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CN116440876A - Amidoxime MOFs composite membrane material, and preparation method and application thereof - Google Patents

Amidoxime MOFs composite membrane material, and preparation method and application thereof Download PDF

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Publication number
CN116440876A
CN116440876A CN202310573616.7A CN202310573616A CN116440876A CN 116440876 A CN116440876 A CN 116440876A CN 202310573616 A CN202310573616 A CN 202310573616A CN 116440876 A CN116440876 A CN 116440876A
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pan
uio
composite membrane
membrane material
dimethylformamide
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Inventor
李祎亮
毕常芬
侯文彬
尚海花
魏会强
宁洪鑫
勾文峰
郭江红
陈乐园
李敏
侯越
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Institute of Radiation Medicine of CAMMS
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/44—Materials comprising a mixture of organic materials
    • B01J2220/445—Materials comprising a mixture of organic materials comprising a mixture of polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds

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Abstract

The invention provides an amidoxime MOFs composite membrane material and a preparation method thereof, wherein the preparation method comprises the following steps: the cyano-modified metal-organic framework composite membrane material is obtained by combining an electrostatic spinning technology and an in-situ growth method; and then implementing the construction of the target composite membrane material through amidoxime reaction. The method has the advantages of simplicity, easiness in industrial application and the like. The amidoxime metal-organic framework composite membrane material prepared by the invention has good removal efficiency for uranyl ions in water, and has good application value.

