound;
as shown in FIG. 7, the adsorption curve shows that, in the range of 0.1-5mg/L of the N-heterocyclic bactericide, the adsorption amount of the functionalized MOF to five N-heterocyclic bactericides is continuously increased along with the increase of the initial solution concentration, and in the range of 5-20mg/L, the adsorption amount increase trend of the functionalized MOF to the N-heterocyclic bactericide is gentle and the adsorption balance is basically achieved. Although the magnetic functional MOF has a certain adsorption effect on five nitrogen heterocyclic bactericides, the adsorption capacity on pyraclostrobin is slightly higher than that of other pesticides, and the adsorption capacity on epoxiconazole is the worst. The possible reason for this is that the amino group of chitosan can selectively adsorb pyraclostrobin having more nitrogen and oxygen atoms through hydrogen bonding.
Example 2
The difference from the example 1 is only the mixture ratio of the second step reactants, which is as follows:
magnetic graphene oxide-chitosan nanoparticles: zn2+：NH2-H2BDC is 0.2g: 320 mg: 460 mg.
Through characterization, an infrared spectrum and an XRG diffraction pattern of M-GO-Chit-MOFs are basically consistent with those of example 1, and the adsorption quantity of pyraclostrobin on the pyraclostrobin is shown in Table 1.
Example 3
The difference from the example 1 is only the mixture ratio of the second step reactants, which is as follows:
magnetic graphene oxide-chitosan nanoparticles: zn2+：NH2-H2BDC is 0.4g: 240 mg: 460 mg.
Through characterization, an infrared spectrum and an XRG diffraction pattern of M-GO-Chit-MOFs are basically consistent with those of example 1, and the adsorption quantity of pyraclostrobin on the pyraclostrobin is shown in Table 1.
Example 4
The difference from the example 1 is only that the reaction conditions of the second step are different, and the reactant proportion is the same, which is as follows:
suspending magnetic graphene oxide-chitosan nanoparticles in 20mL DMF, and adding Zn dissolved in the DMF2+The solution was stirred and adsorbed for 1 h. Dropwise addition of NH under mechanical stirring2-H2BDC solution 10mL, room temperature continued self-assembly for 3h, added triethylamine (1.0-2.4mL) and continued the reaction for 3 h. And (3) obtaining the functional metal organic framework porous structure material (M-GO-Chit-MOFs) after magnetic adsorption separation, alternate washing with DMF and absolute ethyl alcohol for 3 times and vacuum drying.
Through characterization, an infrared spectrum and an XRG diffraction pattern of M-GO-Chit-MOFs are basically consistent with those of example 1, and the adsorption quantity of pyraclostrobin on the pyraclostrobin is shown in Table 1.
Example 5
The difference from the example 1 is only the mixture ratio of the first step reactants, which is as follows:
and (3) graphene oxide: and (3) chitosan: high purity water: FeCl3·6H2O：FeCl2·4H2O: 0.2g of ammonia water, 0.15g of ammonia water, 250mL of ammonia water, 1.6g of ammonia water, 0.50g of ammonia water, and 10mL of ammonia water.
Through characterization, an infrared spectrum and an XRG diffraction pattern of M-GO-Chit-MOFs are basically consistent with those of example 1, and the adsorption quantity of pyraclostrobin on the pyraclostrobin is shown in Table 1.
Example 6
The difference from the example 1 is only the mixture ratio of the first step reactants, which is as follows:
and (3) graphene oxide: and (3) chitosan: high purity water: FeCl3·6H2O：FeCl2·4H2O: 0.4g of ammonia water, 0.15g of ammonia water, 250mL of ammonia water, 1.6g of ammonia water, 1g of ammonia water, and 15mL of ammonia water.
Through characterization, an infrared spectrum and an XRG diffraction pattern of M-GO-Chit-MOFs are basically consistent with those of example 1, and the adsorption quantity of pyraclostrobin on the pyraclostrobin is shown in Table 1.
Example 7
The difference from the example 1 is only that the reaction conditions in the first step are different, and the reactant ratio is the same, which is as follows:
uniformly mixing oxidized graphene and a certain volume of high-purity water, placing the mixture into a 500mL three-necked bottle, adding a chitosan solution under mechanical stirring, and carrying out electrostatic self-assembly for 0.5 h. Then FeCl is added respectively3·6H2O and FeCl2·4H2And O, continuously stirring for 0.5h at the temperature of 90 ℃, then adding a certain volume of ammonia water (mass fraction of 28%), continuously reacting for 1h, and protecting by using nitrogen in the whole experimental process. And magnetic adsorption separation, solvent washing and vacuum drying are carried out to obtain the magnetic graphene oxide-chitosan nanoparticles. The specific washing process is as follows: 1) suspending the precipitate obtained by magnetic separation in anhydrous ethanol, oscillating and vortexing for 2min, and removing the upper solution after magnetic adsorption; 2) suspending the precipitate obtained by magnetic separation in ultrapure water, oscillating and vortexing for 2min, and washing away water-soluble substances and unreacted ammonia water; 3) repeating the above 1) and 2) alternately3 times; the volume ratio of the absolute ethyl alcohol to the ultrapure water used in each washing is 15mL:30-50 mL.
Through characterization, an infrared spectrum and an XRG diffraction pattern of M-GO-Chit-MOFs are basically consistent with those of example 1, and the adsorption quantity of pyraclostrobin on the pyraclostrobin is shown in Table 1.
