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CN-121155682-B - Efficient near-infrared response photocatalytic composite crystal and preparation method and application thereof

CN121155682BCN 121155682 BCN121155682 BCN 121155682BCN-121155682-B

Abstract

The invention provides a high-efficiency near-infrared response photocatalytic composite crystal and a preparation method and application thereof, and belongs to the technical field of preparation of non-traditional semiconductor crystals. The method comprises the steps of fusing up-conversion nano particles NaYF 4 , yb, tm and MOF to obtain an up-conversion functionalized MOF nano composite material, preparing the multifunctional MOF nano composite material through amidation reaction and reversible addition-fragmentation chain transfer polymerization, and finally fusing the composite nano particles with silver phosphate crystals to obtain the multifunctional ternary composite silver phosphate crystals through a bionic synthesis strategy. The method solves the problems of limitation of the wavelength range of light absorbed by silver phosphate and photo-corrosion, and the photocatalysis composite crystal can effectively degrade rhodamine B under near infrared light, and has excellent cycle stability while keeping the leading near infrared photocatalysis activity.

Inventors

  • NING YIN
  • CEN YIMING

Assignees

  • 暨南大学

Dates

Publication Date
20260512
Application Date
20251009

Claims (10)

  1. 1. The preparation method of the high-efficiency near-infrared response photocatalytic composite crystal is characterized by comprising the following steps of: Dispersing NaYF 4 Yb and Tm up-conversion nano particles in a solution 1, and reacting 1 to obtain an up-conversion functionalized MOF nano composite material, wherein the solute in the solution 1 is zirconium salt, an organic ligand and a regulator, and the organic ligand is 2-amino terephthalic acid; The up-conversion functionalized MOF nanocomposite is subjected to amidation reaction with a chain transfer agent CPCP under the action of a coupling agent to obtain an up-conversion functionalized MOF nanocomposite grafted with CPCP; The up-conversion functionalized MOF nanocomposite grafted with CPCP and a polymerization monomer are subjected to polymerization reaction under the action of an initiator to obtain a multifunctional MOF nanocomposite, wherein the polymerization monomer is a methacrylic compound; the multifunctional MOF nanocomposite is dispersed in silver-ammonia solution to obtain a mixed solution, and then disodium hydrogen phosphate is added into the mixed solution to perform standing reaction to obtain the photocatalysis composite crystal.
  2. 2. The method according to claim 1, wherein the NaYF 4 Yb, tm up-conversion nanoparticle is prepared by adding rare earth salt, ammonium fluoride, sodium chloride and a capping agent to a solvent for reaction 2.
  3. 3. The preparation method according to claim 2, wherein the rare earth salt comprises 77-98% of Y 3+ , 1-21% of Yb 3+ and the balance of Tm 3+ in terms of mole percentage, the end capping agent is a branched polymer, the solvent is ethylene glycol, the mole ratio of the rare earth salt, ammonium fluoride, sodium chloride and the end capping agent is (0.1-0.8): 0.3-5): 0.1-2): 0.001-0.01, the temperature of the reaction 2 is 150-200 ℃ and the time is 1-3 h.
  4. 4. The preparation method according to claim 1, wherein the zirconium salt is zirconium tetrachloride, the regulator is glacial acetic acid, the mass ratio of the zirconium tetrachloride, the 2-amino terephthalic acid and the glacial acetic acid is (50-150): (70-200): (6-30), and after NaYF 4 :Yb and Tm up-conversion nano-particles are dispersed in the solution 1, the obtained mixed solution contains NaYF 4 :Yb and Tm up-conversion nano-particles with the content of 5-60 mg; The temperature of the reaction 1 is 100-150 ℃ and the time is 1.5-3.5 h.
  5. 5. The preparation method according to claim 1, wherein the coupling agent is 4- (4, 6-dimethoxy triazine-2-yl) -4-methylmorpholine hydrochloride, the mass ratio of the coupling agent to the chain transfer agent CPCP is (2-6): 1, the mass ratio of the chain transfer agent CPCP to the up-conversion functionalized MOF nanocomposite is (2.5-6.5): 1, and the amidation reaction temperature is room temperature and the time is 6-24 h.
  6. 6. The preparation method according to claim 1, wherein the initiator is azo initiator, and the ratio of the up-conversion functionalized MOF nanocomposite to the polymerization monomer to the initiator is 50-70 mg:24-27 mmol:0.04-0.06 mmol; The temperature of the polymerization reaction is 50-70 ℃ and the time is 6-24 h.
  7. 7. The preparation method according to claim 1, wherein the multifunctional MOF nanocomposite has a content of 0.2-2.4 g/L, an ammonia content of 5-30 g/L and a silver ion concentration of 5-20 g/L in the mixed solution, and the mass ratio of the multifunctional MOF nanocomposite to disodium hydrogen phosphate is 1 (20-23).
  8. 8. The method according to claim 1, wherein the temperature of the standing reaction is 20 to 30 ℃ and the time is 8 to 48 h.
  9. 9. A highly effective near infrared responsive photocatalytic composite crystal prepared by the method of any one of claims 1-8.
  10. 10. Use of the high-efficiency near-infrared response photocatalytic composite crystal according to claim 9 in photocatalytic degradation of rhodamine B.

