Phenol-amine synergistic functional polyphenylenediamine adsorption material, preparation method thereof, adsorption film and application of adsorption film in extraction of uranium from seawater

Abstract

The invention relates to the technical field of functional adsorption film materials and seawater resource utilization, in particular to a phenol-amine synergistic functional polyphenylenediamine adsorption material, a preparation method of the phenol-amine synergistic functional polyphenylenediamine adsorption material, an adsorption film and application of uranium extraction from seawater. Phenolic hydroxyl groups and amino groups are introduced into a formed polyphenylenediamine structure through a phenol-amine functional compound to construct various coordination active sites, so that the coordination capability of the material to uranyl ions is improved, and the adsorption capability of the adsorption material to uranyl ions is remarkably enhanced. And a dialdehyde compound is adopted as a cross-linking agent to carry out cross-linking treatment on the phenol-amine functional compound modified polyphenylenediamine material, so that a more stable cross-linked network is established between material particles and between polymeric chains. The obtained adsorption material or adsorption film has the advantages of being stable in structure, good in operation stability and high in uranium adsorption capacity, is applied to extraction of uranium from seawater, and can achieve excellent uranium adsorption capacity and high uranium selectivity.

Description

Technical Field

[0001] This invention relates to the field of functional adsorption membrane materials and seawater resource utilization technology, specifically to a phenol-amine synergistic functionalized polyphenylene diamine adsorption material and its preparation method, as well as the application of the adsorption membrane in seawater uranium extraction. Background Technology

[0002] Uranium is a crucial raw material for nuclear energy, and the demand for uranium resources continues to grow with the development of the nuclear energy industry. Traditional uranium mines have limited reserves, while seawater contains abundant uranium resources, estimated at approximately 4.5 billion tons. Its total reserves far exceed those of terrestrial uranium mines, amounting to thousands of times the total terrestrial reserves. Therefore, seawater uranium extraction is considered one of the important future pathways for uranium resource acquisition, and developing efficient seawater uranium extraction technology has become a potential method for achieving sustainable uranium resource development. Furthermore, seawater uranium extraction not only has strategic significance in ensuring energy security but also offers environmental advantages, avoiding the environmental pollution problems associated with traditional uranium mining. With continuous technological advancements, seawater uranium extraction is expected to become a new growth engine in the upstream of the nuclear energy industry chain, injecting core momentum into my country's energy security and low-carbon development.

[0003] However, the concentration of uranium in seawater is extremely low, typically only about 3.3 μg / L. –1 At the same time, seawater also contains a large number of competing ions, such as Na+. + Ca 2+ Mg 2+ This poses a significant challenge to the efficient and selective enrichment of uranium.

[0004] Currently, common methods for uranium extraction from seawater include adsorption, membrane separation, and chemical precipitation. Among these, adsorption has attracted widespread attention due to its simplicity, low cost, and high selectivity. In recent years, researchers have developed various functional materials for uranium adsorption, such as acylated polymers, metal-organic frameworks, and functionalized porous materials. However, these materials still face challenges in practical applications, including complex preparation, high cost, and insufficient stability.

[0005] Polyphenylene diamine (PPD) is a class of functional polymer materials with good chemical stability and abundant nitrogen elements. Its molecular structure contains a large number of aromatic rings and amino functional groups, giving it potential adsorption capacity for metal ions. However, traditional PPD materials have a limited number of adsorption sites, making it difficult to achieve efficient capture of uranyl ions in seawater. Summary of the Invention

[0006] To overcome the shortcomings of the prior art, the first objective of this invention is to provide a method for preparing phenol-amine synergistic functionalized polyphenylene diamine adsorbent materials. This method is simple to operate, has mild conditions, is easy to industrialize, and the obtained phenol-amine synergistic functionalized polyphenylene diamine adsorbent materials have the advantages of stable structure and strong uranium adsorption capacity.

[0007] To overcome the shortcomings of the prior art, the second objective of this invention is to provide a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material, which has the advantages of structural stability and strong uranium adsorption capacity.

[0008] A third objective of this invention is to provide an adsorption membrane.

[0009] The fourth objective of this invention is to provide a method for preparing an adsorption membrane.

[0010] The fifth objective of this invention is to provide an application of phenol-amine synergistic functionalized polyphenylene diamine adsorbent material or adsorbent membrane in seawater uranium extraction.

[0011] To achieve the first objective of the invention, the technical solution adopted by the present invention is as follows:

[0012] This invention provides a method for preparing phenol-amine synergistic functionalized polyphenylene diamine adsorbent material, comprising the following steps:

[0013] S1. Constructing a hybrid cross-linked network system: Dissolve m-phenylenediamine in water to form a monomer solution, add a phenol-amine functional compound, mix and then add a metal salt to react, then add an oxidant to react again to obtain a suspension, thus forming a hybrid cross-linked network system.

[0014] S2. Material separation and washing: The suspension obtained in S1 is centrifuged and washed to obtain phenol-amine functional compound modified polyphenylene diamine material;

[0015] S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water, and a dialdehyde compound is added as a crosslinking agent. After mixing, a dispersion is obtained. Then, the dispersion is heated to carry out a crosslinking reaction, thereby obtaining the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0016] The present invention discloses a method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material. By constructing a hybrid cross-linked network system, phenolic hydroxyl and amino groups are introduced into the formed polyphenylene diamine structure through phenol-amine functional compounds. This enriches the surface of the hybrid cross-linked network structure with phenolic hydroxyl and amino functional groups, thereby constructing a variety of coordination active sites. These coordination active sites can form stable complexes or coordination interactions with uranyl ions, thereby significantly enhancing the adsorption capacity of the prepared adsorbent material for uranyl ions.

