CN114307973A - A kind of preparation method and application of post-modified ZIF-8 material - Google Patents

A kind of preparation method and application of post-modified ZIF-8 material Download PDF

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CN114307973A
CN114307973A CN202111655411.0A CN202111655411A CN114307973A CN 114307973 A CN114307973 A CN 114307973A CN 202111655411 A CN202111655411 A CN 202111655411A CN 114307973 A CN114307973 A CN 114307973A
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张兰
吴雅萍
陈晖�
丁青青
张文敏
李青青
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Fuzhou University
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Abstract

The invention discloses a preparation method and application of a post-modified ZIF-8 material. The material is based on a zeolite imidazole ester framework material, and post-modified ZIF-8 is prepared by acid etching. The etched ZIF-8 exposes more unsaturated Zn sites, has stronger adsorption effect on DA, has better dispersibility in water, is favorable for enriching domoic acid, and is detected by combining a liquid chromatogram-tandem triple quadrupole mass spectrometry. The post-modified ZIF-8 material prepared by the invention has the advantages of good thermal stability, rich adsorption active sites, large specific surface area, good selectivity and good dispersion in water, and the established method can be used for measuring domoic acid in a complex matrix. Therefore, the material has good application prospect in the field of analytical chemistry.

Description

Preparation method and application of post-modified ZIF-8 material
Technical Field
The invention particularly relates to a simple preparation method of a post-modified metal organic framework (ZIF-8) and application of the post-modified metal organic framework to separation and enrichment of domoic acid.
Background
Domoic Acid (DA) is a natural neurogenic amino acid produced primarily by certain marine diatoms of the genus prototheca and the genus rhomboheptum. The clam, mussel and fish in the water can enrich domoic acid generated by algae in the water, and have strong tolerance to the domoic acid, and the domoic acid can affect the ecological environment of the area after being enriched by a food chain, and cause the morbidity and mortality of animals. In addition, people eating poisoned shellfish can cause memory loss, dizziness, coma and even death. Therefore, the monitoring of domoic acid in water is necessary. However, the concentration of DA in a water sample is very low, and the matrix of the sample is relatively complex, so that the detection of the sample is difficult to a certain extent, and therefore, the sample needs to be pretreated to realize the enrichment and detection of trace DA in water.
The MOFs is a novel material formed by self-assembling organic ligands and metal ions or clusters through coordination bonds. Has the advantages of unsaturated metal sites, large specific surface area, structural and functional diversity and the like, and has important application in the fields of hydrogen storage, gas adsorption and separation, sensors, drug slow release, catalytic reaction and the like. However, most MOFs materials have poor stability in water, which greatly limits the development of MOFs materials. ZIF-8 consists of Zn and 2-methylimidazole, and has relatively high thermal and chemical stability compared with other MOFs. ZIF-8 has higher water stability and unsaturated Zn sites, so that the ZIF-8 has good adsorption effect and certain selectivity on DA. However, the ZIF-8 has poor dispersibility in an aqueous solution due to strong hydrophobicity, which is not favorable for the ZIF-8 to be applied to the enrichment of DA in water. Based on the method, the hydrophobicity of the ZIF-8 is changed through specific acid etching, the dispersibility of the ZIF-8 in water is enhanced, and more Zn sites are exposed. The specific acid of the invention is specifically selected from tannic acid, ascorbic acid and camphorsulfonic acid, the acids have hydroxyl groups and are similar to DA structures, and the molecular imprinting effect can be generated by etching ZIF-8 by using the acids, so that the enrichment effect of ZIF-8 on DA is improved.
Disclosure of Invention
The invention aims to provide a preparation method and application of a post-modified ZIF-8 material. The material is further etched on the basis of a 2-methylimidazole zinc salt material (ZIF-8) to obtain the ZIF-8 adsorption material with enhanced dispersibility. The built post-modified ZIF-8-SPE method enriches domoic acid and detects the domoic acid by a liquid chromatography-tandem triple quadrupole mass spectrometry (HPLC-MS/MS). According to the invention, through acid etching, the dispersibility of ZIF-8 in an aqueous solution is increased, more Zn sites are exposed, and the enrichment effect of ZIF-8 on DA is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a synthetic method of a post-modified ZIF-8 material is characterized in that the surface of a particle with a shimidazolium ester skeleton structure is negatively charged and a large number of carboxyl groups are introduced, and the method comprises the following steps:
(a) dispersing a ZIF-8 sample in 0.01-1g/L etching solution, and magnetically stirring for 10-120min at room temperature;
(b) the obtained product is centrifugally washed for 3 times by methanol;
(c) and drying the obtained solid for 24h at 60 ℃ to obtain the post-modified ZIF-8 material.
