CN114210308B - Core-shell structure material and preparation method and application thereof - Google Patents

Core-shell structure material and preparation method and application thereof Download PDF

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CN114210308B
CN114210308B CN202111352242.3A CN202111352242A CN114210308B CN 114210308 B CN114210308 B CN 114210308B CN 202111352242 A CN202111352242 A CN 202111352242A CN 114210308 B CN114210308 B CN 114210308B
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core
zif
shell
mil
shell structure
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CN114210308A (en
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郑裕基
钟钰琨
穆学良
江腾
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Southern University of Science and Technology
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    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract

The invention discloses a core-shell structure material and a preparation method and application thereof. The core-shell structure material is a hybridized core-shell structure material and comprises a core and a shell, wherein the core comprises ZIF-8, and the shell comprises MIL-100. Compared with single MOFs material, the core-shell structure material disclosed by the invention has the characteristic of multiple adsorption sites, can adsorb various substances and has strong adsorption capacity. And, because of the different micropore mesoporous properties of ZIF-8 and MIL-100, the core-shell structure material can adsorb two or more substances with different sizes.

Description

Core-shell structure material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a core-shell structure material and a preparation method and application thereof.
Background
In the last decades, metal-organic frameworks (MOFs) self-assembled by organic ligands and metal nodes play an important role in separation, storage and adsorption processes in many fields due to the mild synthesis conditions, various structures, high stability and large specific surface area of the MOFs. As one of the most attractive MOFs, ZIF-8 is often used as an adsorbent to remove pollutants in wastewater due to its advantages of easy synthesis, unique pore structure, and excellent thermal/chemical stability. However, at present, most MOFs materials have relatively single adsorption sites, single adsorption performance, weak adsorption capacity, poor water resistance and unstable structure, and limit the application of MOFs to a certain extent.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a core-shell structure material which has the characteristics of multiple adsorption sites, strong adsorption capacity and stable structure.
The invention also provides a preparation method of the core-shell structure material.
The invention also provides application of the core-shell structure material.
In a first aspect of the invention, a core-shell structural material is provided, which is a hybrid core-shell structural material and comprises a core and a shell, wherein the core comprises ZIF-8, and the shell comprises MIL-100.
For convenience of description, X@Y is used herein to denote a core-shell structure material, for example, ZIF-8@mils-100, and denotes a core-shell structure material using ZIF-8 as a core and MILs-100 as a shell.
The core-shell structural material provided by the embodiment of the invention has at least the following beneficial effects:
compared with single MOFs material, the core-shell structure material disclosed by the invention has the characteristic of multiple adsorption sites, can adsorb various substances and has strong adsorption capacity. And because of the difference of the mesoporous properties of ZIF-8 and MIL-100 micropores, the core-shell structure material can adsorb two or more substances with different sizes.
As MIL-100 has better water resistance than ZIF-8, ZIF-8 has higher specific surface area than MIL-100. Therefore, the core-shell structure material disclosed by the invention has the advantages of ZIF-8 and MIL-100, not only has the specific surface area and water resistance superior to those of ZIF-8 and MIL-100, but also has the advantages that the ratio of ZIF-8 to MIL-100 in the core-shell structure material is different, so that the core-shell structure material can have specific adsorption on specific materials, such as adsorption difference of positive, negative and middle-electrical organic molecules (namely the organic molecules are in positive, negative or middle-electrical property after being ionized or dissolved in a system where the organic molecules are located, such as positive, negative or molecular state, and the like, and the organic molecules are in positive, negative or middle-electrical property in short. Therefore, the adsorption of specific organic molecules such as dyes, antibiotics or other types of medicines can be satisfied by adjusting the ratio of ZIF-8 to MIL-100 according to actual needs.
Wherein the specific materials include, but are not limited to, RHB, MB, XCFF, BB-1, CBB, NGB, SD-III, AF, OG, EBBR, RR-120, OG-II, RBBR, MO, MY, ACBK, CR, MX-5B, MB-13, CB, FA in organic molecular dyes with positive, negative and medium electrical properties. The classification of a portion of the organic molecular dyes is detailed in table 1 below:
table 1 part of the organic molecular dye classification table
In addition, the core-shell structure material disclosed by the invention has a stable structure and can be recycled. In summary, the core-shell structure material disclosed by the invention has great application potential in the technical fields of adsorption materials, catalysts, magnetic materials, sensors or micro/nano devices.
