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CN-119570044-B - CuBDC nano-sheet and preparation method and application thereof

CN119570044BCN 119570044 BCN119570044 BCN 119570044BCN-119570044-B

Abstract

The invention discloses a CuBDC nanosheet and a preparation method and application thereof. The CuBDC nanosheets are single-layer two-dimensional CuBDC nanosheets, and the aspect ratio of the CuBDC nanosheets is 80-400. The CuBDC nanosheets are single-layer, have higher aspect ratio and large specific surface area. The preparation method is simple, the materials are cheap and easy to obtain, the cost is low, and the preparation method is easy for mass preparation. The CuBDC nanosheets are suitable for the fields of gas storage, adsorption separation, heterogeneous catalysis, electrochemistry and analysis.

Inventors

  • WANG XUELI
  • ZHANG HUICHENG
  • LING FENGXIANG
  • YANG WEIYA
  • WANG SHAOJUN

Assignees

  • 中国石油化工股份有限公司
  • 中石化（大连）石油化工研究院有限公司

Dates

Publication Date
20260505
Application Date
20230905

Claims (10)

  1. 1. The CuBDC nanosheets are single-layer two-dimensional CuBDC nanosheets, wherein the aspect ratio of the CuBDC nanosheets is 100-400, the specific surface area of the CuBDC nanosheets is 580-630 m 2 /g, the length of the CuBDC nanosheets is 2-6 mu m, and the thickness of the CuBDC nanosheets is 15-25 nm.
  2. 2. The CuBDC nanosheets of claim 1, wherein the CuBDC nanosheets are 4-5 μm in length and 18-22 nm in thickness.
  3. 3. A method for preparing the CuBDC nanosheets of any one of claims 1-2, comprising: (1) The method adopts a thin film reactor, wherein a thin film component is arranged in the thin film reactor, and the reactor is divided into an upper layer area and a lower layer area by the thin film component; (2) Placing copper ion solution in an upper layer area of a film reactor, placing ligand solution in a lower layer area of the film reactor, dripping the copper ion solution into the ligand solution through holes of a film component, reacting in the lower layer area of the reactor, and separating to obtain the CuBDC nanosheets; In the step (1), the pore diameter of the pore on the film component is 3-5 mu m, the porosity is 80-90%, and the pore thickness is 30-60 mu m; in the step (2), the reaction is carried out under microwave heating, wherein the temperature of the microwave heating is 40-55 ℃ and the time is 3-6 hours.
  4. 4. The method according to claim 3, wherein in the step (2), the copper ion solution comprises an inorganic copper salt, N-dimethylformamide and acetonitrile.
  5. 5. The preparation method according to claim 4, wherein in the step (2), the copper ion solution comprises 0.8% -1.5% of inorganic copper salt, 22% -27% of N, N-dimethylformamide and 72% -77% of acetonitrile based on the mass of the copper ion solution.
  6. 6. A process according to claim 3, wherein in step (2) the ligand solution comprises phthalic acid, N-dimethylformamide and acetonitrile.
  7. 7. The method according to claim 6, wherein in the step (2), the ligand solution comprises 0.8% -1.5% of terephthalic acid, 72% -77% of N, N-dimethylformamide and 22% -27% of acetonitrile based on the mass of the ligand solution.
  8. 8. The method according to claim 3, wherein in the step (2), the mass ratio of the copper ion solution to the ligand solution is 0.8 to 1.2.
  9. 9. The method according to claim 3, wherein in the step (2), the copper ion solution is dropped for 100 to 120 minutes.
  10. 10. Use of CuBDC nanoplatelets according to any of claims 1-2 or prepared by the preparation method according to any of claims 3-9 in the fields of gas storage, adsorptive separation, heterogeneous catalysis, electrochemistry or analysis.