Further, the etching solution in the step (a) includes an aqueous solution containing tannic acid or ascorbic acid or camphorsulfonic acid.
Further, the rotation speed of the magnetic stirring in the step (a) is 600 rpm.
Further, the rotation speed of the centrifugal washing in the step (b) is 7000 rpm, and each washing time is 3 min.
Further, the preparation method of the ZIF-8 comprises the following steps:
(1) solution A: is provided with Zn (NO)3)2Performing ultrasonic treatment on the methanol solution to obtain a uniform solution;
(2) and B, liquid B: preparing a methanol solution containing 2-methylimidazole, adding 1-methylimidazole, and performing ultrasonic treatment to obtain a uniform solution;
(3) adding the solution B into the solution A, magnetically stirring for 20s, and standing at room temperature for 24 h;
(4) centrifugally washing the product obtained in the step (3) with methanol for 3 times, wherein the centrifugal rotation speed is 7000 rpm, and the washing time is 3 min each time;
(5) and drying the obtained solid for 24h at 60 ℃ to obtain the ZIF-8 material.
The post-modified ZIF-8 material prepared by the preparation method.
The application comprises the following steps: the obtained acid etched ZIF-8 material is used as an adsorbent, and is combined with HPLC-MS/MS to detect trace domoic acid in water.
The invention has the advantages that:
1) the preparation method is simple, the raw materials are easy to obtain and low in price, and the prepared post-modified 2-methylimidazole zinc salt material can quickly enrich the domoic acid.
2) The material obtained by the invention has excellent thermal stability, chemical stability and mechanical stability, and can be repeatedly used for many times.
3) The acid etching method provided by the invention increases the dispersibility of the ZIF-8 material in water, facilitates the contact of the material and a target object, and makes the adsorption effect more obvious.
4) The post-modified ZIF-8 material obtained by the invention has the advantages that a large number of unsaturated Zn sites are exposed on the surface, the interaction between the material and a target object is enhanced, and the material has a good enrichment effect on the target object.
5) The invention utilizes etched ZIF-8 material to extract domoic acid and realizes the detection of low-concentration DA in complex substrates (seawater and marine products) by combining with HPLC-MS/MS.
Drawings
FIG. 1 is a scanning electron micrograph of a ZIF-8 material.
FIG. 2 is a scanning electron micrograph of the post-modified ZIF-8 material prepared in example 4.
FIG. 3 shows Zeta potentials of (a) ZIF-8, (b) post-modified ZIF-8 prepared in example 1, and (c) post-modified ZIF-8 after DA adsorption.
FIG. 4 is XRD spectra of (a) ZIF-8, (b) post-modified ZIF-8 prepared in example 4, (c) post-modification prepared in example 5, and (d) post-modified ZIF-8 prepared in example 1.
FIG. 5 is a chromatogram showing (a) an eluate obtained after the post-modification ZIF-8 analysis prepared in example 1, (b) an eluate obtained after the ZIF-8 analysis, and (c) 5.0ng mL-1DA standard solution of (1).
FIG. 6 is a chromatogram obtained by labeling mussel at different concentrations, wherein (a) is not labeled, (b) is 10 pg/mL, (c) is 100 pg/mL, and (d) is 500 pg/mL.
FIG. 7 is contact angle charts of (a) ZIF-8, (b) post-modified ZIF-8 prepared in example 4, (c) post-modified ZIF-8 prepared in example 5, and (d) post-modified ZIF-8 prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are not intended to limit the invention, but are intended to facilitate the understanding thereof.
Example 1:
a synthetic method of a post-modified ZIF-8 material comprises the following steps:
1) preparing a ZIF-8 material:
(a) solution A: the 200.0 mL of the composition contained 2.9736g of Zn (NO)3)2Performing ultrasonic treatment for 5 min to obtain a uniform solution;
(b) and B, liquid B: preparing 200.0 mL of methanol solution containing 3.2424g of 2-methylimidazole, adding 3.2424g of 1-methylimidazole, and performing ultrasonic treatment for 5 min to obtain a uniform solution;
(c) adding the solution B into the solution A, magnetically stirring the mixed solution for 20s, and standing at room temperature for 24 h;
(d) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(e) and drying the obtained solid for 24h at 60 ℃ to obtain the ZIF-8 material.