Description

Efficient near-infrared response photocatalytic composite crystal and preparation method and application thereof Technical Field The invention relates to the technical field of preparation of unconventional semiconductor crystals, in particular to a high-efficiency near-infrared response photocatalytic composite crystal, and a preparation method and application thereof. Background Semiconductors can absorb photons in solar energy with energy equal to or exceeding their band gap, generate electron-hole pairs and drive a variety of photoinduced chemical transformations, making such materials important in achieving the "solar to chemical energy" conversion process. However, the semiconductor photocatalyst has many problems such as low separation efficiency of photo-generated electron-hole pairs, slow migration rate, serious photo-corrosion, unstable chemistry, limited light absorption range, etc., which are key challenges to limit its practical application. Breaking through these bottlenecks is important to promote the application of semiconductor photocatalysis in the fields of energy conversion and environmental management. In nature, organisms can precisely regulate the formation and structure of biological minerals through precise interaction between biological macromolecules and mineral crystals. The multi-component hierarchical structure thus produced gives the biomineral excellent mechanical properties and functional flexibility. In light of this, scientists are actively exploring biomimetic mineralization strategies to artificially synthesize high-performance composite crystals. However, biomimetic mineralization still faces a great challenge because of how to rationally regulate the interaction of the organic matrix and mineral crystals at the molecular level, thereby breaking through the interfacial incompatibility remains an unsolved problem. Disclosure of Invention In view of the above, the present invention aims to provide a high-efficiency near-infrared response photocatalytic composite crystal, a preparation method and an application thereof. In order to achieve the above object, the present invention provides the following technical solutions: according to one of the technical schemes, the preparation method of the high-efficiency near-infrared response photocatalytic composite crystal comprises the following steps: dispersing NaYF 4 Yb and Tm up-conversion nano particles in a solution 1, and reacting 1 to obtain an up-conversion functionalized MOF nano composite material, wherein solutes in the solution 1 are zirconium salt, organic ligand and glacial acetic acid; The up-conversion functionalized MOF nanocomposite is subjected to amidation reaction with a chain transfer agent CPCP under the action of a coupling agent to obtain an up-conversion functionalized MOF nanocomposite grafted with CPCP; The up-conversion functionalized MOF nanocomposite grafted with CPCP and a polymerization monomer are subjected to polymerization reaction under the action of an initiator to obtain a multifunctional MOF nanocomposite; the multifunctional MOF nanocomposite is dispersed in silver-ammonia solution to obtain a mixed solution, and then disodium hydrogen phosphate is added into the mixed solution to perform standing reaction to obtain the photocatalysis composite crystal. According to the second technical scheme, the high-efficiency near-infrared response photocatalytic composite crystal prepared by the preparation method is provided. The third technical scheme of the invention is the application of the high-efficiency near-infrared response photocatalysis composite crystal in the photocatalytic degradation of rhodamine B. The invention discloses the following technical effects: The high-efficiency near-infrared response photocatalysis composite crystal is a ternary composite silver phosphate crystal, and the preparation method comprises the specific steps of modifying a high molecular chain on the surface of NaYF 4:Yb, tm@MOF to obtain a multifunctional MOF nanocomposite material with excellent colloid stability, and then fusing the multifunctional MOF nanocomposite material serving as guest nanoparticles with a silver phosphate host crystal through a bionic synthesis-embedding strategy. The method solves the problems of limitation of the wavelength range of light absorbed by silver phosphate (the traditional silver phosphate cannot use near infrared light) and poor circularity. The ternary composite silver phosphate crystal is prepared by an embedded strategy of biological teaching, and is used for effectively degrading rhodamine B under near infrared light. The catalyst has excellent cycle stability while keeping the advanced near infrared photocatalytic activity. Providing an effective strategy for rationally designing next generation photocatalysts to break through the existing challenges. Drawings In order to more clearly illustrate the embodiments of the present invention or the technical solutions in