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CN-121972227-A - Carboxyl micromolecule compound modified MPM material, preparation method and application

CN121972227ACN 121972227 ACN121972227 ACN 121972227ACN-121972227-A

Abstract

The invention relates to the technical field of photocatalytic materials, and provides a carboxyl small molecular compound modified MPM material, a preparation method and application thereof. Compared with the prior art, the preparation method of the carboxyl micromolecule compound modified MPM material has the advantages that the amino-containing MPM material and the carboxyl micromolecule compound are subjected to amidation reaction to carry out bridging connection, so that the modified MPM material with enhanced photocatalytic performance is formed, the carboxyl micromolecule compound can be used as molecular glue, the coordination bond and hydrogen bond synergistic effect of metal-carboxylic acid of the MPM material are combined to enhance frame connectivity and structural order, the separation and migration of photo-generated charges are effectively promoted, the rapid recombination of photo-generated electron-hole pairs is successfully restrained, and therefore, the photon efficiency is improved, and the photocatalytic performance is remarkably improved.

Inventors

  • ZHAO YUE
  • LIN CUNGUO
  • ZHANG JINWEI
  • ZHOU XINYA
  • QIU ZHENGHUI
  • WANG LI

Assignees

  • 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所)

Dates

Publication Date
20260505
Application Date
20260128

Claims (10)

  1. 1. A preparation method of a carboxyl micromolecule compound modified MPM material is characterized in that the preparation method is characterized in that the MPM material containing amino and the carboxyl micromolecule compound undergo amidation reaction to form the carboxyl micromolecule compound modified MPM material.
  2. 2. The preparation method of the carboxyl small molecular compound modified MPM material as claimed in claim 1, wherein the preparation method comprises the following steps: s1, adenine, copper nitrate trihydrate and an anion source compound are stirred and reacted in a mixed solvent to obtain MPM material mother liquor; S2, adding carboxyl micromolecule compound powder into the MPM material mother liquor, stirring, dissolving and reacting to obtain the MPM material mother liquor modified by the carboxyl micromolecule compound; And S3, centrifuging and drying the mother liquor of the MPM material modified by the small carboxyl molecular compound to obtain the MPM material modified by the small carboxyl molecular compound.
  3. 3. The preparation method of the carboxyl small molecular compound modified MPM material according to claim 2, wherein the concentration of adenine in the MPM material mother liquor is 2.0-3.0 g/L, the concentration of copper nitrate trihydrate in the MPM material mother liquor is 1.5-2.0 g/L, the concentration of the anion source compound in the MPM material mother liquor is 1.5-2.0 g/L, and the concentration of the carboxyl small molecular compound in the MPM material mother liquor is 1.0-1.5 g/L.
  4. 4. The method for preparing the carboxyl small molecular compound modified MPM material according to claim 2, wherein the carboxyl small molecular compound is at least one of trimesic acid, oxalic acid, maleic acid and phthalic acid.
  5. 5. The method for preparing a carboxyl small molecular compound modified MPM material according to claim 2, wherein the anion source compound is one of copper chloride and ammonium fluotitanate.
  6. 6. The method for preparing a carboxyl micromolecular compound modified MPM material according to claim 2, wherein the mixed solvent is at least two of water, ethanol, N-dimethylformamide and acetonitrile.
  7. 7. The preparation method of the carboxyl micromolecule compound modified MPM material according to claim 2 is characterized in that in the step S1, the reaction temperature is 20-80 ℃, the reaction time is 2-24 h, and in the step S2, the reaction temperature is 20-80 ℃ and the reaction time is 2-24 h.
  8. 8. The preparation method of the carboxyl micromolecule compound modified MPM material according to claim 2, wherein in the step S3, the drying temperature is 40-150 ℃, and the drying time is 1-10 h.
  9. 9. The carboxyl small molecular compound modified MPM material is characterized in that the carboxyl small molecular compound modified MPM material is prepared by the preparation method of the carboxyl small molecular compound modified MPM material according to any one of claims 1-8.
  10. 10. An application of a carboxyl small molecular compound modified MPM material as claimed in claim 9 in the field of photocatalysis.