Description

CuBDC nano-sheet and preparation method and application thereof Technical Field The invention belongs to the field of nano materials, and particularly relates to a CuBDC nano-sheet and a preparation method and application thereof. Background Metal Organic Frameworks (MOFs) are organic-inorganic hybrid porous crystalline materials composed of metal ion centers and organic ligands. The two-dimensional (2D) MOF nanosheets are anisotropic MOFs with a two-dimensional layered structure, and have the physicochemical properties of ultrathin lamellar thickness, good solubility and dispersibility, excellent photoelectric properties, easy functionalized pore surfaces and the like. Compared with the traditional isotropic MOF, the porous and pore-diameter-adjustable MOF material not only has the characteristics of adjustable porosity and pore diameter, but also has the long-range order and the anisotropy of the crystal material, high porosity, large specific surface area and the like, and can be widely applied to the fields of energy storage, catalysis, sensing, adsorption separation and the like. 2D-MOF is a novel class of materials with great potential. Copper terephthalate (CuBDC) material is a typical 2D MOF with a structured lamellar structure, and much literature has been reported. Although the appearance and the properties are excellent, the synthesis steps are difficult to control, reproduction is difficult, and the two-dimensional nano-sheets with excellent appearance can be obtained only by precisely controlling the solution concentration and the reaction rate of metal ions and ligands, and the CuBDC nano-sheets synthesized by most of the current documents need secondary treatment or have low aspect ratio. CN106252663B discloses a preparation method of CuBDC nanosheets, which comprises the steps of firstly weighing copper nitrate solid, mixing the copper nitrate solid, p-dibenzoic acid solid, acetonitrile serving as an organic solvent and N, N-dimethylformamide, secondly heating and stirring the mixture obtained in the first step in a water bath, and thirdly, drying the solution obtained in the second step in an oven to obtain the CuBDC nanosheets serving as the metal-organic framework material. According to the method disclosed by the invention, cu salt is directly dissolved into a solvent, the initial crystal nucleus is formed rapidly, the crystal nucleus shape is not easy to control, the obtained CuBDC nano-sheets are stacked and are difficult to strip, and the shape regularity is poor. The method adopts conventional heating methods such as water bath, etc., and has longer time consumption in the crystal growth process and lower efficiency and yield. CN114288879A discloses a preparation method of two-dimensional CuBDC-NH 2, which comprises the steps of firstly adding anhydrous copper acetate into a mixed solution A for dissolution to obtain an anhydrous copper acetate solution, secondly adding 2-amino terephthalic acid into a mixed solution B for dissolution to obtain a 2-amino terephthalic acid solution, thirdly spraying the anhydrous copper acetate solution into the 2-amino terephthalic acid solution through an ultrasonic spraying device, standing to obtain a solid substance, and washing and filtering the solid substance to obtain a two-dimensional CuBDC-NH 2 solid. The feeding mode of the ultrasonic spraying device used in the invention still shows macroscopic drop feeding, the control effect on the metal precursor is limited, the nucleation process and the product structure still have the problem of difficult control, the obtained CuBDC nanometer sheets are serious in agglomeration, larger in thickness of the sheets, easy to stack and low in aspect ratio. In the existing preparation method, no effective method is provided for controlling the contact reaction rate of the metal solution and the ligand solution, the obtained CuBDC nanometer sheet layer is thicker, the aspect ratio is lower, the reaction is difficult to complete, and the yield is lower. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a CuBDC nanosheet as well as a preparation method and application thereof. The CuBDC nanosheets are single-layer, have higher aspect ratio and large specific surface area. The preparation method is simple, the materials are cheap and easy to obtain, the cost is low, and the preparation method is easy for mass preparation. The CuBDC nanosheets are suitable for the fields of gas storage, adsorption separation, heterogeneous catalysis, electrochemistry and analysis. The first aspect of the present invention provides a CuBDC nanoplatelet. The CuBDC nanosheets are single-layer two-dimensional CuBDC nanosheets, the aspect ratio of the CuBDC nanosheets is 80-400, preferably 100-300, and the aspect ratio is the ratio of the length to the thickness of the nanosheets. According to the invention, the specific surface area of the CuBDC nanosheets is 580-630 m 2/g. According to the inv