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CN-121974431-A - Flexible Fe/Cu-MOF@CC composite film material and preparation method and application thereof

CN121974431ACN 121974431 ACN121974431 ACN 121974431ACN-121974431-A

Abstract

The invention discloses a flexible Fe/Cu-MOF@CC composite film material and a preparation method and application thereof, wherein the method removes impurities on the surface of a flexible substrate (carbon cloth) through ultrasonic cleaning of acetone, ethanol and deionized water, hydrophilic groups are introduced through nitric acid activation, feCl 3 ·6H 2 O、CuCl 2 ·2H 2 O and 2, 5-dihydroxyterephthalic acid are dissolved in a DMF/methanol system to form a precursor solution, and an Fe/Cu-MOF film is grown on an activated substrate in situ through a hydrothermal method. According to the technology, by introducing the Fe/Cu bimetal coordination center, the MOF electronic structure is effectively regulated and controlled, the problems of weak intervention capability and low dissociation efficiency of a water molecule hydrogen bond network caused by a single metal site and a fixed electronic structure in the traditional MOFs are solved, the interfacial water evaporation performance of the material under a complex working condition is remarkably improved, and the technology is suitable for solar-driven sea water desalination and wastewater treatment.

Inventors

  • ZHANG RONGRONG
  • WANG WEIKE
  • Jing Zhuohang
  • YAN RUIHANG
  • Su Pengchao
  • ZHANG XUELIAN
  • WANG MENGYU

Assignees

  • 陕西科技大学

Dates

Publication Date
20260505
Application Date
20260327

Claims (10)

  1. 1. The preparation method of the flexible Fe/Cu-MOF@CC composite film is characterized by comprising the following steps of: S1, sequentially adopting acetone, ethanol and deionized water to clean a flexible substrate in an ultrasonic environment to remove pollutants and impurities on the surface of the flexible substrate; s2, placing the cleaned flexible substrate in nitric acid, and performing activation treatment on the flexible substrate; S3, dissolving FeCl 3 ·6H 2 O, 2, 5-dihydroxyterephthalic acid and CuCl 2 ·2H 2 O in DMF, adding methanol, carrying out ultrasonic homogenization to obtain Fe/Cu-MOF precursor solution, immersing the activated flexible substrate in the Fe/Cu-MOF precursor solution, and carrying out hydrothermal reaction to obtain the flexible Fe/Cu-MOF@CC composite film.
  2. 2. The preparation method of the flexible Fe/Cu-MOF@CC composite film according to claim 1, wherein the frequency of an ultrasonic instrument is 30-50 kHz during ultrasonic treatment.
  3. 3. The method for preparing the flexible Fe/Cu-MOF@CC composite film according to claim 1, wherein the temperature of the activation treatment is 70-85 ℃ and the treatment time is 3-5 hours.
  4. 4. The method for preparing the flexible Fe/Cu-MOF@CC composite film according to claim 1, wherein the concentration of FeCl 3 ·6H 2 O in the Fe/Cu-MOF precursor solution is 0.04-0.08M, the concentration of 2, 5-dihydroxyterephthalic acid is 0.034-0.068M, and the concentration of CuCl 2 ·2H 2 O is 0.04-0.08M.
  5. 5. The preparation method of the flexible Fe/Cu-MOF@CC composite film according to claim 1, wherein the molar ratio of FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 O to 2, 5-dihydroxyterephthalic acid is 1 (1-2) (0.85-1.7).
  6. 6. The method for preparing the flexible Fe/Cu-MOF@CC composite film according to claim 5, wherein the molar ratio of FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 O to 2, 5-dihydroxyterephthalic acid is 1:1 (0.85-1.7).
  7. 7. The method for preparing the flexible Fe/Cu-MOF@CC composite film according to claim 1, wherein the reaction temperature of the hydrothermal reaction is 120-150 ℃ and the reaction time is 12-36 h.
  8. 8. The method for preparing the flexible Fe/Cu-MOF@CC composite film according to claim 6, wherein the reaction temperature of the hydrothermal reaction is 120 ℃ and the reaction time is 24 hours.
  9. 9. A flexible Fe/Cu-mof@cc composite film, characterized by being produced by the method of any one of claims 1 to 8.
  10. 10. The use of a flexible Fe/Cu-mof@cc composite film as claimed in claim 9 for interfacial solar water evaporation.