[0017] The reaction principle for constructing the hybrid crosslinked network system is as follows: During the reaction, m-phenylenediamine first undergoes oxidative polymerization to form a poly-m-phenylenediamine structure, and the phenol-amine functional compound is simultaneously oxidized to a reactive intermediate and further undergoes self-polymerization or coupling; at the same time, the oxidized intermediate of the phenol-amine functional compound can couple with the amino groups on m-phenylenediamine or poly-m-phenylenediamine through Schiff base reaction, Michael addition and non-covalent interaction, thereby forming a hybrid crosslinked network containing a polyphenylenediamine backbone and derived structural units of the phenol-amine functional compound.

[0018] In constructing a hybrid cross-linked network system, the main role of introducing metal ions through metal salts is to promote polymerization and network structure formation through coordination bridging. Metal ions can coordinate with the amino groups in the m-phenylenediamine monomer to form transient coordination complexes, which bridge different monomers or polymer chains, thereby promoting the connection between m-phenylenediamine monomers and accelerating the construction of the polymer network.

[0019] In addition, the present invention provides a method for preparing a phenol-amine co-functionalized polyphenylene diamine adsorbent material, which uses a dialdehyde compound as a crosslinking agent to crosslink the phenol-amine functionalized polyphenylene diamine material. The crosslinking reaction principle is as follows: the dialdehyde compound contains active aldehyde groups at both ends, which can react with the amino groups in the polyphenylene diamine and phenol-amine functionalized polyphenylene diamine material molecules to form Schiff base bonds (C=N) and other chemical connections, thereby establishing a more stable crosslinking network between material particles and polymer chains.

[0020] Furthermore, in step S1, the mass ratio of the m-phenylenediamine, phenol-amine functional compound, metal salt and oxidant is (1~1.5):(0.6~1.0):(0.8~1.2):(3~5).

[0021] Furthermore, in step S1, the phenol-amine functional compound is at least one of dopamine, norepinephrine, levodopa, epinephrine, tyramine, o-aminophenol, p-aminophenol, and their derivatives or salt forms; wherein, the phenol-amine functional compound has a phenolic hydroxyl structure, which can form stable coordination complexes with various metal ions; at the same time, the amino group contained in the phenol-amine functional compound can provide additional coordination sites and improve the hydrophilicity of the material. Therefore, by synergistically introducing phenolic hydroxyl groups and amino groups into the poly(m-phenylene diamine) structure, an adsorbent material with multiple active sites can be constructed, thereby significantly improving the adsorption capacity for uranyl ions.

[0022] In the reaction process of constructing the hybrid cross-linked network system, m-phenylenediamine first undergoes oxidative polymerization to form a poly-m-phenylenediamine structure. Simultaneously, phenol-amine functional compounds are oxidized to reactive intermediates and further undergo self-polymerization or coupling. Specifically, dopamine, norepinephrine, levodopa, epinephrine, and their derivatives or salts are oxidized to quinone / semiquinone intermediates; o-aminophenol, p-aminophenol, and their derivatives or salts are oxidized to quinone imine intermediates; and tyramine and its derivatives or salts are oxidized to form phenoxy radical intermediates.

[0023] The metal salt is at least one of copper chloride, ferric chloride, cobalt chloride, zinc chloride, manganese chloride, copper sulfate, or copper nitrate; and / or

[0024] The oxidant is at least one of sodium periodate, sodium iodate, hydrogen peroxide, potassium persulfate, ammonium persulfate, or potassium permanganate.

[0025] Further, in step S1, m-phenylenediamine is dissolved in water to form a monomer solution, a phenol-amine functional compound solution is added, and the mixture is stirred for 1 to 3 minutes. Then, a metal salt solution is added and reacted for 1 to 3 minutes. Next, an oxidant solution is added, and the reaction is carried out under stirring at 200 to 300 rpm for 4 to 6 hours to obtain a suspension, thus forming a hybrid cross-linked network; and / or

[0026] The concentration of the monomer solution is 20 g / L to 30 g / L, and / or the concentration of the phenol-amine functional compound solution is 20 g / L to 30 g / L, and / or the concentration of the metal salt solution is 10 g / L to 15 g / L, and / or the concentration of the oxidant solution is 90 g / L to 110 g / L.

[0027] Furthermore, in step S2, the centrifugal separation speed is 7000 rpm to 9000 rpm; and / or

[0028] The washing process involves using deionized water; and / or

[0029] The centrifugation and washing process is repeated 2-3 times.

[0030] Furthermore, in step S3, the mass of the dialdehyde compound is 1% to 3% of the mass of the dispersion; and / or

[0031] The concentration of the phenol-amine functional compound-modified polyphenylene diamine material dispersed in water is 0.05 mg / mL to 0.1 mg / mL; and / or

[0032] The dialdehyde compound is at least one of glutaraldehyde, glyoxal, succinaldehyde, azelaic acid, adipaldehyde, or terephthalaldehyde. The aldehyde groups in these dialdehyde compounds can undergo a Schiff base reaction with the amino groups in the polyphenylene diamine and phenol-amine functional compound-modified polyphenylene diamine material molecules, thereby establishing a stable chemical cross-linking network. Furthermore, these dialdehyde compounds, as cross-linking agents for amino-containing materials, react under relatively mild conditions, and can be carried out in an aqueous phase at medium to low temperatures, making the operation convenient.

[0033] The crosslinking reaction is carried out at a temperature of 55℃ to 65℃ and for a time of 50 min to 80 min.

[0034] To achieve the second objective of the invention, the technical solution adopted by the present invention is as follows:

[0035] This invention provides a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material, which is prepared by the above-described method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0036] To achieve the third objective of the invention, the technical solution adopted by the present invention is as follows:

[0037] This invention provides a phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane, which is prepared from the phenol-amine synergistic functionalized polyphenylene diamine adsorption material described above.