In some embodiments of the invention, the core-shell structural material comprises a zinc-iron based composite core-shell structural material, wherein the core is ZIF-8, and the shell is MIL-100.
By the implementation mode, the zinc-iron-based composite core-shell structure material with the core of ZIF-8 and the shell of MIL-100 is superior to the specific surface area and the water resistance of a pure iron-based material (MIL-100) and a pure zinc-based material (ZIF-8), and has better performance.
In some preferred embodiments of the present invention, the core of the core-shell structural material is ZIF-8 and the shell is MIL-100 (Fe).
In some preferred embodiments of the present invention, the core-shell structure material is in P/P O Is 300-1300 m in the interval of 0.0-0.1 2 Specific surface area per gram.
In some embodiments of the invention, the ratio of the amount of ZIF-8 to MIL-100 (Fe) species in the core-shell structural material is 1 (1-8).
In some preferred embodiments of the present invention, the ratio of the amount of ZIF-8 to MIL-100 (Fe) in the core-shell structural material is 1 (2-8).
In some preferred embodiments of the present invention, the core-shell structural material has a ratio of ZIF-8 to MIL-100 (Fe) species of about 1:4.
In a second aspect of the present invention, a method for preparing a core-shell structure material is provided, including the following steps: and preparing ZIF-8 in an organic phase, thermally activating the ZIF-8, preparing a material I of the shell MIL-100 coated core ZIF-8 in a water phase by taking the thermally activated ZIF-8 as a core, and thermally activating the material I to obtain the core-shell structural material.
The preparation method of the core-shell structure material has at least the following beneficial effects:
because of obvious potential difference and hydrophobicity of the ZIF-8 and the MIL-100, the preparation method comprises the steps of preparing the core ZIF-8 in an organic phase, preparing the shell MIL-100 in a water phase to coat the core ZIF-8, and the MIL-100 and the ZIF-8 are not simply mixed and comprise a hybridization process, so that the core-shell structure material is obtained.
In addition, compared with the synthesis of MOFs materials in the related art, the MOFs materials are generally prepared through hydrothermal reaction at a high temperature (such as 80-100 ℃), and the MOFs materials can be prepared at a lower temperature (such as normal temperature). The preparation method is green and safe, and ZIF-8@MIL-100 doped in a core-shell structure mode can be manufactured at normal temperature, so that the MOFs material is hybridized on the basis of simplifying the preparation method, the structural stability is ensured, and the adsorption capacity of the MOFs material is obviously enhanced.
In some embodiments of the present invention, the ZIF-8 has a thermal activation temperature of 100 to 200deg.C and the material I has a thermal activation temperature of 100 to 200deg.C.
Through the implementation mode, the method can carry out heat activation treatment on the obtained MOFs material at the temperature of 100-200 ℃, reduces the difficulty of the preparation process, saves energy and is environment-friendly.
In some embodiments of the present invention, the ZIF-8 preparation, thermal activation process, comprises the steps of:
s1-1, carrying out ultrasonic treatment on an organic mixed solution of 2-methylimidazole and zinc salt at 0-8 ℃ and oscillating at 2-8 ℃ to obtain a mixture I;
s1-2, centrifuging the mixture I to obtain a precipitate I, soaking the precipitate I in an organic solvent I for heat activation treatment, and drying to obtain the core ZIF-8.
In some preferred embodiments of the present invention, in step S1-1, a methanol solution of 2-methylimidazole is mixed with a methanol solution of zinc nitrate hexahydrate to obtain the organic mixed solution.
In some more preferred embodiments of the present invention, in step S1-1, the organic mixed solution is sonicated at 0 to 8℃for 0.5 to 2 hours, and then oscillated in a constant temperature shaking table at 100 to 200rpm for more than 8 hours at 2 to 8 ℃.
In some more preferred embodiments of the present invention, in step S1-1, the organic mixed solution is sonicated in an ice-water bath for 0.5 to 2 hours, and then is oscillated in a constant temperature shaking table at a rotation speed of 100 to 200rpm at 2 to 8℃for more than 8 hours.
In some more preferred embodiments of the invention, the temperature of the ice water bath is about 0 ℃.