2) Preparing a post-modification ZIF-8 material:
(a) dispersing 100.0 mg of the obtained ZIF-8 sample in 15mL of 0.5g/L camphorsulfonic acid solution, and magnetically stirring for 30min at room temperature, wherein the rotating speed of the magnetic stirring is 600 rpm;
(b) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(c) and drying the obtained solid for 24h at 60 ℃ to obtain the acid etched ZIF-8 material.
Example 2:
a synthetic method of a post-modified ZIF-8 material comprises the following steps:
1) preparing a ZIF-8 material:
(a) solution A: the 200.0 mL of the composition contained 2.9736g of Zn (NO)3)2Performing ultrasonic treatment for 5 min to obtain a uniform solution;
(b) and B, liquid B: preparing 200.0 mL of methanol solution containing 3.2424g of 2-methylimidazole, adding 3.2424g of 1-methylimidazole, and performing ultrasonic treatment for 5 min to obtain a uniform solution;
(c) adding the solution B into the solution A, magnetically stirring the mixed solution for 20s, and standing at room temperature for 24 h;
(d) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(e) and drying the obtained solid for 24h at 60 ℃ to obtain the ZIF-8 material.
2) Preparing a post-modification ZIF-8 material:
(a) dispersing 100.0 mg of the obtained ZIF-8 sample in 15mL of 1g/L camphorsulfonic acid solution, and magnetically stirring for 30min at room temperature, wherein the rotating speed of the magnetic stirring is 600 rpm;
(b) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(c) and drying the obtained solid for 24h at 60 ℃ to obtain the acid etched ZIF-8 material.
Example 3:
a synthetic method of a post-modified ZIF-8 material comprises the following steps:
1) preparing a ZIF-8 material:
(a) solution A: the 200.0 mL of the composition contained 2.9736g of Zn (NO)3)2Performing ultrasonic treatment for 5 min to obtain a uniform solution;
(b) and B, liquid B: preparing 200.0 mL of methanol solution containing 3.2424g of 2-methylimidazole, adding 3.2424g of 1-methylimidazole, and performing ultrasonic treatment for 5 min to obtain a uniform solution;
(c) adding the solution B into the solution A, magnetically stirring the mixed solution for 20s, and standing at room temperature for 24 h;
(d) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(e) and drying the obtained solid for 24h at 60 ℃ to obtain the ZIF-8 material.
2) Preparing a post-modification ZIF-8 material:
(a) dispersing 100.0 mg of the obtained ZIF-8 sample in 15mL of 0.5g/L camphorsulfonic acid solution, and magnetically stirring for 60min at room temperature, wherein the rotating speed of the magnetic stirring is 600 rpm;
(b) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(c) and drying the obtained solid for 24h at 60 ℃ to obtain the acid etched ZIF-8 material.
Example 4:
a synthetic method of a post-modified ZIF-8 material comprises the following steps:
1) preparing a ZIF-8 material:
(a) solution A: the 200.0 mL of the composition contained 2.9736g of Zn (NO)3)2Performing ultrasonic treatment for 5 min to obtain a uniform solution;
(b) and B, liquid B: preparing 200.0 mL of methanol solution containing 3.2424g of 2-methylimidazole, adding 3.2424g of 1-methylimidazole, and performing ultrasonic treatment for 5 min to obtain a uniform solution;
(c) adding the solution B into the solution A, magnetically stirring the mixed solution for 20s, and standing at room temperature for 24 h;
(d) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(e) and drying the obtained solid for 24h at 60 ℃ to obtain the ZIF-8 material.
2) Preparing a post-modification ZIF-8 material:
(a) dispersing 100.0 mg of the obtained ZIF-8 sample in 15mL of 0.5g/L tannic acid solution, and magnetically stirring for 30min at room temperature, wherein the magnetic stirring speed is 600 rpm;
(b) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(c) and drying the obtained solid for 24h at 60 ℃ to obtain the acid etched ZIF-8 material.
Example 5:
a synthetic method of a post-modified ZIF-8 material comprises the following steps:
1) preparing a ZIF-8 material:
(a) solution A: the 200.0 mL of the composition contained 2.9736g of Zn (NO)3)2Performing ultrasonic treatment for 5 min to obtain a uniform solution;
(b) and B, liquid B: preparing 200.0 mL of methanol solution containing 3.2424g of 2-methylimidazole, adding 3.2424g of 1-methylimidazole, and performing ultrasonic treatment for 5 min to obtain a uniform solution;
(c) adding the solution B into the solution A, magnetically stirring the mixed solution for 20s, and standing at room temperature for 24 h;
(d) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(e) and drying the obtained solid for 24h at 60 ℃ to obtain the ZIF-8 material.