[0038] To achieve the fourth objective of the invention, the technical solution adopted by the present invention is as follows:

[0039] This invention provides a method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane, comprising the following steps: forming a membrane structure on the surface of a base membrane by means of pressure filtration of the phenol-amine synergistic functionalized polyphenylene diamine adsorption material described above, and performing compaction treatment using an inert atmosphere, thereby obtaining the phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane.

[0040] To achieve the fifth objective of the invention, the technical solution adopted by the present invention is as follows:

[0041] This invention provides a phenol-amine synergistic functionalized polyphenylene diamine (PPD) adsorbent material or a phenol-amine synergistic functionalized PPD adsorbent material prepared by the preparation method described above, or the application of a phenol-amine synergistic functionalized PPD adsorbent membrane prepared by the preparation method described above in seawater uranium extraction.

[0042] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0043] (1) A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material according to the present invention involves constructing a hybrid cross-linked network system. Phenolic hydroxyl and amino groups are introduced into the formed polyphenylene diamine structure via phenol-amine functional compounds, thereby enriching the surface of the hybrid cross-linked network structure with phenolic hydroxyl and amino functional groups to construct multiple coordination active sites. These coordination active sites can form stable complexes or coordination interactions with uranyl ions, enhancing the material's coordination ability for uranyl ions and significantly strengthening the adsorption capacity of the prepared adsorbent material for uranyl ions. Furthermore, by using a dialdehyde compound as a cross-linking agent to cross-link the phenol-amine functionalized polyphenylene diamine material, a more stable cross-linked network is established between material particles and between polymer chains.

[0044] (2) The preparation method of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material of the present invention has the characteristics of simple operation, mild conditions, easy industrial production, and suitable for large-scale production.

[0045] (3) The phenol-amine synergistic functionalized polyphenylene diamine adsorbent material of the present invention has the advantages of stable structure and good operational stability, good stability in water environment, and strong uranium adsorption capacity.

[0046] (4) The phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane of the present invention has the advantages of stable structure and good operational stability, good stability in the water environment, strong uranium adsorption capacity, and simple preparation method, which is easy to industrialize.

[0047] (5) Application of a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material or membrane of the present invention. When applied to uranium extraction from seawater, this phenol-amine synergistic functionalized polyphenylene diamine adsorbent material or membrane can achieve excellent uranium adsorption capacity and high uranium selectivity. Therefore, this phenol-amine synergistic functionalized polyphenylene diamine adsorbent material or membrane has good application prospects. Attached Figure Description

[0048] To more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0049] Figure 1 SEM images of the nylon-based membrane of the present invention, the adsorption membrane of Example 8, and the comparative examples 1-2.

[0050] Figure 2 The graph shows the water contact angle test results of the adsorption membranes in Example 8 and Comparative Examples 1-2 of the present invention.

[0051] Figure 3 The graphs show the adsorption kinetics of uranium on the adsorption membranes of Example 8 and Comparative Examples 1-2 in the adsorption performance test of the simulated uranium solution of this invention.

[0052] Figure 4 This is a comparison chart showing the adsorption performance of the adsorption membranes of Example 8 and Comparative Examples 1-2 in a real seawater competitive ion system.

[0053] Figure 5 The graph shows the adsorption performance of the adsorption membranes of Example 8 and Comparative Examples 1-2 for uranium in real seawater. Detailed Implementation

[0054] To make the technical problem to be solved, the technical solution, and the beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.

[0055] The terminology used in the embodiments of this invention is for the purpose of describing particular embodiments only and is not intended to limit the invention. In this invention, the singular forms “a,” “described,” and “the” as used in the embodiments and appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0056] In this embodiment of the invention, a method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material includes the following steps:

[0057] S1. Constructing a hybrid cross-linked network system: Dissolve m-phenylenediamine in water to form a monomer solution, add a phenol-amine functional compound, mix and then add a metal salt to react, then add an oxidant to react again to obtain a suspension, thus forming a hybrid cross-linked network system.

[0058] S2. Material separation and washing: The suspension obtained in S1 is centrifuged and washed to obtain phenol-amine functional compound modified polyphenylene diamine material;

[0059] S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water, and a dialdehyde compound is added as a crosslinking agent. After mixing, a dispersion is obtained. Then, the dispersion is heated to carry out a crosslinking reaction, thereby obtaining the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0060] In some embodiments, in step S1, the mass ratio of the m-phenylenediamine, phenol-amine functional compound, metal salt and oxidant is (1~1.5):(0.6~1.0):(0.8~1.2):(3~5).

[0061] In some embodiments, in step S1, the phenol-amine functional compound is at least one of dopamine, norepinephrine, levodopa, epinephrine, tyramine, o-aminophenol, p-aminophenol, and their derivatives or salt forms; and / or

[0062] The metal salt is at least one of copper chloride, ferric chloride, cobalt chloride, zinc chloride, manganese chloride, copper sulfate, or copper nitrate; and / or

[0063] The oxidant is at least one of sodium periodate, sodium iodate, hydrogen peroxide, potassium persulfate, ammonium persulfate, or potassium permanganate.

[0064] In some embodiments, in step S1, m-phenylenediamine is dissolved in water to form a monomer solution, a phenol-amine functional compound solution is added, and the mixture is stirred for 1 to 3 minutes. Then, a metal salt solution is added and reacted for 1 to 3 minutes. Finally, an oxidant solution is added, and the reaction is carried out under stirring at 200 to 300 rpm for 4 to 6 hours to obtain a suspension, thus forming a hybrid crosslinked network; and / or

[0065] The concentration of the monomer solution is 20 g / L to 30 g / L, and / or the concentration of the phenol-amine functional compound solution is 20 g / L to 30 g / L, and / or the concentration of the metal salt solution is 10 g / L to 15 g / L, and / or the concentration of the oxidant solution is 90 g / L to 110 g / L.