In some preferred embodiments of the present invention, in step S1-2, the mixture I is centrifuged to remove supernatant, and after washing with methanol and centrifuging 3 to 8 times, a pellet I is obtained, wherein the centrifugation speed is 3000 to 5000rpm and the centrifugation time is 2 to 3 minutes each time.
In some preferred embodiments of the present invention, in step S1-2, the precipitate i is immersed in methanol and subjected to an activation treatment at about 120 ℃ for more than 8 hours under sealed conditions in a high temperature and high pressure reaction vessel, wherein the initial pressure in the high temperature and high pressure reaction vessel is normal pressure.
In some preferred embodiments of the present invention, in step S1-2, the drying treatment is performed at 80℃or higher.
In some embodiments of the present invention, the MIL-100 is MIL-100 (Fe), and the preparation and thermal activation processes of the shell MIL-100 coated core ZIF-8 comprise the following steps:
s2-1, mixing the prepared ZIF-8 with water to obtain a dispersion liquid I, and mixing the dispersion liquid I with sodium trimesic acid to obtain a dispersion liquid II, wherein the ZIF-8 is in a dispersion state in the dispersion liquid II;
s2-2, carrying out oscillation treatment on a mixed solution of an aqueous solution of ferric salt and the dispersion liquid II at the temperature of 2-8 ℃ to obtain a mixture II;
s2-3, centrifuging the mixture II to obtain a precipitate II, soaking the precipitate II in an organic solvent II for heat activation treatment, and drying to obtain the core-shell structural material of the shell MIL-100 coated core ZIF-8.
According to the embodiment, the MIL-100 is prepared by using sodium trimesic acid as a raw material, and compared with the prior art that acid such as hydrofluoric acid is used for providing a reaction environment, the reaction speed is faster, and the reaction condition is milder.
In some preferred embodiments of the present invention, in step S2-2, the mixture of the aqueous solution of iron salt and said dispersion II is shaken in a thermostatic shaker at a speed of 100-200 rpm at 2-8℃for more than 8 hours.
In some preferred embodiments of the present invention, in step S2-2, the mixture II is centrifuged to remove supernatant, and after washing with methanol and water alternately, centrifugation is performed 3 to 8 times to obtain a pellet II, wherein the centrifugation speed is 2000 to 4000rpm, and the centrifugation time is 2 to 3 minutes each time.
In some preferred embodiments of the present invention, in step S2-3, the precipitate ii is immersed in methanol and subjected to an activation treatment at about 120 ℃ for more than 8 hours under sealed conditions in a high temperature and high pressure reaction vessel, wherein the initial pressure in the high temperature and high pressure reaction vessel is normal pressure.
In some preferred embodiments of the present invention, in step S2-3, the drying treatment is performed at 80℃or higher.
In a third aspect of the present invention, applications of the core-shell structure material in the technical fields of adsorption materials, catalysts, magnetic materials, sensors or micro/nano devices are provided.
In some embodiments of the invention, the core-shell structure material is applied to the technical fields of gas adsorption materials and wastewater treatment.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a graph showing the microstructure test results of the core-shell structure material prepared in example 1 of the present invention;
FIG. 2 is a graph showing the microstructure test results of the core-shell structure material prepared in example 2 of the present invention;
FIG. 3 is a graph showing the microstructure test results of the core-shell structure material prepared in example 3 of the present invention;
FIG. 4 is a graph showing BET nitrogen adsorption test results of the core-shell structured materials prepared in examples 1 to 4 of the present invention, ZIF-8 prepared in comparative example 1 and MIL-100 prepared in comparative example 2;
FIG. 5 is a graph showing the results of multi-dye adsorption performance test of the core-shell structured materials prepared in examples 1-4 of the present invention;
fig. 6 is a graph showing the test results of the "adsorption-desorption" cycle test of the core-shell structure material prepared in example 3 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the meaning of a number is one or more, the meaning of a number is two or more, and greater than, less than, exceeding, etc. are understood to exclude the present number, and the meaning of a number is understood to include the present number. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The embodiment discloses a core-shell structure material, which is a hybridized ZIF-8@MIL-100 (Fe) core-shell structure material, wherein the mass ratio of ZIF-8 to MIL-100 (Fe) substances in the core-shell structure material is 1:1.
