CN-117143305-B - NH (NH)2-COFs@ZnS photocatalytic material and preparation method and application thereof

Abstract

The invention discloses an NH 2 -COFs@ZnS photocatalytic material, and a preparation method and application thereof. Synthesizing a NH 2 -COFs material by a Schiff base reaction on a polyamino aromatic ligand and a polyaldehyde aromatic ligand, and performing a hydrothermal reaction on the NH 2 -COFs material, zinc salt and a sulfur source to obtain the NH 2 -COFs@Zn photocatalytic material. The NH 2 -COFs@ZnS photocatalytic material has the advantages of excellent photocatalytic activity, good structural stability, reusability and the like, can be applied to photocatalytic reduction of CO 2 , and has the advantages of simple preparation method, low cost and the like, and meets the requirement of industrial production.

Inventors

• HUANG JIANHAN
• LIU YOUNIAN
• WANG YOU
• LIU ZHONGXING
• ZHANG LUOYU
• WANG JIAJIA
• CAO YIWEN
• YANG FAN
• LI JIAWEI
• ZHOU FA

Assignees

• 中南大学

Dates

Publication Date

20260508

Application Date

20230831

Claims (6)

1. 1. A preparation method of an NH 2 -COFs@ZnS photocatalytic material is characterized in that a polyamino aromatic ligand and a polyaldehyde aromatic ligand are reacted through Schiff base to synthesize an NH 2 -COFs material, and the NH 2 -COFs material, zinc salt and a sulfur source are subjected to hydrothermal reaction to obtain the material; the polyamino aromatic ligand is at least one of 2,4, 6-tri (aminophenyl) -1,3, 5-triazine and 1,3, 5-tri (aminophenyl) benzene; The polyaldehyde aromatic ligand is at least one of 2, 5-dibromoterephthalaldehyde, 2, 5-dimethoxy terephthalaldehyde, 2, 5-dihydroxyterephthalaldehyde and terephthalaldehyde; the molar ratio of the polyamino aromatic ligand to the polyaldehyde aromatic ligand is 1.2-2:1; The ratio of the NH 2 -COFs material to the zinc salt to the sulfur source is measured according to the mass ratio of the NH 2 -COFs material to the generated ZnS of 1-4:10.
2. 2. The preparation method of the NH 2 -COFs@ZnS photocatalytic material according to claim 1, wherein the condition of the Schiff base reaction is that the reaction is carried out for 72-96 hours at the temperature of 20-120 ℃.
3. 3. The preparation method of the NH 2 -COFs@ZnS photocatalytic material according to claim 1 or 2, wherein the hydrothermal reaction condition is that the reaction is carried out for 12-24 hours at a temperature of 100-120 ℃.
4. 4.A NH 2 -COFs@ZnS photocatalytic material, which is characterized by being prepared by the preparation method according to any one of claims 1-3.
5. 5. The NH 2 -COFs@ZnS photocatalytic material according to claim 4, wherein the specific surface area of the NH 2 -COFs@ZnS photocatalytic material is 700-1600 m 2 /g, the pore volume is 0.5-1.0 cm 3 /g, the average pore diameter is 1.0-4.0 nm, the ultraviolet visible light absorption range is >500 nm, and the forbidden bandwidth is <2.6 eV.
6. 6. The application of the NH 2 -COFs@ZnS photocatalytic material as claimed in claim 4 or 5, which is characterized by being applied to photocatalytic reduction of CO 2 .

Description

NH 2 -COFs@ZnS photocatalytic material and preparation method and application thereof Technical Field The invention relates to a photocatalytic material, in particular to a NH 2 -COFs@ZnS photocatalytic material, and particularly relates to a NH 2 -COFs@ZnS photocatalytic material based on COFs finite field high dispersion ZnS, a preparation method and application thereof in the reduction of photocatalytic CO 2, belonging to the technical field of functional polymer synthesis. Background Carbon dioxide (CO 2) is a major greenhouse gas responsible for global warming, and its excessive emissions raise a series of global environmental problems threatening human survival and development. Atmospheric CO 2 is derived mainly from the combustion of fossil fuels, which account for about 40% of the total emissions of CO 2 worldwide. Although clean energy is currently being released, fossil fuels remain dominant. Thus, it is also difficult to achieve "carbon-to-peak carbon neutralization" in the short term by reducing the use of fossil fuels. On the other hand, CO 2 is a green renewable C1 resource with a rich reserve. The CO 2 is catalytically converted into chemical products such as CO, CH 4, methanol, olefin and the like, so that not only can the dependence of human on fossil energy be reduced, but also the emission of CO 2 can be effectively reduced, and the method is a research hotspot in the fields of current chemical industry, environment, energy and the like. The method for catalytic conversion of CO 2 mainly comprises the steps of photocatalytic conversion, thermocatalytic conversion, electrocatalytic conversion, biocatalytic conversion and the like, wherein the photocatalytic conversion of CO 2 is favored by researchers due to the advantages of mild conditions, simple process, environmental friendliness and the like, a high-activity, high-selectivity and high-stability photocatalytic system is developed, and the efficient and rapid conversion of CO 2 into CO, CH 4, methanol or other chemicals is a scientific front-end problem to be solved in the fields of current resource chemical industry and environmental chemical industry. Inorganic semiconductors such as metal oxides, metal sulfides, metal nitrides and the like are widely used for CO 2 photocatalytic conversion due to the advantages of simple preparation, strong visible light absorption capability, stable physical and chemical properties and the like. In addition, the light response range can be further widened through means of microstructure adjustment, surface modification, heterojunction construction and the like, the recombination of electron-hole pairs is inhibited, the photocatalysis efficiency is improved, and the high-selectivity conversion of a target product is realized. ZnS is a photocatalyst excellent in performance, and has been rapidly developed in recent years, but its own serious photo-generated carrier recombination causes its poor photocatalytic activity to be difficult to be effectively solved. The covalent organic frameworks (Covalent Organic Frameworks, COFs) are organic porous crystalline materials connected by covalent bonds, and the rigid structure of the crosslinked network of the covalent organic frameworks endows the organic porous crystalline materials with higher specific surface area and rich pore structures, and the covalent organic frameworks are uniform in pore channels and controllable in size. The good conjugation structure of COFs can widen the photoresponse range, show high-efficiency electron mobility and improve the separation efficiency of photogenerated carriers. COFs have the advantages of designability of organic units, diversity and adjustability of grid structures, and the like, and provide possibility for structural design and custom-made function development of photocatalytic materials, but related reports of amino-functionalized COFs-supported ZnS photocatalysts are not seen so far. Disclosure of Invention Aiming at the defects that the inorganic semiconductor photocatalytic material and the COFs are difficult to efficiently convert the CO 2 and the like in the prior art, the first aim of the invention is to provide the NH 2 -COFs@ZnS photocatalytic material, the inorganic ZnS photocatalyst is firmly limited or packaged in or on the nano pore canal of the inorganic ZnS photocatalyst by utilizing the amino functionalized COFs, perfect combination of the ZnS and the COFs is realized, the inorganic semiconductor photocatalytic material and the COFs are effectively coupled in structure to generate an interface heterojunction, the photocatalytic performance of the inorganic semiconductor photocatalytic material and the COFs are cooperatively improved, the efficient separation of photo-generated carriers can be promoted by means of adjusting the microstructure, the vacancy defect and the like of the ZnS, the combination of electron-hole pairs is inhibited, the photocatalytic efficiency is improved, the conjugated