[0066] In some embodiments, in step S2, the centrifugal separation speed is 7000 rpm to 9000 rpm; and / or

[0067] The washing process involves using deionized water; and / or

[0068] The centrifugation and washing process is repeated 2-3 times.

[0069] In some embodiments, in step S3, the mass of the dialdehyde compound is 1% to 3% of the mass of the dispersion; and / or

[0070] The concentration of the phenol-amine functional compound-modified polyphenylene diamine material dispersed in water is 0.05 mg / mL to 0.1 mg / mL; and / or

[0071] The dialdehyde compound is at least one of glutaraldehyde, glyoxal, succinaldehyde, azelaic acid, adipaldehyde, or terephthalaldehyde; and / or

[0072] The crosslinking reaction is carried out at a temperature of 55℃ to 65℃ and for a time of 50 min to 80 min.

[0073] In this embodiment of the invention, a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material is prepared by the above-described preparation method of a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0074] In this embodiment of the invention, a phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane is prepared from the phenol-amine synergistic functionalized polyphenylene diamine adsorption material described above.

[0075] In this embodiment of the invention, a method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane includes the following steps: forming a membrane structure on the surface of a base membrane by pressure filtration of the aforementioned phenol-amine synergistic functionalized polyphenylene diamine adsorption material, and then performing a compaction treatment using an inert atmosphere to obtain the phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane.

[0076] In this embodiment of the invention, the application of a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material or a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material prepared by the above-described preparation method, or the application of a phenol-amine synergistic functionalized polyphenylene diamine adsorbent membrane or a phenol-amine synergistic functionalized polyphenylene diamine adsorbent membrane prepared by the above-described preparation method in seawater uranium extraction.

[0077] The following description is based on specific embodiments. Example 1

[0078] A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material includes the following steps:

[0079] S1. Construction of a hybrid cross-linked network system: m-phenylenediamine was dissolved in water to form a 25 g / L monomer solution. A 25 g / L dopamine hydrochloride solution was added, and the mixture was stirred for 2 min. Then, a 12.5 g / L copper chloride solution was added and reacted for 2 min. Next, a 100 g / L sodium periodate solution was added, and the mixture was reacted at 250 rpm for 5 h to obtain a suspension, thus forming the hybrid cross-linked network system. In this embodiment, the mass ratio of m-phenylenediamine, dopamine hydrochloride, copper chloride solution, and sodium periodate was 1.2:0.8:1:4.

[0080] S2. Material separation and washing: The suspension obtained in S1 was centrifuged at 8000 rpm and then washed with deionized water. The centrifugation and washing were repeated 3 times to obtain the phenol-amine functional compound modified polyphenylene diamine material.

[0081] S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water at a concentration of 0.08 mg / mL, and glutaraldehyde is added as a crosslinking agent. After mixing, a dispersion is obtained. Then, the dispersion is heated to 60℃ for a crosslinking reaction for 70 min to obtain the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0082] In this embodiment, the mass of glutaraldehyde is 2% of the mass of the dispersion. Example 2

[0083] A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material includes the following steps:

[0084] S1. Construction of a hybrid cross-linked network system: m-phenylenediamine was dissolved in water to form a 20 g / L monomer solution. A 20 g / L norepinephrine hydrochloride solution was added, and the mixture was stirred for 1 min. Then, a 10 g / L ferric chloride solution was added and reacted for 1 min. Next, a 90 g / L sodium iodate solution was added, and the reaction was carried out at 200 rpm for 6 h to obtain a suspension, thus forming the hybrid cross-linked network system. In this embodiment, the mass ratio of m-phenylenediamine, norepinephrine hydrochloride, ferric chloride, and sodium iodate was 1:0.6:0.8:3.

[0085] S2. Material separation and washing: The suspension obtained in S1 is centrifuged at 7000 rpm and then washed with deionized water. The centrifugation and washing are repeated twice to obtain phenol-amine functional compound modified polyphenylene diamine material.

[0086] S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water at a concentration of 0.05 mg / mL, and glyoxal is added as a crosslinking agent. After mixing, a dispersion is obtained. Then, the dispersion is heated to 55°C for crosslinking reaction for 80 min to obtain the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0087] In this embodiment, the mass of glyoxal is 1% of the mass of the dispersion. Example 3

[0088] A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material includes the following steps:

[0089] S1. Construction of a hybrid cross-linked network system: m-phenylenediamine was dissolved in water to form a 30 g / L monomer solution. A 30 g / L epinephrine hydrochloride solution was added, and the mixture was stirred for 3 min. Then, a 15 g / L cobalt chloride solution was added and reacted for 3 min. Next, a 110 g / L hydrogen peroxide solution was added, and the reaction was carried out at 300 rpm for 4 h to obtain a suspension, thus forming the hybrid cross-linked network system. In this embodiment, the mass ratio of m-phenylenediamine, epinephrine hydrochloride, cobalt chloride, and hydrogen peroxide was 1.5:1.0:1.2:5.

[0090] S2. Material separation and washing: The suspension obtained in S1 is centrifuged at 9000 rpm and then washed with deionized water. The centrifugation and washing are repeated 3 times to obtain phenol-amine functional compound modified polyphenylene diamine material.

[0091] S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water at a concentration of 0.1 mg / mL, and butanol is added as a crosslinking agent. After mixing, a dispersion is obtained. Then, the dispersion is heated to 65°C for a crosslinking reaction for 50 min to obtain the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0092] In this embodiment, the mass of succinaldehyde is 3% of the mass of the dispersion. Example 4

[0093] A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material includes the following steps:

[0094] S1. Construction of a hybrid cross-linked network system: m-phenylenediamine was dissolved in water to form a 23 g / L monomer solution. A 23 g / L tyramine hydrochloride solution was added, and the mixture was stirred for 1.5 min. Then, an 11 g / L metal salt solution (a mixture of zinc chloride and manganese chloride) was added and reacted for 1.5 min. Finally, a 95 g / L potassium persulfate solution was added, and the mixture was reacted at 230 rpm for 5.5 h to obtain a suspension, thus forming the hybrid cross-linked network system. In this embodiment, the mass ratio of m-phenylenediamine, tyramine hydrochloride, metal salt, and potassium persulfate was 1.1:0.7:0.9:3.5.