The core-shell structural material is prepared by the embodiment, and the specific process is as follows:
(1) Dissolving 4g of sodium hydroxide powder in 8mL of deionized water, completely dissolving to prepare a concentrated solution, and cooling to room temperature to obtain a sodium hydroxide concentrated solution;
(2) Slowly adding 7g of trimesic acid powder into the obtained sodium hydroxide concentrated solution, stirring by using an iron ladle until the reaction is complete, and cooling to room temperature;
(3) The filtrate was recovered by filtration through a needle filter (aqueous phase 0.22 μm);
(4) Adding excessive absolute ethyl alcohol into the filtrate and generating white precipitate until the ethanol is added and no precipitate is separated out;
(5) Centrifuging to remove supernatant, washing with ethanol, centrifuging for 5 times at 3000rpm for 3 min;
(6) Collecting solid, mixing with excessive diethyl ether to obtain slurry, placing in an evaporation dish, and oven drying at 45deg.C;
(7) And (3) grinding the product obtained in the step (6) into white powder, and preserving the white powder in a moisture-proof manner to finish the preparation of the sodium trimesic acid solid.
(8) 3.25g of 2-methylimidazole powder is weighed and dissolved in 40mL of methanol to prepare solution A, and 1.5g of zinc nitrate hexahydrate powder is weighed and dissolved in 20mL of methanol to prepare solution B;
(9) Adding A, B liquid into a 250mL conical flask with a cover, uniformly mixing to obtain an organic mixed liquid, carrying out ultrasonic treatment on the organic mixed liquid in an ice-water bath for 1h, then transferring to a constant-temperature shaking table, oscillating at 200rpm at 4 ℃ overnight (more than 8 hours), and obtaining a mixture I after the reaction is finished;
(10) Centrifuging the mixture I to remove supernatant, washing with methanol, centrifuging for 5 times at a speed of 3000rpm for 3 minutes to obtain white precipitate I;
(11) Immersing the precipitate I in 60mL of methanol, placing the precipitate I in a 100mL high-temperature high-pressure reaction kettle, sealing the precipitate I, and placing the precipitate I in 120 ℃ overnight (more than 8 hours);
(12) And taking out the sample after the reaction kettle is cooled, sufficiently drying at 110 ℃, grinding into white powder, and preserving at normal temperature in a moisture-proof way to finish the preparation of the core ZIF-8.
(13) Weighing 0.23g ZIF-8 (the mass of the material is 1 mmol) prepared in the step (12), grinding, and fully dispersing ZIF-8 powder into 50mL deionized water by using an ultrasonic method to prepare a dispersion liquid I;
(14) Weighing sodium trimesic acid, dissolving in the dispersion liquid I, adding 0.41g (the amount of substances is 1.5 mmol) to prepare a dispersion liquid II, and keeping the ZIF-8 powder in a fully dispersed state during the preparation process;
(15) Weighing ferrous sulfate heptahydrate, dissolving in 50mL of deionized water, and preparing into ferrous sulfate aqueous solution, wherein the concentration is 0.45g/50mL (the corresponding mass concentration is 1.6mmol/50 mL);
(16) Adding dispersion liquid II and ferrous sulfate aqueous solution into a 250mL conical flask with a cover, uniformly mixing, transferring to a constant temperature shaking table, oscillating at 200rpm at 4 ℃ overnight (more than 8 hours), and obtaining a mixture II after the reaction is finished;
(17) Centrifuging the mixture II to remove supernatant, alternately washing and centrifuging with methanol and deionized water for 5 times, wherein the centrifuging speed is 3000rpm, and the centrifuging time is 3 minutes to obtain reddish brown precipitate II;
(18) Soaking the precipitate II in 60mL of methanol, placing the precipitate II in a 100mL high-temperature high-pressure reaction kettle, sealing the precipitate II, and placing the precipitate II in 120 ℃ overnight (more than 8 hours);
(19) And taking out the sample after the reaction kettle is cooled, sufficiently drying at 110 ℃, grinding into reddish brown powder, and preserving at normal temperature in a moisture-proof way to finish the preparation of the shell MIL-100 coated core ZIF-8.
The coating ratio of the core-shell structure sample obtained in the embodiment is 1:1.
