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 PDFInfo
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical class [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 72
- VZFRNCSOCOPNDB-AJKFJWDBSA-N domoic acid Chemical compound OC(=O)[C@@H](C)\C=C\C=C(/C)[C@H]1CN[C@H](C(O)=O)[C@H]1CC(O)=O VZFRNCSOCOPNDB-AJKFJWDBSA-N 0.000 claims abstract description 39
- VZFRNCSOCOPNDB-UHFFFAOYSA-N domoic acid Natural products OC(=O)C(C)C=CC=C(C)C1CNC(C(O)=O)C1CC(O)=O VZFRNCSOCOPNDB-UHFFFAOYSA-N 0.000 claims abstract description 38
- VZFRNCSOCOPNDB-OXYNIABMSA-N isodomoic acid D Natural products CC(C=C/C=C(/C)C1CNC(C1CC(=O)O)C(=O)O)C(=O)O VZFRNCSOCOPNDB-OXYNIABMSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005530 etching Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 53
- 238000005406 washing Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 claims description 6
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 4
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract 1
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- JVTMLBYYQYMFLV-UHFFFAOYSA-N 2-methyl-1h-imidazole;zinc Chemical compound [Zn].CC1=NC=CN1 JVTMLBYYQYMFLV-UHFFFAOYSA-N 0.000 description 2
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- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
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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
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)
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