2) Preparing a post-modification ZIF-8 material:
(a) dispersing 100.0 mg of the obtained ZIF-8 sample in 15mL of 0.5g/L ascorbic acid solution, and magnetically stirring for 30min at room temperature, wherein the rotating speed of the magnetic stirring is 600 rpm;
(b) centrifugally washing the obtained product with methanol for 3 times at 7000 rpm for 3 min;
(c) and drying the obtained solid for 24h at 60 ℃ to obtain the acid etched ZIF-8 material.
Examples of the applications
The solid-phase extraction of DA in water by using the ZIF-8 material etched by camphorsulfonic acid obtained in the example 1 is combined with HPLC-MS/MS, and the detection of DA is applied, and the specific steps are as follows:
(1) 40.0. mu.L of the DA standard solution was put into a 10.0 mL centrifuge tube to prepare 8.0 mL of 5 ppb DA standard solution.
(2) 8mg of the prepared camphorsulfonic acid etched ZIF-8 material was placed in 8.0 mL of 5 ppb DA standard solution in (1) and vortexed for 10 min.
(3) Centrifuging the suspension (7000 rpm, 3 min) to collect solid, adding 1 mL of eluent (3 mM histidine solution), vortexing for 5 min, centrifuging the suspension (7000 rpm, 3 min), and collecting supernatant; detection was performed using HPLC-MS/MS injection.
(4) Under the set chromatographic method, C is applied18(aq)Chromatographic column, mobile phase A is 0.1% formic acid water solution; b is 0.1% formic acid acetonitrile solution, A phase: phase B is 80%: 20%, the sample injection amount is 10.0 mu L, the flow rate of the mobile phase is 200.0 mu L/min, and the optimized mass spectrum conditions are as follows: ion source temperature: 300 ℃, sheath gas: 35, auxiliary gas: 10, capillary temperature: at 350 ℃.
The detection result is shown in fig. 5, the chromatographic peak response of DA in the eluate separated after the treatment of the camphorsulfonic acid etched ZIF-8 material is far higher than that of the DA standard substance, and the calculated recovery rate is 89.6%, which indicates that the material has excellent adsorption capacity for DA.
Comparative application example
Only replacing the camphorsulfonic acid etched ZIF-8 in the application example with the ZIF-8 material which is prepared in the step 1) in the embodiment 1 and is not etched by acid, and the other steps are the same as the application example.
The detection result is shown in fig. 5, the response of the chromatographic peak of DA in the eluent separated after the ZIF-8 material is treated is higher than that of the DA standard product, but is obviously lower than that of DA in the eluent separated after the ZIF-8 material is treated by camphorsulfonic acid etching, the calculated recovery rate is 61.8%, and the ZIF-8 exposes more adsorption sites after acid etching, so that the adsorption of DA is facilitated.
FIG. 1 is an SEM photograph of ZIF-8 prepared in step 1) of example 1, in which the prepared ZIF-8 particles are distinct and smooth in surface and have a size of about 3 μm.
FIG. 2 SEM picture of post-modified ZIF-8 prepared in example 4 shows that the surface of the etched ZIF-8 is rough and porous, which proves the success of the post-modified ZIF-8 preparation.
FIG. 3 shows that, as seen from the Zeta potential spectrum, the post-modified ZIF-8 prepared in example 1 has a significantly higher potential than ZIF-8 not subjected to acid etching, which increases from 20.5 to 29.7, and has better electropositivity, while the post-modified ZIF-8 has a significantly lower potential after adsorbing DA, indicating that the surface of the post-etched ZIF-8 has more Zn2+DA can be adsorbed by electrostatic interaction.
As shown in the XRD spectrum of fig. 4, the post-modified ZIF-8 prepared in examples 1, 4 and 5 still has strong diffraction peaks at the same positions, indicating that the crystal structure is not significantly changed by acid etching.
FIG. 5 is a graph showing adsorption effects, in which 8mL of 5.0ng/mL DA standard solution was subjected to adsorption treatment using 8mg of ZIF-8 and 8mg of post-modified ZIF-8 material prepared in example 1, respectively, and the results showed that the recovery rate of adsorption using ZIF-8 was 61.8%, and the recovery rate of adsorption using post-modified ZIF-8 prepared in example 1 was 89.6%
FIG. 6 shows that the labeling experiments were performed at 3 concentration levels of 10, 100 and 500pg/mL as indicated by the labeled chromatograms of mussels at different concentrations, and the labeled recovery rate was 88.5-97.6%, and the RSD was 6.5% or less (n = 5), indicating that the established method has good accuracy and repeatability.