Example 2
The difference between the core-shell structure material prepared in this example and that in example 1 is that steps 14-16 are different, specifically:
(14) Weighing sodium trimesic acid, dissolving in the dispersion liquid I, adding 0.82g (the amount of substances is 3 mmol), and preparing a dispersion liquid II, wherein the ZIF-8 powder is kept in a fully dispersed state;
(15) Weighing ferrous sulfate heptahydrate, dissolving in 50mL of deionized water, and preparing into ferrous sulfate aqueous solution, wherein the concentration is 0.89g/50mL (the corresponding mass concentration is 3.2mmol/50 mL);
(16) Adding dispersion liquid II and ferrous sulfate aqueous solution into a 250mL conical flask with a cover, uniformly mixing, transferring to a constant temperature shaking table, oscillating at 200rpm at 4 ℃ overnight (more than 8 hours), and obtaining a mixture II after the reaction is finished;
the coating ratio of the core-shell structure sample obtained in the embodiment is 1:2.
Example 3
The difference between the core-shell structure material prepared in this example and that in example 1 is that steps 14-16 are different, specifically:
(14) Weighing sodium trimesic acid, dissolving in the dispersion liquid I, adding 1.64g (the amount of substances is 6 mmol) to prepare a dispersion liquid II, and keeping the ZIF-8 powder in a fully dispersed state during the preparation process;
(15) Weighing ferrous sulfate heptahydrate, dissolving in 50mL of deionized water, and preparing into ferrous sulfate aqueous solution, wherein the concentration is 1.78g/50mL (the corresponding mass concentration is 6.4mmol/50 mL);
(16) Adding dispersion liquid II and ferrous sulfate aqueous solution into a 250mL conical flask with a cover, uniformly mixing, transferring to a constant temperature shaking table, oscillating at 200rpm at 4 ℃ overnight (more than 8 hours), and obtaining a mixture II after the reaction is finished;
the coating ratio of the core-shell structure sample obtained in the embodiment is 1:4.
Example 4
The difference between the core-shell structure material prepared in this example and that in example 1 is that steps 14-16 are different, specifically:
(14) Weighing sodium trimesic acid, dissolving in the dispersion liquid I, adding 3.28g (the amount of substances is 12 mmol) to prepare a dispersion liquid II, and keeping the ZIF-8 powder in a fully dispersed state during the preparation process;
(15) Weighing ferrous sulfate heptahydrate, dissolving in 50mL of deionized water, and preparing into ferrous sulfate aqueous solution, wherein the concentration is 3.56g/50mL (the corresponding mass concentration is 12.8mmol/50 mL);
(16) Adding dispersion liquid II and ferrous sulfate aqueous solution into a 250mL conical flask with a cover, uniformly mixing, transferring to a constant temperature shaking table, oscillating at 200rpm at 4 ℃ overnight (more than 8 hours), and obtaining a mixture II after the reaction is finished;
the coating ratio of the core-shell structure sample obtained in the embodiment is 1:8.
Comparative example 1
The ZIF-8 material is prepared according to the comparative example, and the specific process is as follows:
(1) 3.25g of 2-methylimidazole powder is weighed and dissolved in 40mL of methanol to prepare solution A, and 1.5g of zinc nitrate hexahydrate powder is weighed and dissolved in 20mL of methanol to prepare solution B;
(2) Adding A, B liquid into a 250mL conical flask with a cover, uniformly mixing to obtain an organic mixed liquid, carrying out ultrasonic treatment on the organic mixed liquid in an ice-water bath for 1h, then transferring to a constant-temperature shaking table, oscillating at 200rpm at 4 ℃ overnight (more than 8 hours), and obtaining a mixture I after the reaction is finished;
(3) Centrifuging the mixture I to remove supernatant, washing with methanol, centrifuging for 5 times at a speed of 3000rpm for 3 minutes to obtain white precipitate I;
(4) Immersing the precipitate I in 60mL of methanol, placing the precipitate I in a 100mL high-temperature high-pressure reaction kettle, sealing the precipitate I, and placing the precipitate I in 120 ℃ overnight (more than 8 hours);
(5) And taking out the sample after the reaction kettle is cooled, sufficiently drying at 110 ℃, grinding into white powder, and preserving at normal temperature in a moisture-proof way to finish the preparation of ZIF-8.