[0095] S2. Material separation and washing: The suspension obtained in S1 was centrifuged at 7500 rpm and then washed with deionized water. The centrifugation and washing were repeated 3 times to obtain the phenol-amine functional compound modified polyphenylene diamine material.

[0096] S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water at a concentration of 0.06 mg / mL, and azelaic acid is added as a crosslinking agent. After mixing, a dispersion is obtained. The dispersion is then heated to 58°C for a crosslinking reaction for 75 min to obtain the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0097] In this embodiment, the mass of azelaic aldehyde is 1.5% of the mass of the dispersion. Example 5

[0098] A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material includes the following steps:

[0099] S1. Construction of a hybrid cross-linked network system: m-phenylenediamine was dissolved in water to form a 28 g / L monomer solution. 27 g / L levodopa solution was added, and the mixture was stirred for 2.5 min. Then, 14 g / L copper sulfate solution was added, and the reaction was carried out for 2.5 min. Next, 105 g / L ammonium persulfate solution was added, and the reaction was carried out at 280 rpm for 4.5 h to obtain a suspension, thus forming the hybrid cross-linked network system. In this embodiment, the mass ratio of m-phenylenediamine, levodopa, copper sulfate, and ammonium persulfate was 1.4:0.9:1.1:4.5.

[0100] S2. Material separation and washing: The suspension obtained in S1 is centrifuged at 8500 rpm and then washed with deionized water. The centrifugation and washing are repeated twice to obtain phenol-amine functional compound modified polyphenylene diamine material.

[0101] S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water at a concentration of 0.09 mg / mL, and hexamethylenetetramine is added as a crosslinking agent. After mixing, a dispersion is obtained. The dispersion is then heated to 62°C for a crosslinking reaction for 60 min to obtain the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0102] In this embodiment, the mass of adipaldehyde is 2.5% of the mass of the dispersion. Example 6

[0103] A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material includes the following steps:

[0104] S1. Construction of a hybrid cross-linked network system: m-phenylenediamine was dissolved in water to form a 26 g / L monomer solution. A 28 g / L p-aminophenol solution was added, and the mixture was stirred for 2 min. Then, a 13 g / L copper nitrate solution was added, and the reaction was allowed to proceed for 1.8 min. Next, a 98 g / L potassium permanganate solution was added, and the reaction was carried out at 260 rpm for 4.8 h to obtain a suspension, thus forming the hybrid cross-linked network system. In this embodiment, the mass ratio of m-phenylenediamine, p-aminophenol, copper nitrate, and potassium permanganate was 1.3:0.7:1:3.8.

[0105] S2. Material separation and washing: The suspension obtained in S1 was centrifuged at 7800 rpm and then washed with deionized water. The centrifugation and washing were repeated 3 times to obtain the phenol-amine functional compound modified polyphenylene diamine material.

[0106] S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water at a concentration of 0.07 mg / mL, and terephthalaldehyde is added as a crosslinking agent. After mixing, a dispersion is obtained. The dispersion is then heated to 61°C for a crosslinking reaction for 73 min to obtain the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0107] In this embodiment, the mass of terephthalaldehyde is 2.2% of the mass of the dispersion. Example 7

[0108] A phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane is prepared from any one of the phenol-amine synergistic functionalized polyphenylene diamine adsorption materials in Examples 1 to 6. Example 8

[0109] A method for preparing a phenol-amine co-functionalized polyphenylene diamine adsorption membrane includes the following steps: A phenol-amine co-functionalized polyphenylene diamine adsorption material of Example 1 is used to form a membrane structure on the surface of a base membrane (nylon membrane with a pore size of 220 nm) by pressure filtration. Specifically, the phenol-amine co-functionalized polyphenylene diamine adsorption material is poured into a self-made filter cup containing a nylon membrane, and the membrane is formed by filtration under 1 bar argon pressure. Then, the membrane is compacted under 1 bar argon pressure for 10 min to obtain the phenol-amine co-functionalized polyphenylene diamine adsorption membrane (denoted as DA-PmPD). Example 9

[0110] Application of any one of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent materials in Examples 1 to 6 or any one of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent membranes in Examples 7 to 8 in seawater uranium extraction.

[0111] Comparative Example 1

[0112] A method for preparing a polyphenylene diamine adsorbent material is disclosed. This method differs from Example 1 in that it does not include the addition of a phenol-amine functional compound, specifically dopamine hydrochloride solution. All other preparation steps are the same as in Example 1, resulting in the preparation of a polyphenylene diamine adsorbent material.

[0113] A method for preparing a polyphenylene diamine (PPD) adsorption membrane is disclosed. This method differs from Example 8 in that the PPD adsorption material prepared in this comparative example is used instead of the phenol-amine synergistic functionalized PPD adsorption material in Example 8. All other preparation methods are the same as in Example 8, resulting in a PPD adsorption membrane (denoted as PmPD).

[0114] Comparative Example 2

[0115] A method for preparing tannic acid-modified polyphenylene diamine adsorbent material is disclosed. The difference between this method and Example 1 is that a tannic acid solution is used instead of the hydrochloric acid-dopamine solution in Example 1. In this comparative example, the mass ratio of m-phenylenediamine, tannic acid, copper chloride solution, and sodium periodate is 1.6:0.4:1:4. All other preparation methods are the same as in Example 1, thus obtaining the tannic acid-modified polyphenylene diamine adsorbent material.