TABLE 1
Figure BDA0001612641720000121
Note: the adsorption quantity in the table refers to the adsorption quantity of M-GO-Chit-MOFs on pyraclostrobin with the concentration of 10 mg/L.
As is clear from Table 1, the porous materials of examples 1 to 5 all had high adsorption amounts, and the adsorption amount of example 1 was the largest.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (18)

1. The functionalized metal organic framework porous material is characterized by consisting of a carrier and a metal organic framework loaded on the carrier;
the carrier is magnetic graphene oxide/chitosan composite nanoparticles;
the ligand of the metal organic framework is amino terephthalic acid;
the magnetic graphene oxide/chitosan composite nanoparticle is prepared by the following method:
mixing the graphene oxide water dispersion liquid with the chitosan solution in an inert gas atmosphere to perform electrostatic self-assembly reaction, and then adding Fe into the mixture3+And Fe2+Reacting the solution at 60-90 ℃, and then adding inorganic substancesAlkali, continuing to react, and then performing magnetic adsorption separation to obtain a target product;
wherein, the graphene oxide: and (3) chitosan: fe3+：Fe2+The mass ratio of (A) to (B) is 0.2-0.6: 0.15-0.2: 0.3-0.35: 0.14-0.28;
the preparation method of the functionalized metal organic framework porous material comprises the following steps:
mixing magnetic graphene oxide/chitosan composite nanoparticles with a metal ion solution in an organic solvent, then adding a solution of amino terephthalic acid, carrying out continuous self-assembly, then adding a phase transfer catalyst for reaction, and then carrying out magnetic adsorption separation to obtain a target product;
wherein, the magnetic graphene oxide/chitosan composite nanoparticle: metal ions: the mass ratio of the amino terephthalic acid is as follows: 0.2-0.4: 0.24-0.32: 0.46 of;
the metal ion is Zn2+；
The functionalized metal-organic framework porous material has an average pore diameter of 7-10 nm and a specific surface area of 100-130 m/g.
2. The functionalized metal-organic framework porous material according to claim 1, wherein the functionalized metal-organic framework porous material has the crystal structure parameters of:
2 θ = 30.30 ° ± 0.5 °, 35.87 ° ± 0.5 °, 43.21 ° ± 0.5 °, 53.69 ° ± 0.5 °, 57.43 ° ± 0.5 ° and 62.97 ° ± 0.5 ° diffraction peaks corresponding to Fe, respectively3O4(220), (311), (400), (422), (511) and (440); the (002) diffraction peak at 2 θ = 13.5 ° ± 0.3 ° is a graphene characteristic peak.
3. The functionalized metal-organic framework porous material according to claim 1, wherein the functionalized metal-organic framework porous material has an average pore size of 8.5 to 10 nm; specific surface area is 115.5126~130 m/g.
4. The functionalized metal-organic framework porous material according to claim 1, wherein the magnetic graphene oxide/chitosan composite nanoparticles: metal ions: the mass ratio of the amino terephthalic acid is as follows: 0.2-0.3: 0.3-0.32: 0.46.
5. the functionalized metal-organic framework porous material of claim 1, wherein the organic solvent is DMF.
6. The functionalized metal organic framework porous material according to claim 1, wherein the reaction temperature of the continuous self-assembly is 15-35 ℃ and the reaction time is 3-6 h.
7. The functionalized metal organic framework porous material according to claim 1, wherein the mixing time of the magnetic graphene oxide/chitosan composite nanoparticles and the metal ion solution is more than 1h, and stirring is performed during the mixing process.
8. The functionalized metal-organic framework porous material according to claim 1, wherein the phase transfer catalyst is triethylamine.
9. The functionalized metal-organic framework porous material of claim 1, further comprising after the magnetic adsorptive separation: washing with DMF and absolute ethanol alternately for several times.
10. The functionalized metal-organic framework porous material of claim 1, wherein the weight ratio of graphene oxide: and (3) chitosan: fe3+：Fe2+The mass ratio of (A) to (B) is 0.2-0.6: 0.15-0.2: 0.33: 0.14-0.28.
11. The functionalized metal organic framework porous material according to claim 1, wherein the inorganic base is 25-28% by mass of ammonia water.
12. The functionalized metal-organic framework porous material according to claim 11, characterized in thatThe adding amount of the ammonia water is as follows: 0.3-0.35 g Fe each3+Adding 10-15 mL of ammonia water.
13. The functionalized metal-organic framework porous material according to claim 1, wherein the reaction time of the electrostatic self-assembly is 0.5h or more.
14. The functionalized metal-organic framework porous material according to claim 1, wherein the reaction time after the addition of the inorganic base is 1 hour or more.
15. The functionalized metal-organic framework porous material according to claim 1, wherein the concentration of graphene oxide in the aqueous dispersion of graphene oxide is 0.8-2.4 mg/mL.
16. Use of the functionalized metal-organic framework porous material according to any one of claims 1 to 3, characterized in that it is used for the adsorption or separation of nitrogen-containing heterocyclic compounds.
17. Use of the functionalized metal organic framework porous material according to claim 16, characterized in that a nitrogenous heterocyclic bactericide is adsorbed or isolated.
18. Use of a functionalized metal organic framework porous material according to claim 17, characterized in that epoxiconazole, fenbuconazole, pyraclostrobin, difenoconazole, thiabendazole are adsorbed or separated.
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