CN113522363B - Preparation method and application of metal ion modified MOF micro/nano structure in hydrogel - Google Patents
Preparation method and application of metal ion modified MOF micro/nano structure in hydrogel Download PDFInfo
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 35
- 239000000017 hydrogel Substances 0.000 title claims abstract description 32
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 31
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
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- 238000003756 stirring Methods 0.000 claims description 8
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 abstract 3
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- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 6
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Abstract
The invention discloses a preparation method and application of a metal ion modified MOF micro/nano structure in hydrogel, belonging to the field of organic nano photocatalysis. The invention makes porphyrin ligand react with metal cluster to obtain porphyrin MOF micro/nano structure, then mixes it with Sodium Alginate (SA) water solution, freezes and shapes, and places in excess divalent metal salt (M) 2+ ) The solution is crosslinked and solidified to obtain SA-M 2+ -MOF hydrogel spheres. By utilizing the method of coordinating the cross-linked metal ions and porphyrin molecules, the MOF micro/nano structure is effectively modified and is uniformly and firmly embedded into the SA hydrogel spherical frameworkIn particular, the recyclability is improved. The method is simple and feasible, and provides experimental basis for controllable and integral assembly of the organic nano material. By subjecting the obtained SA-M to 2+ The application of MOF in photocatalytic degradation of organic dyes is studied, and the result shows that the structure has high-efficiency photocatalytic activity. Provides possibility for being widely applied to pollution control and energy exhaustion.
Description
Technical Field
The invention belongs to the field of organic nano photocatalysis, and particularly relates to a preparation method and application of a metal ion modified porphyrin MOF micro/nano structure in hydrogel.
Background
With the development of economic society, fossil energy is widely used and consumed, environmental pollution threatening human survival and energy crisis are increasingly severe, and a low-cost clean renewable energy source is needed to be found, and the environmental problem is solved by using a novel efficient technology.
Compared with inorganic semiconductor materials, the Organic semiconductor photocatalyst has lower price and simpler and more convenient preparation process, and shows excellent visible light catalytic pollutant degradation performance due to structural diversity and wide solar spectrum absorption (Organic Photocatalysts for the Oxidation of Pollutants and Model Compounds, M.Luisa Marin, lucas Santos-Juananes, antonio arrays, CHEMICAL REVIEWS,2011, 1710-1747.). In recent years, metal-organic frameworks (MOFs) have helped researchers design photocatalysts (CO-organic frameworks) from the chemical structure level due to their unique structural advantages, such as porosity, structural adjustability, functionability, etc 2 reduction and photodegradation OF organic dies.Ch.Venkata Red, kakarla Raghava Red, V.V.N.Harish.INTERNATIONAL JOURNAL OF HYDROGEN ENGY, 2020, 7656-7679.) the specific surface area OF the organic structure after nanocrystallization is large, the porosity is high, and more external substances can be adsorbed for degradation; the carrier mobility is improved, and better degradation capability can be shown; solves the problem of recycling the active molecules of the organic homogeneous system,the reuse rate of the material system is improved.
The porphyrin MOF serving as a novel photocatalyst with good photoelectric property has the unique advantages of widening the spectral response range of porphyrin and reducing the photo-generated electron-hole recombination rate, and also has the advantages of multiple pores, adjustable pore size and large specific surface area of the MOF material. More and more researches show that the nano-modification can modify the morphology of the porphyrin MOF, reduce the size and improve the degradation efficiency, and the recycling rate (Metal-Organic structures for the application of distance between active sites in the Organic photo-catalysis. Gong X, shu Y, jiang Z. ANGE WANDTE CHEMIE,2020, 5326-5331.) but the MOF powder has poor recoverability, and the MOF loaded hydrogel synthesized by various methods has poor overall performance and the MOF falls off.
At present, no literature and patent reports exist about a preparation method of metal ion modified MOF micro/nano structures in hydrogel, and the application of the metal ion modified MOF micro/nano structures in the field of photocatalysis is proposed.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a preparation method of metal ion modified MOF micro/nano structures in hydrogel. Aiming at the problems of overlarge aggregate size, imperfect crystal form and the like caused by an excessively fast self-assembly process in the existing preparation method of the MOF nano structure, the invention provides a preparation method of a metal ion modified MOF micro/nano structure in hydrogel, which can effectively control the appearance and size, perfect the crystal form and pore structure and improve the dispersibility and recoverability of the crystal form and pore structure.