Comparative example 2
The MIL-100 material is prepared according to the comparative example, and the specific process is as follows:
(1) 1.86g of sodium trimesic acid powder is weighed and dissolved in 125mL of pure water to prepare sodium trimesic acid aqueous solution, and 2.25g of ferrous sulfate powder is weighed and dissolved in 125mL of pure water to prepare ferrous sulfate aqueous solution;
(2) Adding sodium trimesic acid aqueous solution and ferrous sulfate aqueous solution into a 500mL conical flask with a cover, uniformly mixing to obtain a mixed solution, oscillating the mixed solution at a constant temperature shaking table at a rotating speed of 200rpm at 4 ℃ overnight (more than 8 hours), and obtaining a mixture III after the reaction is finished;
(3) Centrifuging the mixture III to remove supernatant, alternately washing with methanol and pure water, centrifuging for 3 times at a speed of 3000rpm for 3 minutes each time to obtain brownish red precipitate III;
(4) Immersing the precipitate III in 60mL of methanol and placing the precipitate III in a 100mL high-temperature high-pressure reaction kettle, sealing the precipitate III and placing the precipitate III in 120 ℃ overnight (more than 8 hours);
(5) And taking out the sample after the reaction kettle is cooled, sufficiently drying at 110 ℃, grinding into brownish red powder, and preserving at normal temperature in a moisture-proof way to finish the preparation of MIL-100.
Test examples
The test example tests the microstructure, specific surface, zeta potential, multiple dye adsorption and adsorption-desorption cycle performance of the core-shell structure materials prepared in the examples and the comparative examples. Wherein:
all batch adsorption tests were performed in the absence of light to prevent photodegradation of organic contaminants in aqueous solutions, resulting in uv-vis spectrophotometric reading errors. Typically, the mixture of adsorbent and organic contaminant is placed in a cassette thermostatted shaker at 20℃and shaken at 200 rpm.
The sampling method used was: sampling is performed at a predetermined time. Immediately after sampling, the adsorbent was centrifuged. Absorbance at 251nm (AMX), 357nm (TC), 464nm (MO), 556nm (RHB), 507nm (SD-III) and 666nm (MB) was recorded using an ultraviolet-visible spectrophotometer, and the residual concentration was determined using a calibration curve. The adsorption equilibrium data of the contaminants on the ZIF-MILs samples fit three recognized kinetic models, namely, quasi-primary kinetics, quasi-secondary kinetics, and intra-particle diffusion models.
The test experiment specifically comprises the following steps:
the microstructure of the core-shell structured material prepared in examples 1-3 was tested and the test results are shown in FIGS. 1-3.
BET specific surface area and pore size analysis: the test items comprise mesopores, micropores and specific surface areas; the device model was U.S. microphone-ASAP 2460; the test information comprises: pretreatment conditions-temperature: pretreatment conditions-time at 150 ℃): 6H, adsorbing gas: nitrogen N 2 。
BET nitrogen adsorption experiments were performed on the core-shell structure materials prepared in examples 1 to 4, the ZIF-8 prepared in comparative example 1 and the MIL-100 prepared in comparative example 2, respectively, and the experimental results are shown in FIG. 4.
Single point surface area tests were performed on the core-shell structured materials prepared in examples 1-4, ZIF-8 prepared in comparative example 1, and MIL-100 prepared in comparative example 2, respectively, and the test results are shown in Table 2 below:
table 2 single point surface area test results table
Zeta potential tests were performed on the core-shell structured materials prepared in examples 1 to 4, the ZIF-8 prepared in comparative example 1 and the MIL-100 prepared in comparative example 2, respectively, and the test results are shown in Table 3 below:
TABLE 3Zeta potential test results Table
Material Zeta potential/mV
ZIF-8 +32
MIL-100 -17.3
ZIF-8@MIL-100(1:1) -6
ZIF-8@MIL-100(1:2) -9.7
ZIF-8@MIL-100(1:4) -13.3
ZIF-8@MIL-100(1:8) -17
The core-shell structured materials prepared in examples 1 to 4 were respectively subjected to multiple dye adsorption performance tests, and the test results are shown in fig. 5. The testing method comprises the following steps: the absorption properties of different organic contaminants were tested by adding 1mg of ZIF-MILs series samples to different contaminant solutions having an initial concentration of 100.0mg/L, respectively, wherein the contaminant solutions comprise six types: two cationic contaminant solutions (aqueous RHB-containing solution, MB-containing solution), one anionic contaminant solution (MO-containing solution) and three organic contaminant solutions (AMX aqueous solution, TC aqueous solution, SD-III ethanol solution), where TC is tetracycline.