Description

Amidoxime MOFs composite membrane material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano material preparation and application, relates to a metal uranium purification technology, and in particular relates to a novel amidoxime MOFs composite membrane material which has various advantages of MOFs materials and membrane materials and shows good adsorption performance and application prospects in separating uranium in water.
Background
The report of the "energy technical prospect 2020" issued by the International Energy Agency (IEA) shows that nuclear energy is an efficient and clean energy source, and is indispensable in future global energy layout and transformation. Uranium is an indispensable important strategic resource in the development of the nuclear industry. The seawater contains about 45 hundred million tons of rich uranium resources which are 1000 times of land uranium resources. But the concentration of uranium in seawater is as low as-3 ppb, and the uranium is matched with carbonate to form a compact complex. Therefore, reasonable recovery of uranium from low-concentration seawater is very important, and various methods for recovering uranium from seawater, such as adsorption, filtration and electrolysis, have the advantages of low cost, simple operation, high efficiency and the like. Therefore, the research and development of the uranium extraction material from the seawater has important significance.
Metal organic frameworks (Metal Organic Frameworks, MOFs) are a classCrystalline porous materials having a periodic network structure. MOFs have an ultra-high specific surface area (somewhat in excess of 6000m compared to conventional porous materials 2 And (g) and porosity (up to 90% free volume), pore size adjustability, topological diversity, predictability, etc., and exhibit great potential applications in the radionuclide adsorption and separation fields. Since the first use of MOFs (UiO-68) to separate uranium from water by the 2013 Lin Wen group, researchers have developed a variety of MOFs or derivatized adsorbent materials, such as ZIF-90-AO, PN-PCN-222, using strategies such as group chelating (carboxyl, phosphate, amidoxime, etc.), spatial structure selective recognition, reduction, and the like. Among them, uiO-66 series MOFs materials are resistant to strong acids and medium basicities, and are receiving extensive attention from researchers. For example, feng et al utilized the tunability of MOFs to introduce selective recognition sites in the structure, prepared MUU re Has uranium adsorption selectivity 18.38 times higher than that of vanadium; yuan et al, inspired by the binding of SUP protein to uranium, prepared for the first time UiO-66-3C4N containing a nanoflake, which showed a high adsorption capacity of 6.85mg/g in natural seawater. Although significant progress has been made in the UiO-66 series MOFs adsorbent materials, the powdered UiO-66 series materials also present problems of difficult recovery, easy agglomeration, and clogging of the tubing, which are a great challenge for future practical use. The electrostatic spinning is a mature technology capable of directly and continuously preparing nano/microfibers, and has the advantages of low cost, simple operation, strong functionality and the like. Obtaining the integral MOFs composite nanofiber membrane through the electrospinning technology and combining other preparation methods (mixed matrix method, in-situ growth method, secondary growth method and the like) is considered to be an effective way for widening the application of MOFs.
In view of this, the invention adopts a method of combining electrostatic spinning and in-situ growth to anchor UiO-66 nano particles on PAN, and then obtains the UiO-66-NH (AO)/PAO composite membrane material after amidoxime functionalization. The influence of the pH, adsorption time, initial concentration and the like of the solution on the adsorption effect of the material is explored by adopting a static method, and the adsorption kinetics and thermodynamic model is analyzed to further clarify the adsorption mechanism of the material on uranyl ions.
Noun interpretation in the present invention: MOFs are abbreviations for metal-organic frameworks (english name Metal Organic Frameworks), PAN is abbreviations for Polyacrylonitrile (english name polyacrylonitriles), DMF is abbreviations for N, N-Dimethylformamide (english name N).
Disclosure of Invention
Aiming at the defects of the amidoxime base material for adsorbing uranium in the prior art, the invention aims to provide a novel amidoxime base MOFs composite membrane material (UiO-66-NH (AO)/PAO), which utilizes a polymer as a substrate to anchor MOFs, so that the recoverability of the MOFs material is greatly improved.
A second object of the present invention is to provide a method for preparing a composite membrane material, which is simple in steps and easy for industrial application.
The invention provides an application of the amidoxime MOFs composite membrane material in the aspects of uranium adsorption of uranium-containing wastewater or seawater, and the amidoxime MOFs composite membrane material has high selective adsorption of uranium in the seawater, is high in adsorption capacity and adsorption rate, can be reused, and is suitable for extracting uranium in the seawater.