[0116] Tannic acid contains only phenolic hydroxyl groups and no amino groups.

[0117] The preparation method of the tannic acid-modified polyphenylene diamine adsorption membrane differs from that of Example 8 in that the tannic acid-modified polyphenylene diamine adsorption material prepared in this comparative example is used instead of the phenol-amine synergistic functionalized polyphenylene diamine adsorption material of Example 8. All other preparation methods are the same as in Example 8, thus obtaining the tannic acid-modified polyphenylene diamine adsorption membrane (denoted as TA-PmPD).

[0118] Comparative Example 3

[0119] A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material is disclosed. This method differs from Example 1 in that the crosslinking treatment in step S3 is omitted. The remaining preparation methods are the same as in Example 1, thus obtaining a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

[0120] A phenol-amine synergistic functionalized polyphenylene diamine (PPD) adsorption membrane is disclosed. The difference between this preparation method and Example 8 is that the phenol-amine synergistic functionalized PPD adsorption material prepared in this comparative example is used instead of the phenol-amine synergistic functionalized PPD adsorption material in Example 8. All other preparation methods are the same as in Example 8, thus obtaining a phenol-amine synergistic functionalized PPD adsorption membrane.

[0121] According to experimental testing, the phenol-amine co-functionalized polyphenylene diamine adsorption membrane prepared in Comparative Example 3 without cross-linking treatment is prone to problems such as loosening, swelling, and loss of active components in water environment or dynamic filtration process. This not only affects the stability of the adsorption membrane structure, but also reduces the effective adsorption sites of the adsorption membrane and affects the adsorption performance of uranyl ions.

[0122] Structural morphology characterization

[0123] (I) Morphological characterization by scanning electron microscopy

[0124] The morphology of the nylon-based membrane, the phenol-amine co-functionalized polyphenylene diamine adsorption membrane (DA-PmPD) of Example 8, the polyphenylene diamine adsorption membrane (PmPD) of Comparative Example 1, and the tannic acid-modified polyphenylene diamine adsorption membrane (TA-PmPD) of Comparative Example 2 were characterized by scanning electron microscopy (SEM). The SEM images are shown below. Figure 1 As shown.

[0125] Depend on Figure 1 As can be seen, the nylon subatrate exhibits a distinct three-dimensional fiber network structure, with numerous interconnected pores between the fibers. The open pore structure and large pore size provide a good supporting framework for the subsequent loading of adsorbent materials. After constructing a PmPD adsorption membrane on the nylon subatrate surface, it can be observed that the membrane surface is uniformly covered by a large number of fine particulate structures, obscuring the original fiber structure. This indicates that the polyphenylene diamine adsorbent material was successfully deposited on the nylon subatrate surface and formed a dense functional layer. The modified TA-PmPD and DA-PmPD adsorption membranes still exhibit a particulate structure on the surface, uniformly distributed. The overall morphology shows no structural damage compared to the PmPD adsorption membrane, indicating that the modification process using tannic acid and dopamine hydrochloride did not destroy the original polyphenylene diamine membrane structure. All three adsorption membranes exhibit a relatively rough surface structure, which is beneficial for increasing surface active sites and also promotes the contact between uranyl ions in the solution and the adsorption membrane surface.

[0126] Performance testing

[0127] (a) Water contact angle test of adsorption membrane

[0128] Water contact angle tests were performed on the phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane (DA-PmPD) of Example 8, the polyphenylene diamine adsorption membrane (PmPD) of Comparative Example 1, and the tannic acid modified polyphenylene diamine adsorption membrane (TA-PmPD) of Comparative Example 2. The test results are as follows: Figure 2 As shown.

[0129] from Figure 2It can be seen that the water contact angle of the PmPD film is about 36°, indicating that the surface of the adsorption film has certain hydrophilicity. This is mainly attributed to the presence of polar groups such as amino groups in the structure of poly(p-phenylenediamine), which can form hydrogen bond interactions with water molecules. After introducing tannic acid modification, the water contact angle of the TA-PmPD adsorption film decreases to about 29°, indicating that the hydrophilicity of the adsorption film prepared after tannic acid modification is significantly enhanced. This is mainly because tannic acid molecules contain a large number of phenolic hydroxyl groups (–OH), which can significantly increase the polarity of the film surface, thereby enhancing the interaction with water molecules. When modified with dopamine hydrochloride, the water contact angle of the DA-PmPD film further decreases to about 23°, indicating that the adsorption film prepared after modification with phenolic-amine functional compounds has the optimal hydrophilic performance. This is because phenolic-amine functional compounds contain hydrophilic functional groups such as phenolic hydroxyl groups and amino groups, enabling more hydrogen bond interaction sites to be formed on the surface of the adsorption film. Generally speaking, the hydrophilicity of the three adsorption films is in the order of: PmPD < TA-PmPD < DA-PmPD. The enhanced hydrophilicity is conducive to promoting the mass transfer process of water molecules and uranyl ions on the surface of the adsorption film, increasing the contact probability between uranyl ions in the solution and the active sites on the surface of the adsorption film, thereby helping to improve the adsorption performance of the adsorption film.

[0130] (II) Adsorption performance test of simulated uranium solution

[0131] The phenolic-amine synergistically functionalized poly(p-phenylenediamine) adsorption film (DA-PmPD) of Example 8, the poly(p-phenylenediamine) adsorption film (PmPD) of Comparative Example 1, and the tannic acid-modified poly(p-phenylenediamine) adsorption film (TA-PmPD) of Comparative Example 2 were used for uranium ion adsorption experiments to evaluate their adsorption performance.