The second technical problem to be solved by the invention is to provide an application of porphyrin MOF hydrogel.
The invention solves the first technical problem, and adopts a preparation method of metal ion modified MOF micro/nano structure in hydrogel, which is characterized in that the preparation process is as follows: obtaining a porphyrin MOF micro/nano structure through traditional solvothermal reaction, then mixing the porphyrin MOF micro/nano structure with an SA aqueous solution, uniformly stirring, freezing and shaping, and placing in an excessive divalent metal salt solution for crosslinking and curing to obtain SA-M 2+ -MOF hydrogel spheres.
The preparation method of the metal ion modified MOF micro/nano structure in the hydrogel is characterized by comprising the following steps:
s1: preparation of porphyrin MOF micro/nano structures
Reacting ZrCl 4 And Porphyrin (TCPP) matrix are dissolved in N, N-Dimethylformamide (DMF), acetic acid and deionized water are added, the mixture is stirred uniformly at room temperature, and then the uniform solution is heated for 5 to 15 hours at the temperature of 100 to 200 ℃.
S2: preparation of SA-M by metal ion modification method 2+ -MOF hydrogel spheres:
dispersing the prepared porphyrin MOF micro/nano structure in deionized water, uniformly mixing with an SA aqueous solution, freezing and shaping the mixed solution, and then placing the frozen and shaped mixed solution into 10-100ml of metal salt solution for crosslinking and solidification.
Further, the porphyrin molecule described in S1 is 5,10,15,20-tetrakis- (4-carboxyphenyl) porphyrin (TCPP).
Further, zrCl is contained in S1 4 And TCPP in an amount of 0 to 20mg, and DMF in an amount of 1 to 10mL, respectively.
Furthermore, the addition amount of SA in S2 is 10-100mg, and the addition amount of porphyrin MOF is 1-10mg.
Further, the intercalation ions in S2 are Zn 2+ 、Co 2+ 、Cu 2+ 、Fe 2+ 、Pt 2+ 、Ru 2+ 、Ba 2+ 、Pb 2+ 、Ra 2+ 、Sn 2 + 、Mn 2+ 、Ni 2+ Divalent metal cations are equal, the concentration of the metal ions is 0.1-0.5mol/L, and the volume is 10-100mL.
Further, the stirring is magnetic stirring, and the stirring time is 5-30 minutes.
Further, the resulting porphyrin MOF micro/nano-structure size in S2 is about 50-5000nm, SA-M 2+ The MOF hydrogel is spherical in shape.
In order to solve the second technical problem, the SA-M of the invention 2+ -MOF hydrogel spheres are used as photocatalysts in the photodegradation of organic substances.
The invention has the advantages of
1. The invention obtains the porphyrin MOF micro/nano structure with uniform appearance and size by a simple and easy solvothermal reaction method.
2. SA-M obtained by simple and easy metal ion modification method 2+ The MOF hydrogel spheres show high-efficiency photocatalytic performance in the application of degrading Methylene Blue (MB), and the overall structure of the hydrogel spheres greatly improves the recyclability of the photocatalyst.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of porphyrin MOF micro/nano structures prepared by the conventional solvothermal reaction in example 1.
FIG. 2 Zn in example 2 2+ Preparation of SA-M as modified Metal ion 2+ Photographs of MOF hydrogel spheres.
FIG. 3 Zn in example 2 2+ Preparation of SA-M as modified Metal ion 2+ -Scanning Electron Microscopy (SEM) pictures of MOF hydrogel microspheres.
FIG. 4. Conventional solvothermal reaction of porphyrin MOF micro/nano-structures prepared in example 1 and Zn in example 2 2+ SA-M prepared as modified metal ion 2+ -graph of the effect of photocatalytic degradation of MB by MOF hydrogel spheres.
Detailed Description
Example 1:
the porphyrin used in this example was TCPP, provided by bekkera technologies ltd, and was not further processed before use, and its structural formula is shown in formula 1:
the preparation method comprises the following specific steps:
1) 0-20mg of ZrCl 4 And 0-20mg TCPP dissolved in 1-10mL DMF solutionThen 50-200. Mu.L of acetic acid and 10-100. Mu.L of deionized water are added.
2) The mixed solution was magnetically stirred at room temperature for 5-30 minutes, and then the solution was sealed and heated at 100-200 ℃. After 5-15 hours of reaction, centrifuging, drying and collecting samples. The size of the porphyrin MOF can be seen in FIG. 1 as 100-800nm.