For the core-shell structured material prepared in example 3, 200mg ZIF-8@MIL-100 (1:4) was used as the adsorbent, the pollution matrixes TC/MO, TC/RHB, RHB/MO, TC/SD-III and RHB/SD-III were mixed with the solvent to obtain mixed pollutant solutions, the selective adsorption of ZIF-8@MIL-100 (1:4) on different pollutants was tested by the mixed pollutant solutions, and the process was monitored by ultraviolet-visible spectroscopy, and the result details are shown in Table 4.
TABLE 4 test results Table for core-shell structured Material removal TC, RHB and SD-III
For the core-shell structure material prepared in example 3, 5 times of adsorption-desorption cycle tests are carried out, and the test results are shown in fig. 6, so that the recyclability and the water resistance of the core-shell structure material disclosed by the invention are proved. The test method involved performing an adsorption/desorption cycle experiment using 200mg ZIF-8@MIL-100 (1:4). The repeated use treatment is to wash the material with methanol five times and then soak it in 200mL methanol at 80 c for 24-48 hours. ZIF-8@MIL-100 (1:4) was again activated overnight in a digestion tank at 100deg.C prior to the next adsorption cycle. The removal rates of TC and RHB for the original ZIF-8@MIL-100 (1:4) were 100% and 95%, respectively. After 5 continuous cycles, the removal rates of TC and RHB are 91% and 100% respectively, which shows that the core-shell structure material has good cycle efficiency.
Combining the test results, the following can be obtained:
compared with single MOFs, the ZIF-8@MIL-100 core-shell structure material disclosed by the invention has the characteristic of multiple adsorption sites, can adsorb various substances and has strong adsorption capacity. And, because of the different micropore mesoporous properties of MIL-100 and ZIF-8, the core-shell structure material of the invention can adsorb two or more substances with different sizes.
As MIL-100 has better water resistance than ZIF-8, ZIF-8 has higher specific surface area than MIL-100. Therefore, the core-shell structure material disclosed by the invention has the advantages of ZIF-8 and MIL-100, not only has the specific surface area and water resistance superior to those of ZIF-8 and MIL-100, but also has the specific water resistance because the water-resistant MIL-100 (synthesized in the water phase) is used as a shell, and the ZIF-8 which is not water-resistant (needs to be synthesized in the organic phase) is coated, so that the protection effect on water is achieved; in addition, in the core-shell structure material, the ZIF-8 and MIL-100 are different in proportion, so that the difference of the core-shell structure material on Zeta potential can enable the core-shell structure material to have specific adsorption on specific materials, such as adsorption difference of positive, negative and middle electric organic molecular dyes. Therefore, the adsorption of specific organic molecules, such as dye, antibiotics or other types of medicines, can be satisfied by adjusting the ratio of ZIF-8 to MIL-100 according to actual needs. Wherein the specific materials include, but are not limited to, RHB, MB, XCFF, BB-1, CBB, NGB, SD-III, AF, OG, EBBR, RR-120, OG-II, RBBR, MO, MY, ACBK, CR, MX-5B, MB-13, CB, FA in organic molecular dyes with positive, negative and medium electrical properties. The classification of a portion of the organic molecular dyes is detailed in Table 1. In addition, the core-shell structure material disclosed by the invention has a stable structure and can be recycled.
The invention is manufactured at normal temperature and activates the ZIF-8 (ZIF-8@MIL-100) doped with Fe in a core-shell structure at the temperature below 200 ℃, thereby hybridizing the MOFs material on the basis of simplifying the preparation method, ensuring the structural stability and obviously enhancing the adsorption capacity. The preparation method is green and safe, and the core-shell structure material can be obtained by using a low-toxicity organic solvent without using high-temperature treatment above 300 ℃. And the zinc-iron-based composite ZIF-8@MIL-100 core-shell structure material is superior to the specific surface area and the water resistance of a pure iron-based material (MIL-100) and a pure zinc-based material (ZIF-8), and has more excellent performance. From the test results of examples 1 to 4, the performance of the core-shell structure material prepared in example 3 was optimal compared to examples 1, 2 and 4, presumably due to the potential and the hierarchical pores.