[0132] The test method is as follows: First, prepare a 150 mL uranyl ion solution with a concentration of 8 mg / L. Install the adsorption film in a self-made filter cup device, and control the circulation of the uranyl ion solution through a peristaltic pump, so that the uranyl ion passes through the adsorption film at a flow rate of 9 mL / min, thereby realizing the dynamic filtration adsorption process. During the experiment, filtrate samples were collected regularly, and the concentration of uranyl ions in them was measured using an inductively coupled plasma emission spectrometer (ICP-MS, iCAP 7000 SERIES, Thermo Fisher Scientific, America). The uranium adsorption capacity was calculated by the following formula I:

[0133] Formula I

[0134] where q e is the uranium adsorption capacity (mg / g), C0 is the initial uranium concentration (mg / L), V is the volume of the uranyl ion solution (mL), and m is the mass of the adsorption material loaded on the adsorption film (mg).

[0135] The uranium adsorption capacity results of the adsorption membranes in Example 8 and Comparative Examples 1-2, measured according to the above test method, are as follows: Figure 3 As shown.

[0136] Figure 3 This section presents the adsorption kinetics curves of three adsorption membranes—PmPD, TA-PmPD, and DA-PmPD—for uranium in a simulated uranium solution; that is, the curves showing the change in adsorption performance over time. Figure 3 It can be seen that the adsorption capacity of uranyl ions by the three adsorption membranes gradually increased with the increase of adsorption time, and tended to stabilize after a certain period of time, indicating that the adsorption process gradually reached an equilibrium state. In the initial stage of adsorption (0-2h), the adsorption capacity of the three adsorption membranes increased rapidly. This is because there are a large number of unoccupied active adsorption sites on the surface of the adsorption membranes, and uranyl ions can quickly coordinate or adsorb with the functional groups on the surface of the adsorption membranes. As the adsorption time increases, the adsorption rate gradually slows down. This is because the active sites on the surface of the adsorption membranes are gradually occupied, and the adsorption process is gradually restricted by the diffusion process. When the adsorption time reaches about 8-10h, the adsorption capacity of each adsorption membrane tends to stabilize, indicating that the system gradually reaches adsorption equilibrium. In terms of adsorption capacity, the three adsorption membranes show significant differences. The equilibrium adsorption capacity of the PmPD adsorption membrane is about 180mg / g; the equilibrium adsorption capacity of the TA-PmPD adsorption membrane increases to about 236mg / g; and the DA-PmPD adsorption membrane shows the highest adsorption performance, with an equilibrium adsorption capacity of about 275mg / g. The adsorption performance of the adsorption membrane prepared by modification with phenol-amine functional compounds in this invention is greatly improved, mainly due to the abundance of functional groups such as phenolic hydroxyl groups and amine groups in the phenol-amine functional compounds. These functional groups can react with uranyl ions (UO2). 2+ The phenol-amine functional compound facilitates coordination, providing more effective adsorption sites. Simultaneously, the hydrophilicity of the adsorption membrane is significantly enhanced after modification with the phenol-amine functional compound, which is beneficial for the mass transfer and diffusion of uranyl ions in solution, thus improving adsorption efficiency. Therefore, this invention, through functional modification of the polyphenylene diamine membrane with the phenol-amine functional compound, can effectively improve the adsorption performance of the membrane for uranyl ions, exhibiting excellent adsorption effects.

[0137] (III) Selectivity test of uranium adsorption by adsorption membrane

[0138] To further evaluate the adsorption performance of the membrane in complex ionic environments, competitive ion adsorption experiments were conducted using a spiked real seawater system to test the selectivity of the membrane for uranium adsorption.

[0139] The testing method is as follows:

[0140] (1) Take 500 mL of real seawater sample, filter out impurities using a 0.22 μm filter membrane, and remove seven metal ions (including UO2). 2+ VO2+ Fe 3+ Co 2+ Cd 2+ Cu 2+ and Zn 2+ Adding Fe to real seawater makes Fe 3+ The concentration is 10 times that of real seawater, and the concentration of other metal ions is 100 times that of real seawater. Mg 2+ Ca 2+ This maintains the original concentration found in real seawater, thus yielding a spiked seawater solution.

[0141] (2) The adsorption membranes of Example 8 and Comparative Examples 1-2 were respectively installed in a self-made filter cup device. The spiked seawater solution was circulated using a peristaltic pump, allowing the spiked seawater solution to pass through the adsorption membrane at a flow rate of 9 mL / min for a dynamic filtration adsorption experiment for 20 h. The selectivity of the three adsorption membranes for uranium adsorption in complex ion systems was evaluated by detecting the changes in the concentrations of uranium ions and competing ions in the spiked seawater solution before and after filtration. The experimental test results are as follows: Figure 4 As shown.

[0142] Depend on Figure 4 It is evident that the adsorption selectivity of the three adsorption membranes for uranium is higher than that for other competing ions. Specifically, the adsorption capacities of PmPD, TA-PmPD, and DA-PmPD membranes for uranium are approximately 11.5 mg / g, 15.5 mg / g, and 18.9 mg / g, respectively. This demonstrates that the phenol-amine co-functionalized polyphenylene diamine adsorption membrane prepared in this invention can effectively adsorb uranyl ions under conditions with a large number of competing ions, exhibiting superior resistance to ion interference and uranium selectivity.

[0143] (iv) Test of uranyl ion adsorption capacity in real seawater

[0144] To verify the application potential of the adsorption membrane in a real seawater environment, the adsorption membranes of Example 8 and Comparative Examples 1-2 were used in uranium adsorption experiments in real seawater systems to test their uranium ion adsorption capacity in real seawater.

[0145] The test method is as follows: An adsorption membrane was installed in a self-made filter cup device, and a peristaltic pump was used to control the flow rate of real seawater solution through the adsorption membrane at 9 mL / min for a 7-day dynamic filtration adsorption experiment. After the experiment, the uranium concentration was measured to evaluate the adsorption membrane's ability to adsorb uranyl ions from real seawater. The experimental results are as follows: Figure 5 As shown.