Description

Carboxyl micromolecule compound modified MPM material, preparation method and application Technical Field The invention relates to the technical field of photocatalytic materials, in particular to a carboxyl micromolecular compound modified MPM material, a preparation method and application. Background The photocatalysis technology has wide prospect in the fields of environmental remediation (such as organic pollutant degradation and marine antifouling) and energy sustainability by utilizing solar energy to drive chemical reaction. The technology relies on the photocatalyst to absorb photons to generate electron-hole pairs so as to drive redox reaction and mineralize refractory pollutants (such as dyes and antibiotics) into harmless substances. However, the wide application of the photocatalysis technology is limited by the problems of rapid recombination of photon-generated carriers, narrow light absorption range (mainly limited to ultraviolet region), poor catalyst stability and cyclicity, and the like. Molecular Porous Materials (MPMs) are a class of solid state materials assembled from discrete molecules through weak interactions (e.g., hydrogen bonding). Such materials were originally developed by the Zaworotko team (J. Am. chem. Soc. 2013,135,10950-10953), representative of which are MPM-1-TIFSIX [ Cu 2(ade)4(TiF6)2 ] and MPM-1-Cl ([ Cu 2(ade)4Cl2]Cl2). From the structural feature, MPMs is mainly constructed by non-covalent bond, which can form intramolecular pore canal and also can generate intermolecular pore canal. Representative materials MPM-1-TIFSIX and MPM-1-Cl have definite porous structures, can promote light capture and reactant diffusion, but still have the problem of low charge separation efficiency, for example, MPM-1-TIFSIX and MPM-1-Cl show rapid photo-generated electron-hole recombination, thereby causing low quantum efficiency and poor photocatalytic effect. In summary, the existing MPM materials exhibit rapid photo-generated electron-hole recombination, which results in low quantum efficiency and poor photocatalytic effect. In view of this, the present invention has been made. Disclosure of Invention The invention aims to provide a carboxyl micromolecule compound modified MPM material, a preparation method and application thereof, and aims to solve the problems that in the prior art, the MPM material shows rapid photo-generated electron-hole recombination, so that the quantum efficiency is low, and the photocatalysis effect is poor. In order to achieve the above purpose, the technical scheme of the invention is realized as follows: A preparation method of a carboxyl micromolecule compound modified MPM material comprises the step of carrying out amidation reaction on an MPM material containing amino and a carboxyl micromolecule compound to form the carboxyl micromolecule compound modified MPM material. Further, the preparation method comprises the following steps: s1, adenine, copper nitrate trihydrate and an anion source compound are stirred and reacted in a mixed solvent to obtain MPM material mother liquor; S2, adding carboxyl micromolecule compound powder into the MPM material mother liquor, stirring, dissolving and reacting to obtain the MPM material mother liquor modified by the carboxyl micromolecule compound; And S3, centrifuging and drying the mother liquor of the MPM material modified by the small carboxyl molecular compound to obtain the MPM material modified by the small carboxyl molecular compound. Further, the concentration of adenine in the MPM material mother liquor is 2.0-3.0 g/L, the concentration of copper nitrate trihydrate in the MPM material mother liquor is 1.5-2.0 g/L, the concentration of the anion source compound in the MPM material mother liquor is 1.5-2.0 g/L, and the concentration of the carboxyl small molecule compound in the MPM material mother liquor is 1.0-1.5 g/L. Further, the small carboxyl molecule compound is at least one of trimesic acid, oxalic acid, maleic acid and phthalic acid. Further, the anion source compound is one of copper chloride and ammonium fluotitanate. Further, the mixed solvent is at least two of water, ethanol, N-dimethylformamide and acetonitrile. Further, in the step S1, the reaction temperature is 20-80 ℃, the reaction time is 2-24 hours, and in the step S2, the reaction temperature is 20-80 ℃ and the reaction time is 2-24 hours. In the step S3, the drying temperature is 40-150 ℃ and the drying time is 1-10 h. In a second aspect of the present invention, a small carboxyl molecule compound modified MPM material is provided, and the small carboxyl molecule compound modified MPM material uses any one of the preparation methods of small carboxyl molecule compound modified MPM material. In a third aspect of the present invention, an application of the small carboxyl molecule compound modified MPM material in the field of photocatalysis is provided. Compared with the prior art, the carboxyl micromolecular compound modified MPM mater