And (3) performance testing:
1) Weighing 1-20mg of porphyrin MOF powder collected by traditional solvothermal reaction, adding into 10-100mL of MB solution with concentration of 0.01-0.1mM, performing adsorption-desorption balance under dark condition, and simulating sunlight (illumination intensity of 100 mW/cm) 2 ) Irradiating for 100 minutes, sampling every 10 minutes, and performing ultraviolet-visible absorption spectrum test; the results of testing the performance for the samples prepared in example 1 are shown in fig. 4.
Example 2:
1) Preparing Zn with excessive concentration 2+ 10-100ml of salt solution, weighing 10-100mg of SA powder and 1-10ml of deionized water. 1-10mg of the porphyrin MOF powder obtained in example 1 was weighed, and 1-10ml of water was added to prepare a MOF dispersion.
2) Mixing the SA water solution in the step 1) with the porphyrin MOF dispersion liquid, stirring for 5-30 minutes, freezing and shaping, and adding Zn in the step 1) 2+ In salt solution, obtained SA-M 2+ See FIGS. 2 and 3 for MOF hydrogel spheres.
And (4) performance testing:
1) SA-M obtained by modifying metal ions 2+ -adding MOF hydrogel spheres into 10-100mL of 0.01-0.1mM MB solution, and after carrying out adsorption-desorption equilibrium under dark conditions, simulating sunlight (illumination intensity of 100 mW/cm) 2 ) Irradiating for 100 minutes, sampling every 10 minutes, and performing ultraviolet-visible absorption spectrum test; the results of testing the performance for the samples prepared in example 1 are shown in fig. 4.
Example 3:
example 2 was repeated, with the only difference that the metal ion in step 1) was Co 2+ 。
Example 4:
example 2 was repeated, with the only difference that the metal ion in step 1) was cu 2+ 。
Example 5:
example 2 was repeated with the only difference that in step 1) the metal ion was Fe 2+ 。
Example 6:
example 2 was repeated, with the only difference that in step 1) the metal ion was Pt 2+ 。
Example 7:
example 2 was repeated, with the only difference that in step 1) the metal ion was Ru 2+ 。
Example 8:
example 2 was repeated with the only difference that in step 1) the metal ion was Ba 2+ 。
Example 9:
example 2 was repeated, with the only difference that in step 1) the metal ion was Pb 2+ 。
Example 10:
example 2 was repeated, with the only difference that in step 1) the metal ion was Ra 2+ 。
Example 11:
example 2 was repeated, with the only difference that in step 1) the metal ion was Sn 2+ 。
Example 12:
example 2 was repeated with the only difference that in step 1) the metal ion was Mn 2+ 。
Example 13:
example 2 was repeated, with the only difference that in step 1) the metal ion was Ni 2+ 。
By comparing the examples 1 and 2, it can be seen that the self-assembly structure of the porphyrin MOF molecules can be effectively improved through ion modification, and the ion modification has important effects on reducing the size of the structure and perfecting the crystal form, thereby improving the photocatalytic activity and the recycling performance of the photocatalyst.
Claims (4)
1. A preparation method of metal ion modified MOF micro/nano structure in hydrogel is characterized by comprising the following steps:
s1: preparation of porphyrin MOF micro/nano structures
Reacting ZrCl 4 Dissolving porphyrin matrix in N, N-dimethylformamide, adding acetic acid and deionized water, stirring at room temperature, and heating the uniform solution at 100-200 deg.C for 5-15 hr; the porphyrin matrix is 5,10,15, 20-tetra- (4-carboxyphenyl) porphyrin; zrCl in S1 4 And 5,10,15, 20-tetra- (4-carboxyphenyl) porphyrin in an amount of 0-20mg respectively, and N, N-dimethylformamide in an amount of 1-10mL;
s2: preparation of SA-M by metal ion modification method 2+ -MOF hydrogel spheres
Dispersing the porphyrin MOF micro/nano structure obtained in the S1 in water, mixing with the SA aqueous solution, uniformly stirring at room temperature, freezing and shaping, and placing in an excessive divalent metal salt solution for crosslinking and curing to obtain SA-M 2+ -MOF hydrogel spheres;
the addition amount of SA is 10-100mg, and the addition amount of the porphyrin MOF micro/nano structure is 1-10mg;
the concentration of metal ions in the divalent metal salt solution is 0.1-0.5mol/L, and the volume of the divalent metal salt solution is 10-100 mL; the metal ion is Zn 2+ 、Co 2+ 、Cu 2+ 、Fe 2+ 、Mn 2+ 、Ni 2+ Any one of them.