FIG. 7 is a water contact angle diagram showing that the water contact angle of ZIF-8 is 78.3, and the water contact angles of post-modified ZIF-8 prepared in examples 1, 4 and 5 are 30.3, 32.4 and 60.3, respectively, indicating that the acid-etched ZIF-8 has better hydrophilicity and stronger dispersibility in water.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (8)

1.一种后修饰ZIF-8材料的制备方法,其特征在于,包括如下步骤:1. a preparation method of post-modified ZIF-8 material, is characterized in that, comprises the steps: (a) 将ZIF-8样品分散在0.01-1g/L的刻蚀溶液中,室温下磁力搅拌10-120min;(a) Disperse the ZIF-8 sample in 0.01-1 g/L etching solution and stir magnetically for 10-120 min at room temperature; (b) 所得产物经甲醇离心洗涤3次;(b) The obtained product was washed 3 times by methanol centrifugation; (c) 将所得固体60℃下干燥24 h,获得后修饰ZIF-8材料。(c) The obtained solid was dried at 60 °C for 24 h to obtain the post-modified ZIF-8 material. 2.根据权利要求1所述的制备方法,其特征在于,步骤(a)中的刻蚀溶液包括含有单宁酸或抗坏血酸或樟脑磺酸的水溶液。2 . The preparation method according to claim 1 , wherein the etching solution in step (a) comprises an aqueous solution containing tannic acid or ascorbic acid or camphorsulfonic acid. 3 . 3.根据权利要求1所述的制备方法,其特征在于,步骤(a)中磁力搅拌的转速为600rpm。3 . The preparation method according to claim 1 , wherein the rotational speed of the magnetic stirring in step (a) is 600 rpm. 4 . 4.根据权利要求1所述的制备方法,其特征在于,步骤(b)中离心洗涤的转速为7000rpm,每次洗涤时间为3 min。4 . The preparation method according to claim 1 , wherein in the step (b), the rotational speed of the centrifugal washing is 7000 rpm, and each washing time is 3 min. 5 . 5.根据权利要求1所述的制备方法,其特征在于,所述ZIF-8的制备方法包括以下步骤:5. preparation method according to claim 1, is characterized in that, the preparation method of described ZIF-8 comprises the following steps: (1) A液:配置含有Zn(NO3)2的甲醇溶液,超声得到均一溶液;(1) Liquid A: configure a methanol solution containing Zn(NO 3 ) 2 , and ultrasonically obtain a homogeneous solution; (2) B液:配置含有2-甲基咪唑的甲醇溶液,并加入1-甲基咪唑,超声得到均一溶液;(2) Liquid B: configure a methanol solution containing 2-methylimidazole, add 1-methylimidazole, and ultrasonically obtain a homogeneous solution; (3) 将B液加入A液中,磁力搅拌20s之后,室温静置24h;(3) Add solution B to solution A, stir magnetically for 20s, and let stand for 24h at room temperature; (4) 将步骤(3)所得产物用甲醇离心洗涤3次,离心转速为7000 rpm,每次洗涤时间为3min;(4) The product obtained in step (3) was centrifuged and washed 3 times with methanol, and the centrifugal speed was 7000 rpm, and each washing time was 3 min; (5) 将所得固体60℃下干燥24 h,获得ZIF-8材料。(5) The obtained solid was dried at 60 °C for 24 h to obtain ZIF-8 material. 6.如权利要求1-5任一项所述的制备方法制得的后修饰ZIF-8材料。6. The post-modified ZIF-8 material prepared by the preparation method according to any one of claims 1-5. 7.如权利要求6所述的后修饰ZIF-8材料在富集软骨藻酸中的应用。7. The application of the post-modified ZIF-8 material as claimed in claim 6 in enriching domoic acid. 8.如权利要求6所述的后修饰ZIF-8材料的应用,其特征在于:所述后修饰ZIF-8材料用做吸附剂,通过与HPLC-MS/MS联用,检测水中痕量软骨藻酸。8. The application of the post-modified ZIF-8 material as claimed in claim 6, wherein the post-modified ZIF-8 material is used as an adsorbent, and is used in conjunction with HPLC-MS/MS to detect trace cartilage in water Alginic acid.
CN202111655411.0A 2021-12-31 2021-12-31 A kind of preparation method and application of post-modified ZIF-8 material Pending CN114307973A (en)

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