The invention discloses an amidoxime MOFs composite membrane material, the preparation flow of which is shown in figure 4 of the specification, and the preparation method is as follows:
adding PAN into N, N-dimethylformamide, and electrospinning to obtain a PAN fiber membrane; PAN fiber film, zrCl 4 ·8H 2 Dispersing O, 12- (2-cyanoethyl) amino terephthalic acid in a mixed solution containing organic acid and N, N-dimethylformamide, and carrying out solvothermal reaction to obtain MOFs composite membrane material UiO-66-NH (CN)/PAN; uiO-66-NH (CN)/PAN, NH 2 OH·HCl、Et 3 N is added into ethanol solution for reaction to obtain MOFs composite membrane material UiO-66-NH (AO)/PAO.
Further, the amidoxime group MOFs composite membrane material disclosed by the invention is prepared by the preparation method as follows:
adding PAN into N, N-dimethylformamide, stirring, electrospinning to obtain PAN fiber membrane, and drying; PAN fiber film, zrCl 4 ·8H 2 Dispersing O, 12- (2-cyanoethyl) amino terephthalic acid in a mixed solution containing organic acid and N, N-dimethylformamide, and a solventAfter the thermal reaction, N, N-dimethylformamide, water and ethanol are washed and dried in sequence to obtain MOFs composite membrane material UiO-66-NH (CN)/PAN; uiO-66-NH (CN)/PAN, NH 2 OH·HCl、Et 3 Adding N into ethanol solution for reaction, cooling, washing with ethanol and water, and drying to obtain MOFs composite membrane material UiO-66-NH (AO)/PAO.
The preparation method is characterized in that the dosage ratio of PAN to N, N-dimethylformamide is 1: (3-27), preferably 1:9.
The preparation method comprises the steps that the organic acid in the mixed solution is selected from any one or a mixture of a plurality of acetic acid and trifluoroacetic acid; the volume ratio of the organic acid to the N, N-dimethylformamide is 1:2;
the preparation method is characterized in that the solvothermal reaction temperature is 90-120 ℃ and the reaction time is 9-24 hours.
The application of the composite membrane material in preparing the amidoxime functionalized metal-organic framework material is provided.
The composite membrane material of the invention is used in the nuclear industry, in particular in uranium separation, for example for separating uranium from water.
Furthermore, the invention discloses the adsorption performance of the composite membrane material I on uranium in the water body.
Still further, the composite material I of the present invention includes, but is not limited to, the following advantages:
(1) The macroscopic membrane material is easy to separate;
(2) Multi-site modification shows higher adsorption capacity.
Drawings
FIG. 1 is an SEM diagram of PAN, uiO-66-NH (CN)/PAN, uiO-66-NH (AO)/PAO, and an EDS diagram of UiO-66-NH (AO)/PAO;
FIG. 2 XRD patterns (a) of PAN, uiO-66-NH (CN)/PA and UiO-66-NH (AO)/PAO, 2- (2-cyanoethyl) amino terephthalic acid and 2-amino terephthalic acid 1 H NMR chart (b), FT-IR chart (c) of PAN, uiO-66-NH (CN)/PAN and UiO-66-NH (AO)/PAO;
FIG. 3 is a graph (a) of UiO-66-NH (CN)/PAN and UiO-66-NH (AO)/PAO removal efficiency at different pH values, a graph (b) of UiO-66-NH (AO)/PAO adsorption capacity to U (VI) at different adsorption times, and a graph (c) of UiO-66-NH (AO)/PAO adsorption capacity at different initial uranium concentrations;
fig. 4 is a flow chart of the composite material I fabrication process of the present invention.
Detailed Description
The following specific examples are intended to further illustrate the present invention, but not to limit the scope of the claims.
Example 1 preparation of PAN fiber membranes
1.0g of PAN was added to 9.0g of DMF and stirred overnight. The PAN spinning solution was electrospun at a voltage of 50 kv, the distance between the two electrode wires was set to 16cm, and the speed of the vessel was set to 40 mm/s. In the electrospinning process, the humidity and temperature were 18±2% and 20±5%, respectively. Drying in vacuum at 80 ℃ to obtain the PAN fiber membrane.
Example 2 preparation of PAN fiber membranes
1.0g of PAN was added to 27.0g of DMF and stirred overnight. The PAN spinning solution was electrospun at a voltage of 50 kv, the distance between the two electrode wires was set to 16cm, and the speed of the vessel was set to 40 mm/s. In the electrospinning process, the humidity and temperature were 18±2% and 20±5%, respectively. Drying in vacuum at 80 ℃ to obtain the PAN fiber membrane.
Example 3 preparation of PAN fiber membranes
1.0g of PAN was added to 3.0g of DMF and stirred overnight. The PAN spinning solution was electrospun at a voltage of 50 kv, the distance between the two electrode wires was set to 16cm, and the speed of the vessel was set to 40 mm/s. In the electrospinning process, the humidity and temperature were 18±2% and 20±5%, respectively. Drying in vacuum at 80 ℃ to obtain the PAN fiber membrane.
Example 4 preparation of UiO-66-NH (CN)/PAN composite fiber film
30mg of the PAN fibrous membrane of example 1, 0.97g ZrCl 4 1.03g of 2- (2-cyanoethyl) amino terephthalic acid was dispersed in 30mL of a mixed solution of acetic acid and water (v Second step /v Water and its preparation method Ultrasound 30min in 1:2), reaction at 100deg.C for 24h. Sequentially washing with DMF, water and ethanol, and vacuum drying at 80deg.C to obtain (UiO-66-NH (CN)/PAN)A composite fiber membrane.
