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CN-122006679-A - Two-dimensional L-FMPBA-MOF, mixed matrix membranes and Rb in adsorbed water+And Cs+Application of aspects

CN122006679ACN 122006679 ACN122006679 ACN 122006679ACN-122006679-A

Abstract

The invention belongs to the technical field of adsorption materials, and provides a two-dimensional L-FMPBA-MOF, a mixed matrix membrane and application thereof in adsorbing Rb + and Cs + in water. The two-dimensional L-FMPBA-MOF is a metal organic framework material with a two-dimensional lamellar structure, metal ions in the metal organic framework material are Fe 3+ and Mn 2+ , and the two-dimensional L-FMPBA-MOF has the diffraction characteristics of Prussian blue analogues in an X-ray diffraction spectrum. The two-dimensional sheet structure of the L-FMPBA-MOF constructs an ultra-short transmission channel for ion exchange, effectively shortens an ion diffusion path and improves ion transmission efficiency, and Fe 3+ and Mn 2+ in the two-dimensional L-FMPBA-MOF are complementary in coordination environment and ion exchange, and the synergistic effect of the Fe 3+ and Mn 2+ reduces specific ion migration energy barrier and obviously improves adsorption quantity of Rb + and Cs + .

Inventors

  • YU JIANGNAN
  • ZHANG GUOHUA
  • HUANG JING
  • ZHAO WENTAO
  • FENG ZHIJUN
  • SUN BINGJIE

Assignees

  • 西安蓝深新材料科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260413

Claims (10)

  1. 1. The two-dimensional L-FMPBA-MOF is characterized in that the two-dimensional L-FMPBA-MOF is a metal organic framework material with a two-dimensional lamellar structure, metal ions in the metal organic framework material are Fe 3+ and Mn 2+ , and the two-dimensional L-FMPBA-MOF has the diffraction characteristic of Prussian blue analogues in an X-ray diffraction spectrum.
  2. 2. The method for preparing the two-dimensional L-FMPBA-MOF according to claim 1, comprising the steps of: s1, carrying out coordination reaction on polyvinylpyrrolidone, soluble manganese salt and soluble ferric salt to obtain FMPBA-MOF precursor; s2, stripping the FMPBA-MOF precursor to obtain the two-dimensional L-FMPBA-MOF.
  3. 3. The method for preparing a two-dimensional L-FMPBA-MOF according to claim 2, wherein S1 specifically comprises: (1) Dissolving polyvinylpyrrolidone in a mixed solution of ethanol and water, adding soluble manganese salt and tertiary butanol, stirring until the soluble manganese salt and tertiary butanol are dissolved to form a solution A; (2) Dropwise adding the solution A into the solution B and mixing to obtain a suspension C; (3) And (3) stirring the suspension C for reaction, then carrying out solid-liquid separation, collecting a solid product D, and drying to obtain FMPBA-MOF precursor.
  4. 4. The method of claim 2, wherein the soluble manganese salt is manganese sulfate monohydrate and the soluble iron salt is potassium ferricyanide.
  5. 5. The method for preparing the two-dimensional L-FMPBA-MOF according to claim 2, wherein the mass ratio of polyvinylpyrrolidone to soluble manganese salt and soluble iron salt is (200-300) mg (140.5-169.5) mg.
  6. 6. The method for preparing the two-dimensional L-FMPBA-MOF according to claim 2, wherein S2 specifically comprises the steps of mixing FMPBA-MOF precursor with hydrochloric acid solution, water and N, N-dimethylformamide, reacting at constant temperature, separating out solid products, washing and drying to obtain the two-dimensional L-FMPBA-MOF.
  7. 7. The method for preparing the two-dimensional L-FMPBA-MOF according to claim 6, wherein the reaction is carried out at a constant temperature, specifically at 60-100 ℃ for 6-28 h.
  8. 8. A mixed matrix membrane characterized in that it uses polyvinylidene fluoride as matrix, and the matrix is filled with the two-dimensional L-FMPBA-MOF according to claim 1.
  9. 9. The mixed matrix membrane of claim 8, wherein the two-dimensional L-FMPBA-MOF is present in the mixed matrix membrane at a mass ratio of 50% to 80%.
  10. 10. Use of the two-dimensional L-FMPBA-MOF of claim 1 or the mixed matrix membrane of claim 8 to adsorb Rb + and/or Cs + in a body of water.