Description

Flexible Fe/Cu-MOF@CC composite film material and preparation method and application thereof Technical Field The invention belongs to the technical field of interface solar water evaporation photo-thermal, and relates to a flexible Fe/Cu-MOF@CC composite film material and a preparation method and application thereof. Background In the context of continuous growth of global population, rapid increase of industrial and agricultural water demand and low water resource utilization efficiency, fresh water shortage has become one of the major challenges restricting sustainable development of society. Seawater desalination and wastewater treatment are regarded as key ways for alleviating the crisis of water resources, and particularly, solar-driven interfacial water evaporation technology is widely focused on due to the characteristics of green and low energy consumption. In this technology, high performance photothermal materials are the core for achieving efficient water evaporation. As a crystalline porous material formed by self-assembly of metal ions/clusters and organic ligands, metal-organic framework Materials (MOFs) have great potential in the fields of catalysis, sensing, energy storage, environmental management and the like due to the ultrahigh specific surface area, adjustable pore channel structure, rich active sites and good hydrophilicity. In recent years, MOFs are widely applied to electrochemical hydrogen production, carbon dioxide reduction, pollutant adsorption and separation, solar water evaporation and other processes, and the unique porous structure of MOFs is not only beneficial to rapid transmission of water molecules, but also realizes activation of interfacial water through interaction of metal nodes and water molecules, so that evaporation energy consumption is reduced. However, although MOFs materials have many advantages, the inherent fixed electronic structure and single metal active center thereof cause limited regulation and control capability on water molecules, and deep intervention and efficient dissociation on a hydrogen bond network are difficult to realize, so that the application performance of the MOFs materials under complex working conditions such as high-salt wastewater treatment, long-term continuous operation and the like is severely restricted. Disclosure of Invention Aiming at the problems in the prior art, the invention provides a flexible Fe/Cu-MOF@CC composite film material and a preparation method and application thereof, thereby solving the technical problems that MOFs in the prior art are difficult to deeply interfere with a water molecule hydrogen bond network and realize high-efficiency dissociation due to inherent fixed electronic structures and single metal active centers and restrict the application of the MOFs in high-efficiency water evaporation under complex working conditions. The invention is realized by the following technical scheme: A preparation method of a flexible Fe/Cu-MOF@CC composite film comprises the following steps: S1, sequentially adopting acetone, ethanol and deionized water to clean a flexible substrate in an ultrasonic environment to remove pollutants and impurities on the surface of the flexible substrate; s2, placing the cleaned flexible substrate in nitric acid, and performing activation treatment on the flexible substrate; S3, dissolving FeCl 3·6H2 O, 2, 5-dihydroxyterephthalic acid and CuCl 2·2H2 O in DMF, adding methanol, carrying out ultrasonic homogenization to obtain Fe/Cu-MOF precursor solution, immersing the activated flexible substrate in the Fe/Cu-MOF precursor solution, and carrying out hydrothermal reaction to obtain the flexible Fe/Cu-MOF@CC composite film. Preferably, during ultrasonic treatment, the frequency of the ultrasonic instrument is 30-50 kHz. Preferably, the temperature of the activation treatment is 70-85 ℃, and the treatment time is 3-5 hours. Preferably, in the Fe/Cu-MOF precursor solution, the concentration of FeCl 3·6H2 O is 0.04-0.08M, the concentration of 2, 5-dihydroxyterephthalic acid is 0.034-0.068M, and the concentration of CuCl 2·2H2 O is 0.04-0.08M. Preferably, the molar ratio of FeCl 3·6H2O、CuCl2·2H2 O to 2, 5-dihydroxyterephthalic acid is 1 (1-2) (0.85-1.7). Preferably, the molar ratio of FeCl 3·6H2O、CuCl2·2H2 O to 2, 5-dihydroxyterephthalic acid is 1:1 (0.85-1.7). Preferably, the reaction temperature of the hydrothermal reaction is 120-150 ℃ and the reaction time is 12-36 h. Preferably, the reaction temperature of the hydrothermal reaction is 120 ℃ and the reaction time is 24 hours. A flexible Fe/Cu-MOF@CC composite film is prepared by the method. The application of the flexible Fe/Cu-MOF@CC composite film in interfacial solar water evaporation is provided. Compared with the prior art, the invention has the following beneficial technical effects: The invention discloses a preparation method of a flexible Fe/Cu-MOF@CC composite film, which effectively solves the problem that the water molecule