Example 5 preparation of UiO-66-NH (AO)/PAO composite fiber Membrane
30mg of UiO-66-NH (CN)/PAN, 0.75g of NH 2 OH·HCl、1.09g Et 3 Adding N into 7.5mL of ethanol solution, reacting for 24 hours at 75 ℃, naturally cooling to room temperature, washing with ethanol and water for several times, and vacuum drying at 80 ℃ to obtain the UiO-66-NH (AO)/PAO composite membrane material, namely the composite membrane material I.
Example 6 characterization of materials
Instrument model: TESCAN MIRA LMS scanning electron microscope, rigaku Smartlab SE multifunctional X-ray diffractometer, bruker AV-300 nuclear magnetic resonance spectrometer, thermo Scientific Nicolet iS Fourier transform infrared spectrometer.
The PAN fiber membrane of example 1, the UiO-66-NH (CN)/PAN composite fiber membrane of example 2, and the UiO-66-NH (AO)/PAO composite fiber membrane of example 3 were SEM and EDS characterized according to the prior art. The results are shown in figure 1 of the specification. From fig. 1a, d and g, it can be seen that the PAN nanofibers prepared by electrospinning have a relatively uniform thickness. From fig. 1b, e and h, it can be seen that the metal-organic framework material UiO-66-NH (CN) on the UiO-66-NH (CN)/PAN prepared by the in-situ growth method is uniformly coated on the surface of the PAN fiber. From fig. 1c, f, i it can be seen that the amidoxime-functionalized modified metal-organic framework material is still coated on the surface of the fiber, possibly because of heating, the fiber swells and thickens, but the material still integrates into a film-like structure.
The PAN fiber membrane of example 1, the UiO-66-NH (CN)/PAN composite fiber membrane of example 2, and the UiO-66-NH (AO)/PAO composite fiber membrane of example 3 were XRD, FT-IR, BET and TGA characterized as per the prior art method. The results are shown in figure 2 of the specification. As can be seen from FIG. 2a, the prepared UiO-66-NH (CN)/PAN has four characteristic peaks at 7.4 DEG, 8.5 DEG and 25.7 DEG, representing corresponding four crystal planes (111), (002) and (006), respectively, consistent with the literature report, indicating that the UiO-66 was successfully prepared. After amidoxime functionalization modification, uiO-66 still maintains excellent stability. The 2- (2-cyanoethyl) amino terephthalic acid referred to in example 2 was subjected to 1 H NMR characterization. The results are shown in figure 2b of the specification. By 2-amino groupsThe 2- (2-cyanoethyl) amino terephthalic acid ligand is successfully synthesized by taking phthalic acid as a raw material. 1 H NMR (400 mhz, dmso-d 6) δ=13.17 (s, 2H), 8.09 (s 1H), 7.91 (d, 1H), 7.31 (d, 1H), 7.15 (dd, 1H), 3.59 (s, 2H), 2.84 (t, 2H). From FIG. 2c, 2240cm is observed -1 The characteristic absorption peak of the nearby cyano group completely disappears after the amidoxime reaction, and the cyano group is successfully converted into an amidoxime group.
Example 7 uranium adsorption Performance test of Material
Instrument model: nexion 2000
The UiO-66-NH (CN)/PAN composite fiber membrane of example 2 and the UiO-66-NH (AO)/PAO composite fiber membrane of example 3 were subjected to measurement of uranium removal efficiency at different pH values. As shown in the figure 3a of the specification, the UiO-66-NH (AO)/PAO composite fiber membrane has good adsorption effect on uranium at the pH value of 4-9, and the removal efficiency is more than 96.4%. The uranium removal efficiency of the UiO-66-NH (CN)/PAN composite fiber membrane increased with increasing pH of the solution, but the highest removal efficiency was 46.6%. The UiO-66-NH (AO)/PAO composite fiber membrane of example 3 was subjected to the measurement of adsorption capacity under different adsorption time conditions. As shown in the figure 3b of the specification, at 27h, the adsorption of uranium by the UiO-66-NH (AO)/PAO composite fiber membrane reaches the equilibrium A. And carrying out model fitting on adsorption kinetics pseudo-first-order, pseudo-second-order and Intraparticle diffusion on the material, wherein the fitting curve variance of a Intraparticle diffusion model of the material is 0.998, which indicates that the adsorption kinetics model of the material is closer to a Intraparticle diffusion model, and indicates that adsorption of uranium on a UiO-66-NH (AO)/PAO composite fiber membrane and inner diffusion of uranyl ions are the main rate control step. The UiO-66-NH (AO)/PAO composite fiber membranes of example 3 were subjected to adsorption capacity measurements at different initial uranium concentrations. As a result, as shown in FIG. 3c of the specification, at a pH of the solution of 8.0, the adsorption amount increased significantly as the initial uranium concentration increased gradually from 2.5ppm to 30 ppm. When the initial concentration of uranium is 30ppm, the adsorption capacity of the UiO-66-NH (AO)/PAO composite fiber membrane to uranium reaches the maximum value of 113mg/g. And (3) fitting an adsorption thermodynamic model on the material, wherein the adsorption process follows a Langmuir isothermal model, which shows that the adsorption of uranium on the UiO-66-NH (AO)/PAO composite fiber membrane is a single-layer surface complexation process.