Description

Two-dimensional L-FMPBA-MOF, mixed matrix membrane and application thereof in adsorbing Rb + and Cs + in water Technical Field The invention belongs to the technical field of adsorption materials, and relates to a two-dimensional L-FMPBA-MOF (Layered-FeMn-PBA-MOF) and a preparation method thereof, a mixed matrix membrane and application thereof in adsorbing Rb + and Cs + in water. Background Rubidium (Rb) and cesium (Cs) are important rare alkali metals, and are widely applied to the fields of precision timing, special glass, catalysis, energy conversion and biological medicine due to the unique physicochemical properties of the metals. In the field of new energy sources, rubidium and cesium and compounds thereof show indispensable values, wherein a rubidium and cesium atomic clock is a core of high-precision time synchronization of satellite navigation, a 5G/6G communication network and an intelligent power grid, stability and scheduling efficiency of renewable energy grid connection are directly affected, cesium compounds are used as high-efficiency photoelectric materials, photoelectric conversion efficiency and long-term stability of perovskite solar cells can be improved, rubidium and cesium alloys are key working media of magnetohydrodynamic power generation and ion propellers, potential application is realized in aerospace and advanced energy systems, and in addition, special functions of rubidium and cesium in novel high-energy density batteries, nuclear energy and energy storage systems are increasingly highlighted. However, rubidium and cesium are extremely low in abundance and highly dispersed in the crust and difficult to economically recover by conventional ore extraction processes. Salt lake brine, especially lithium-rich salt lake old brine, is an important carrier for rubidium and cesium. However, the brine system has the interference of coexisting ions such as high concentration Na +、K+、Mg2+, ca 2+ and the like, and the concentration of Rb + and Cs + is low, the radius of hydrated ions is similar, so that the high-selectivity separation and extraction of Rb + and Cs + face a great challenge. Therefore, developing the efficient Rb + and Cs + adsorption separation technology aiming at salt lake brine is not only important to guaranteeing the supply safety of key raw materials, but also directly supports the core basic links of new energy technology iteration, high-end equipment manufacturing and new generation information technology industry upgrading. Common methods for extracting Rb + and Cs + are precipitation, extraction and adsorption. The adsorption method is a mainstream technology for separating and enriching Rb + and Cs + at present because of the advantages of recycling, convenient operation, high recovery rate, simple process and the like, and the performance core of the adsorption method depends on the design of an adsorption material. The traditional adsorption material is limited by a block structure or a low-efficiency interface design, so that the ion diffusion path is long, the utilization rate of internal active sites is low, the mass transfer resistance is high, and the quick and high-capacity adsorption of low-concentration Rb + and Cs + in a complex brine system is difficult to realize. Meanwhile, the powder material has the problems of difficult solid-liquid separation, easy loss of active components and the like in industrial operation. Particularly, in view of the requirement of new energy industry on large-scale, low-cost and green extraction of key metal resources, the existing Rb + and Cs + adsorption technology is difficult to simultaneously meet multiple challenges of high selectivity, fast dynamics and engineering application reliability. Therefore, development of a novel adsorption material which has an ultra-short transmission channel, is rich in active sites and low in migration energy barrier and can meet the requirements of industrial application is an urgent need for improving the separation efficiency of the salt lake brine Rb + and Cs +. Disclosure of Invention In order to solve the problem that the adsorption material in the prior art is difficult to realize rapid and high-capacity adsorption of low-concentration Rb + and Cs + in a complex brine system, the invention provides a two-dimensional L-FMPBA-MOF, a mixed matrix membrane and application of the two-dimensional L-FMPBA-MOF in the aspect of adsorbing Rb + and Cs + in water. The invention is realized by the following technical scheme: In a first aspect, the present invention provides a two-dimensional L-FMPBA-MOF, the two-dimensional L-FMPBA-MOF being a metal organic framework material having a two-dimensional lamellar structure, metal ions in the metal organic framework material being Fe 3+ and Mn 2+, the two-dimensional L-FMPBA-MOF having diffraction characteristics of prussian blue analogues in an X-ray diffraction pattern. In a second aspect, the invention provides a method for preparing the two