CN-121972235-A - G-C3N4Cu-BTC catalyst, and preparation method and application thereof

Abstract

The invention belongs to the technical field of photocatalytic materials, and particularly relates to a g-C 3 N 4 /Cu-BTC catalyst, a preparation method and application thereof. After Cu-BTC blue powder crystals are prepared by a hydrothermal method, melamine is placed in a muffle furnace to be subjected to high-temperature calcination treatment, so that g-C 3 N 4 in a yellow powder shape can be prepared, then, the prepared Cu-BTC blue powder and the g-C 3 N 4 yellow powder are mixed according to a preset mass ratio by adopting a physical grinding compounding method, and mechanical fusion is realized by fully grinding, so that the g-C 3 N 4 /Cu-BTC catalyst with a compound structure is finally prepared. The preparation process realizes the structural integration and performance synergy of the two functional materials through the synergistic effect of hydrothermal synthesis and high-temperature calcination and the combination of a physical grinding composite process, and provides a preparation path of the high-efficiency composite material for the application of photocatalysis for inhibiting red tide clod algae and the like.

Inventors

• LIU SHUYUAN
• QI KEZHEN
• WU MINGCAN
• LIN SHU
• LV NA

Assignees

• 大理大学

Dates

Publication Date

20260505

Application Date

20260121

Claims (10)

1. 1. A preparation method of a g-C 3 N 4 /Cu-BTC catalyst is characterized by comprising the following steps: S1, uniformly mixing a copper nitrate solution and a trimesic acid solution, and preparing Cu-BTC through crystallization reaction; s2, calcining melamine at a high temperature to obtain g-C 3 N 4 ; S3, uniformly mixing the g-C 3 N 4 and the Cu-BTC, and fully grinding to obtain the g-C 3 N 4 /Cu-BTC catalyst.
2. 2. The method according to claim 1, wherein in S1, the volume ratio of the copper nitrate solution to the trimesic acid solution is 1:1.
3. 3. The preparation method of claim 2, wherein in S1, the concentration of the copper nitrate solution is 0.05 g/mL, the solvent is deionized water, the concentration of the trimesic acid solution is 0.02 g/mL, and the solvent is absolute ethyl alcohol.
4. 4. The preparation method according to claim 1, wherein in S1, the crystallization reaction is carried out at a temperature of 120-150 ℃ for 12-15 hours.
5. 5. The preparation method according to claim 1, wherein in S2, the high-temperature calcination is performed at a temperature rising rate of 5 ℃ per minute, a calcination temperature of 500-550 ℃ and a calcination time of 2-4 h.
6. 6. The preparation method according to claim 1, wherein in S3, the mass of g-C 3 N 4 is 5 to 30% of the mass of Cu-BTC.
7. 7. The g-C 3 N 4 /Cu-BTC catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. 8. The g-C 3 N 4 /Cu-BTC catalyst of claim 7, wherein the g-C 3 N 4 /Cu-BTC catalyst particle size is 300-800 nm.
9. 9. Use of the g-C 3 N 4 /Cu-BTC catalyst of claim 7 or 8 for photocatalytic inhibition of harmful algae.
10. 10. The use according to claim 9, wherein the g-C 3 N 4 /Cu-BTC catalyst has an effective concentration of 1-5 mg/mL.

Description

G-C 3N4/Cu-BTC catalyst, preparation method and application thereof Technical Field The invention belongs to the technical field of photocatalytic materials, and particularly relates to a g-C 3N4/Cu-BTC catalyst, a preparation method and application thereof. Background Harmful Algal Bloom (HABs), particularly those initiated by heterotrimeric algae (Heterosigma akashiwo), has become a ubiquitous ecological crisis in coastal waters worldwide. The algal bloom not only can consume dissolved oxygen and destroy aquatic food networks, but also can secrete fish toxins to cause large-scale death of fishes in aquaculture, so that disastrous economic loss is caused, and marine organism diversity is seriously threatened. Although traditional treatment strategies (such as clay physical flocculation and chemical algicide inactivation) can alleviate algal bloom to some extent, they often have the risks of high operating costs, low efficiency, and more critical secondary pollution to the ecosystem. Therefore, there is a need to develop green, sustainable and efficient techniques to control detrimental algal bloom without compromising environmental safety. Among the new abatement technologies, advanced Oxidation Processes (AOPs) based photocatalytic inactivation technologies have received attention because of the ability to deeply mineralize organic pollutants and microorganisms using solar energy. To date, numerous photocatalysts have been successfully developed and applied to freshwater algal bloom control, and a great deal of research has focused on photocatalytic treatment of cyanobacteria (e.g., microcystis aeruginosa). However, research on photocatalytic inactivation of marine harmful algae is still relatively poor. Unlike fresh water environment, marine environment has the features of high salinity, complex ion background, etc. and has strict requirement on the stability and activity of photocatalyst. Therefore, the development of a high-stability photocatalyst specially designed for ocean red tide control has important scientific and practical significance. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a strategy for combining the visible light response characteristic of g-C 3N4 with the high specific surface area and the regular pore structure of Cu-BTC, and realizes the collaborative optimization of charge dynamics through an S-type heterojunction interface, namely the photo-generated electrons of a g-C 3N4 conduction band directionally migrate to a Cu-BTC valence band under the irradiation of visible light, thereby realizing the unification of high-efficiency photocatalysis performance, wide environmental adaptability and green sustainability and providing an innovative composite catalysis solution for ocean red tide treatment and water body restoration. In order to solve the technical problems, the invention adopts the following technical scheme: the first aspect of the invention provides a preparation method of a g-C 3N4/Cu-BTC catalyst, which comprises the following steps: S1, uniformly mixing a copper nitrate solution and a trimesic acid solution, and preparing Cu-BTC through crystallization reaction; s2, calcining melamine at a high temperature to obtain g-C 3N4; S3, uniformly mixing the g-C 3N4 and the Cu-BTC, and fully grinding to obtain the g-C 3N4/Cu-BTC catalyst. In S1, the volume ratio of the copper nitrate solution to the trimesic acid solution is 1:1. In S1, the concentration of the copper nitrate solution is 0.05 g/mL, the solvent is deionized water, the concentration of the trimesic acid solution is 0.02 g/mL, and the solvent is absolute ethyl alcohol. Specifically, a 1:1 mixture of water and ethanol may form a gradient polarity environment. Cu 2+ is easy to hydrolyze in pure water phase, and the addition of ethanol can adjust the system polarity, promote the dissolution and deprotonation of trimesic acid (H 3 BTC), inhibit excessive hydrolysis of Cu 2+, and ensure that the coordination reaction is efficiently carried out in a proper pH range. Experiments show that the ligand-metal charge transfer efficiency is highest at the ratio, and the stable Cu-BTC three-dimensional network structure is formed. In the step S1, the crystallization reaction is carried out at the temperature of 120-150 ℃ for 12-15 hours. Specifically, the reaction temperature should be controlled at 120-150 ℃ to be suitable for synthesizing Cu-BTC blue powder crystals. The reaction time is controlled to be 12-15 hours, so that the nano particles can be conveniently dispersed. The unreacted precursor is easy to remain after the time is less than 12 hours, and the grain aggregation can be caused after the time is more than 15 hours. In some embodiments of the invention, in S1, the crystallization reaction is performed at a temperature of 120 ℃ for a time of 12 h. In some embodiments of the present invention, after the crystallization reaction is completed in S1, solids are collected by cen