In summary, the core-shell structure material disclosed by the invention has great application potential in the technical fields of adsorption materials, catalysts, magnetic materials, sensors or micro/nano devices.
It should be noted that "normal temperature" or "room temperature" herein, unless otherwise specified, are about 25 ℃; "atmospheric pressure" as used herein refers to one atmosphere of pressure; "8 hours or more" herein may preferably be 8 to 15 hours; the meaning of "about" or "about" a numerical value is herein both an error of 2%.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (10)

1. The application of the core-shell structure material in adsorbing dyes and antibiotics is characterized in that the core-shell structure material is a hybridized core-shell structure material and comprises a core and a shell, wherein the core is ZIF-8, and the shell is MIL-100 (Fe); the ratio of the amount of ZIF-8 to MIL-100 (Fe) substances in the core-shell structural material is 1:4;
the preparation method of the core-shell structure material comprises the following steps:
and preparing ZIF-8 in an organic phase, thermally activating the ZIF-8, preparing a material I of which the shell MIL-100 (Fe) coats the core ZIF-8 in a water phase by taking the thermally activated ZIF-8 as a core, and thermally activating the material I to obtain the core-shell structural material.
2. The use according to claim 1, wherein the core-shell structural material is at P/P O 300 to 1300m is provided in the interval of 0.0 to 0.1 2 Specific surface area per gram.
3. Use according to claim 1, characterized in that the ZIF-8 preparation, thermal activation process comprises the following steps:
s1-1, carrying out ultrasonic treatment on an organic mixed solution of 2-methylimidazole and zinc salt at 0-8 ℃ and oscillating at 2-8 ℃ to obtain a mixture I;
s1-2, centrifuging the mixture I to obtain a precipitate I, soaking the precipitate I in an organic solvent I for heat activation treatment, and drying to obtain the core ZIF-8.
4. Use according to claim 3, characterized in that in step S1-1, a methanolic solution of 2-methylimidazole is mixed with a methanolic solution of zinc nitrate hexahydrate to obtain an organic mixture.
5. The method according to claim 3, wherein in step S1-2, the precipitate I is immersed in methanol and subjected to an activation treatment at 120℃for 8 hours or more under sealed conditions in a high temperature and high pressure reactor having a normal initial pressure.
6. The use according to claim 1, characterized in that the preparation, thermal activation process of the shell MILs-100 (Fe) coated core ZIF-8 comprises the following steps:
s2-1, mixing the prepared ZIF-8 with water to obtain a dispersion liquid I, and mixing the dispersion liquid I with sodium trimesic acid to obtain a dispersion liquid II, wherein the ZIF-8 is in a dispersion state in the dispersion liquid II;
s2-2, carrying out oscillation treatment on a mixed solution of an aqueous solution of ferric salt and the dispersion liquid II at the temperature of 2-8 ℃ to obtain a mixture II;
s2-3, centrifuging the mixture II to obtain a precipitate II, soaking the precipitate II in an organic solvent II for heat activation treatment, and drying to obtain the core-shell structural material of the shell MIL-100 (Fe) coated core ZIF-8.
7. The use according to claim 6, wherein in step S2-2, the mixture of the aqueous solution of iron salt and the dispersion ii is oscillated in a constant temperature shaking table at a rotation speed of 100 to 200rpm at 2 to 8 ℃ for more than 8 hours.
8. The method according to claim 6, wherein in step S2-3, the supernatant is removed by centrifugation, and the precipitate II is obtained after centrifugation for 3-8 times by washing with methanol and water alternately, wherein the centrifugation speed is 2000-4000 rpm and the centrifugation time is 2-3 min each time.
9. The use according to claim 6, wherein in step S2-3, the precipitate ii is immersed in methanol and subjected to an activation treatment at 120 ℃ for more than 8 hours under sealed conditions in a high temperature and high pressure reaction vessel, wherein the initial pressure in the high temperature and high pressure reaction vessel is normal pressure.
10. The method according to claim 6, wherein in step S2-3, the drying process is performed at a temperature of 80 ℃ or higher.
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