Claims (10)

1. An amidoxime MOFs composite membrane material has a structure of UiO-66-NH (AO)/PAO.
2. A method of preparing the composite membrane material of claim 1:
adding PAN into N, N-dimethylformamide, and electrospinning to obtain a PAN fiber membrane;
PAN fiber film, zrCl 4 ·8H 2 O, 12- (2-cyanoethyl) amino-p-benzene tricarboxylic acid is dispersed in a mixed solution containing organic acid and N, N-dimethylformamide, and the solvent is subjected to thermal reaction to obtain MOFs composite membrane material UiO-66-NH (CN)/PAN;
UiO-66-NH (CN)/PAN, NH 2 OH·HCl、Et 3 N is added into ethanol solution for reaction to obtain MOFs composite membrane material UiO-66-NH (AO)/PAO.
3. The method of manufacturing as claimed in claim 2, characterized in that:
adding PAN into N, N-dimethylformamide, stirring, electrospinning to obtain PAN fiber membrane, and drying;
PAN fiber film, zrCl 4 ·8H 2 Dispersing O and 12- (2-cyanoethyl) amino terephthalic acid in a mixed solution containing organic acid and N, N-dimethylformamide, sequentially washing the N, N-dimethylformamide, water and ethanol after solvothermal reaction, and drying to obtain MOFs composite membrane material UiO-66-NH (CN)/PAN;
UiO-66-NH (CN)/PAN, NH 2 OH·HCl、Et 3 Adding N into ethanol solution for reaction, cooling, washing with ethanol and water, and drying to obtain MOFs composite membrane material UiO-66-NH (AO)/PAO.
4. A process according to claims 2-3, characterized in that the PAN is used in a weight ratio to N, N-dimethylformamide of 1:3-27.
5. The process of claim 4, wherein the ratio of PAN to N, N-dimethylformamide is 1:9 by weight.
6. A process according to claims 2-3, characterized in that the organic acid in the mixed solution is selected from any one or a mixture of several of acetic acid and trifluoroacetic acid; the volume ratio of the organic acid to the N, N-dimethylformamide is 1:2.
7. A process according to claims 2-3, characterized in that the solvothermal reaction is carried out at a temperature of 90-120 ℃ for a reaction time of 9-24 hours.
8. Use of the composite membrane material of claim 1 for the preparation of amidoxime-functionalized metal-organic framework materials.
9. Use of the composite membrane material of claim 1 in the nuclear industry.
10. Use of the composite membrane material of claim 8 in uranium separation.
CN202310573616.7A 2023-05-19 2023-05-19 Amidoxime MOFs composite membrane material, and preparation method and application thereof Pending CN116440876A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118142506A (en) * 2024-05-11 2024-06-07 中北大学 Preparation method and application of amidoxime poly-dopamine-phosphate metal organic framework material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118142506A (en) * 2024-05-11 2024-06-07 中北大学 Preparation method and application of amidoxime poly-dopamine-phosphate metal organic framework material

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