[0146] Compared with the simulated system, the concentration of uranyl ions in real seawater is lower, and there are a large number of coexisting ions and complex components. Therefore, higher requirements are placed on the selectivity and stability of the adsorption membrane. Figure 5 The results show that the three adsorption membranes can still effectively enrich uranium in real seawater systems. The uranium adsorption capacities of the PmPD, TA-PmPD, and DA-PmPD membranes are approximately 1.66 mg / g, 2.48 mg / g, and 3.27 mg / g, respectively. It can be seen that the adsorption capacity of the polyphenylene diamine (PPD) membranes for uranium is significantly improved after functionalization modification. Among them, the DA-PmPD membrane, which is functionalized with phenol-amine functional compounds through phenol-amine synergistic modification, exhibits the best adsorption performance and the highest uranium adsorption capacity, significantly superior to the PmPD and TA-PmPD membranes. This indicates that the phenol-amine synergistic functionalized PPD membrane prepared in this invention still possesses excellent adsorption performance and stability in complex seawater environments. These results further demonstrate that PPD membranes modified with phenol-amine functional compounds can more effectively enhance the recognition and adsorption capacity of membrane materials for uranyl ions, thus demonstrating excellent application potential in complex seawater systems.

[0147] In addition, the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material or adsorbent membrane prepared by the present invention can maintain good structural integrity in the above dynamic filtration adsorption experiments. Therefore, the adsorbent material or adsorbent membrane prepared by the present invention has the advantage of good operational stability.

[0148] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material, characterized in that, Includes the following steps: S1. Constructing a hybrid cross-linked network system: Dissolve m-phenylenediamine in water to form a monomer solution, add a phenol-amine functional compound, mix and then add a metal salt to react, then add an oxidant to react again to obtain a suspension, thus forming a hybrid cross-linked network system. S2. Material separation and washing: The suspension obtained in S1 is centrifuged and washed to obtain phenol-amine functional compound modified polyphenylene diamine material; S3. Crosslinking treatment: The phenol-amine functional compound modified polyphenylene diamine material is dispersed in water, and a dialdehyde compound is added as a crosslinking agent. After mixing, a dispersion is obtained. Then, the dispersion is heated to carry out a crosslinking reaction, thereby obtaining the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material.

2. The preparation method of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material as described in claim 1, characterized in that, In step S1, the mass ratio of the m-phenylenediamine, phenol-amine functional compound, metal salt and oxidant is (1~1.5):(0.6~1.0):(0.8~1.2):(3~5).

3. The preparation method of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material as described in claim 1, characterized in that, In step S1, the phenol-amine functional compound is at least one of dopamine, norepinephrine, levodopa, epinephrine, tyramine, o-aminophenol, p-aminophenol and their derivatives or salt forms; and / or The metal salt is at least one of copper chloride, ferric chloride, cobalt chloride, zinc chloride, manganese chloride, copper sulfate, or copper nitrate; and / or The oxidant is at least one of sodium periodate, sodium iodate, hydrogen peroxide, potassium persulfate, ammonium persulfate, or potassium permanganate.

4. The preparation method of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material as described in claim 1, characterized in that, In step S1, m-phenylenediamine is dissolved in water to form a monomer solution, a phenol-amine functional compound solution is added, and the mixture is stirred for 1 min to 3 min. Then, a metal salt solution is added and reacted for 1 min to 3 min. Finally, an oxidant solution is added and the mixture is stirred at 200 rpm to 300 rpm for 4 h to 6 h to obtain a suspension, which forms a hybrid cross-linked network. and / or The concentration of the monomer solution is 20 g / L to 30 g / L, and / or the concentration of the phenol-amine functional compound solution is 20 g / L to 30 g / L, and / or the concentration of the metal salt solution is 10 g / L to 15 g / L, and / or the concentration of the oxidant solution is 90 g / L to 110 g / L.

5. The preparation method of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material as described in claim 1, characterized in that, In step S2, the centrifugal separation speed is 7000 rpm to 9000 rpm; and / or The washing process involves using deionized water; and / or The centrifugation and washing process is repeated 2-3 times.

6. The preparation method of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material as described in claim 1, characterized in that, In step S3, the mass of the dialdehyde compound is 1% to 3% of the mass of the dispersion; and / or The concentration of the phenol-amine functional compound-modified polyphenylene diamine material dispersed in water is 0.05 mg / mL to 0.1 mg / mL; and / or The dialdehyde compound is at least one of glutaraldehyde, glyoxal, succinaldehyde, azelaic acid, adipaldehyde, or terephthalaldehyde; and / or The crosslinking reaction is carried out at a temperature of 55℃ to 65℃ and for a time of 50 min to 80 min.

7. A phenol-amine synergistic functionalized polyphenylene diamine adsorbent material, characterized in that, It is prepared by the method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorbent material as described in claims 1 to 6.

8. A phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane, characterized in that, It is prepared from the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material as described in claim 7.

9. The method for preparing a phenol-amine synergistic functionalized polyphenylene diamine adsorption membrane according to claim 8, characterized in that, The process includes the following steps: forming a membrane structure on the surface of a base membrane by means of pressure filtration of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material as described in claim 7, and then performing a compaction treatment using an inert atmosphere to obtain the phenol-amine synergistic functionalized polyphenylene diamine adsorbent membrane.

10. The phenol-amine synergistic functionalized polyphenylene diamine adsorbent material according to claim 7 or the phenol-amine synergistic functionalized polyphenylene diamine adsorbent material prepared by any one of claims 1 to 6, or the application of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent membrane according to claim 8 or the phenol-amine synergistic functionalized polyphenylene diamine adsorbent membrane prepared by the preparation method of the phenol-amine synergistic functionalized polyphenylene diamine adsorbent membrane according to claim 9 in seawater uranium extraction.

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