2. The method for preparing the metal ion modified MOF micro/nano structure in the hydrogel according to claim 1, wherein the stirring in the steps S1 and S2 is magnetic stirring, and the stirring time is 5-30 minutes.
3. The method for preparing metal ion modified MOF micro/nano-structures in hydrogel according to claim 1, wherein the obtained porphyrin MOF micro/nano-structures have the size of 50-5000nm, and SA-M 2+ The MOF hydrogel is spherical in shape.
4. SA-M obtained by the production method according to claim 1 2+ -use of MOF hydrogel spheres, characterized in that said SA-M 2+ The MOF hydrogel spheres are used as a photocatalyst for photocatalytic degradation of organic matters.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018135200A1 (en) * | 2017-01-17 | 2018-07-26 | 日産化学工業株式会社 | Composition comprising hydrophobic cluster and saccharides |
| CN109320733A (en) * | 2018-10-29 | 2019-02-12 | 广西大学 | A kind of method that magnanimity prepares MOFs@natural polymer advanced composite material (ACM) |
| CN109535436A (en) * | 2018-12-27 | 2019-03-29 | 武汉大学 | A kind of metalloporphyrin frame material and its preparation method and application with hollow nanostructures |
| CN109999915A (en) * | 2019-04-28 | 2019-07-12 | 大连民族大学 | One kind being used for CO2The porphyryl metal-organic framework materials and preparation method thereof of cyclisation catalysis reaction |
| CN110951088A (en) * | 2019-12-13 | 2020-04-03 | 安徽大学 | Zirconium-based metal organic framework material, preparation and application as chromium removal agent |
| CN112871146A (en) * | 2021-01-14 | 2021-06-01 | 常州大学 | Bifunctional metal-organic framework material modified composite membrane and preparation method and application thereof |
-
2021
- 2021-06-29 CN CN202110732145.0A patent/CN113522363B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018135200A1 (en) * | 2017-01-17 | 2018-07-26 | 日産化学工業株式会社 | Composition comprising hydrophobic cluster and saccharides |
| CN109320733A (en) * | 2018-10-29 | 2019-02-12 | 广西大学 | A kind of method that magnanimity prepares MOFs@natural polymer advanced composite material (ACM) |
| CN109535436A (en) * | 2018-12-27 | 2019-03-29 | 武汉大学 | A kind of metalloporphyrin frame material and its preparation method and application with hollow nanostructures |
| CN109999915A (en) * | 2019-04-28 | 2019-07-12 | 大连民族大学 | One kind being used for CO2The porphyryl metal-organic framework materials and preparation method thereof of cyclisation catalysis reaction |
| CN110951088A (en) * | 2019-12-13 | 2020-04-03 | 安徽大学 | Zirconium-based metal organic framework material, preparation and application as chromium removal agent |
| CN112871146A (en) * | 2021-01-14 | 2021-06-01 | 常州大学 | Bifunctional metal-organic framework material modified composite membrane and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| "Highly Stable Zr(IV)-Based Porphyrinic Metal-Organic Frameworks as an Adsorbent for the Effective Removal of Gatifloxacin from Aqueous Solution";chen Jing-Jing et al.，;《Molecules》;20180418;第23卷(第4期);第1-11页 * |
| "Photocatalyticbehaviour of zinc tetraamino phthalocyanine-silver nanoparticles immobilized on chitosan beads";Khoza Phindile et al.，;《Journal of Molecular Catalysis A: Chemical》;20150130;第399卷;第25-32页 * |
| "Preparation of Highly Porous Metal-Organic Framework Beads for Metal Extraction from Liquid Streams";Yang Shuliang et al.;《Journal of the American Chemical Society》;20200711;第142卷(第31期);第13415-13425页 * |
| "Preparation of Highly Porous Thiophene-Containing DUT-68 Beads for Adsorption of CO2 and Iodine Vapor";Xiao, Songtao et al.;《POLYMERS》;20211124;第13卷(第23期);文献号4075 * |
| "锆基金属有机骨架材料及其吸附气体的综述";武越等;《广东化工》;20200528;第47卷(第10期);第69-71+84页 * |
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