CN-117732496-B - FeOOH quantum dot modified amino-rich porous ultrathin g-C3N4Preparation method and application of photo Fenton water purification material

Abstract

The invention discloses a preparation method and application of an FeOOH quantum dot modified amino-rich porous ultrathin graphite-phase carbon nitride (g-C 3 N 4 ) nanosheet efficient photo-Fenton water purification material, and belongs to the technical fields of functional nanomaterial preparation, solar energy utilization and environmental protection. The preparation method of the material comprises the steps of taking commercial nitrogen-rich precursors (cyanamide, dinitrile diamine or melamine and high molecular structure directing agents (CTAB, P123 and polyethylene glycol) as raw materials, uniformly mixing, directly calcining in air, and then carrying out chemical etching treatment to prepare the amino-functionalized modified porous ultrathin g-C 3 N 4 material (AHUCN), and then loading FeOOH quantum dots on the surface of the AHUCN material by using a coprecipitation method to obtain the FeOOH@AHUCN photocatalytic material.

Inventors

• XIAO JUN

Assignees

• 中国科学院金属研究所

Dates

Publication Date

20260512

Application Date

20231207

Claims (8)

1. 1. The application of the FeOOH quantum dot modified amino-rich porous ultrathin g-C 3 N 4 high-efficiency photo-Fenton water purification material is characterized in that the material can be applied to photo-Fenton purification of various antibiotics in water, and the specific preparation process comprises the following steps: (1) Adding the nitrogen-rich precursor and the high molecular structure guiding agent into 50-100 ml of deionized water according to a certain proportion, and strongly stirring under the water bath condition of 60-90 ℃ until the precursor is completely dissolved into a clear solution; (2) Transferring the clarified solution obtained in the step (1) to a drying oven, and drying at 80-90 ℃ for 12-14 hours to obtain white solid powder; (3) Calcining the white solid powder obtained in the step (2) at 500-650 ℃ in an air atmosphere, and preserving heat for 1-6 hours to obtain the porous ultrathin carbon nitride HUCN material; (4) Adding HUCN material obtained in the step (3) into an acid solution, stirring and etching under the condition of constant-temperature water bath, taking out, alternately washing with deionized water and ethanol for 3-5 times, and then vacuum drying at 40-50 ℃ for 10-24 hours to obtain the amino-functionalized modified porous ultrathin g-C 3 N 4 photocatalytic material AHUCN; (5) Adding AHUCN material obtained in the step (4) into ferric chloride FeCl 3 solution, stirring uniformly, adding ammonium bicarbonate NH 4 HCO 3 , stirring, taking out, carrying out alternate washing with deionized water and ethanol for 3-5 times, and then drying at 40-60 ℃ for 10-24 hours to obtain the FeOOH quantum dot modified amino-rich porous ultrathin g-C 3 N 4 photocatalytic material FeOOH@AHUCN.
2. 2. The method of claim 1, wherein the nitrogen-rich precursor is one or more of cyanamide, dinitrile diamine, urea, and melamine.
3. 3. The method of claim 1, wherein the polymeric structure directing agent is one or more of cetyltrimethylammonium bromide (CTAB), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123, and polyethylene glycol.
4. 4. The method of claim 1, wherein the mass ratio of the nitrogen-rich precursor to the polymeric structure directing agent in the step (1) is 10 (0.1-1).
5. 5. The method according to claim 1, wherein the calcination condition in the step (3) is two-step calcination, the first step is that a corundum crucible at 580-650 ℃ is calcined for 1-3 hours by capping, and the second step is that a corundum crucible at 500-520 ℃ is calcined for 4-6 hours without capping.
6. 6. The application of the method according to claim 1, wherein the acid solution in the step (4) is one of hydrochloric acid, sulfuric acid and nitric acid, the final concentration of HUCN added is 0.5-2 g/L, the mass concentration of hydrochloric acid is 36-38%, and the mass concentration of sulfuric acid is more than 98%.
7. 7. The method of claim 1, wherein the mass ratio of AHUCN to FeCl 3 in the step (5) is 1 (0.01-0.1), and the mass ratio of FeCl 3 to NH 4 HCO 3 is 1 (1-10).
8. 8. The method of claim 1, wherein the stirring reaction temperature in the step (5) is 10-60 ℃ and the stirring time is 1-10 hours.

Description

Preparation method and application of FeOOH quantum dot modified amino-rich porous ultrathin g-C 3N4 photo Fenton water purification material Technical Field The invention relates to the technical fields of functional nano material preparation, solar energy utilization and environmental protection, in particular to a preparation method and application of an amino-rich porous ultrathin g-C 3N4 photo-Fenton water purification material modified by FeOOH quantum dots. Background At present, fenton oxidation technology is one of the most effective means for treating organic pollutants in water, but the traditional Fenton oxidation technology has the problems of narrow applicable pH range, easy formation of iron mud and the like. In recent years, the semiconductor-based photocatalytic Fenton water purification and disinfection technology is widely focused on due to the characteristics of mild reaction conditions, high efficiency, environmental friendliness and the like. The mechanism of the photoFenton water purification and disinfection is that a transition metal catalyst loaded on the surface of a semiconductor reacts with H 2O2 in a water body to generate oxygen-containing active species (such as OH, O 2-), and then the oxygen-containing active species are directly oxidized to remove organic pollutants in the water body. Meanwhile, the semiconductor carrier absorbs sunlight to excite and generate electron holes, and then the photo-generated electrons migrate to the surface of the material and undergo a reduction reaction with transition metal loaded on the surface of the material to realize the cyclic use of Fenton active sites. Among the numerous semiconductor photocatalytic materials, the non-metallic polymeric photocatalytic material g-C 3N4 is considered to be one of the most promising materials for practical photocatalytic sterilization due to its visible light absorption properties, environmental friendliness, better thermal and chemical stability and ease of synthesis. Unfortunately, the low electron conductivity, severe photo-generated carrier recombination behavior, and extremely small surface active sites of g-C 3N4 severely limit their further applications. One of the most effective solutions to the above problems is to prepare ultra-thin g-C 3N4 nanoplatelets because ultra-thin structural features can provide a large specific surface area, more exposed active sites, and effectively shorten carrier transport paths, thereby reducing carrier recombination probability. On the other hand, the related reports prove that the separation and transmission efficiency of surface photogenerated electrons can be remarkably improved by carrying out chemical modification on the surface of the carbon nitride. However, although some progress has been made in the synthesis of carbon nitride nanoplatelets and the surface modification thereof, there are relatively few reports of combining two strategies to prepare efficient photo Fenton water purification materials. Disclosure of Invention The invention aims to provide an amino-rich porous ultrathin g-C 3N4 photo Fenton water purification material modified by FeOOH quantum dots, and a preparation method and application thereof. The porous ultrathin g-C 3N4 photocatalytic material is prepared by combining a high molecular structure guiding agent assisted thermal polymerization method with a chemical etching method, and FeOOH quantum dots are loaded on the surface of the photocatalytic material in situ, so that the effective separation of photo-generated electrons and holes and the high-efficiency photo-Fenton water purification activity are realized simultaneously. In the material system, the ultrathin porous structural characteristics can effectively shorten the migration distance of a photon-generated carrier so as to realize the effective separation of a photon-generated electron and a hole, and the surface amino modification can effectively promote the in-situ generation and photon-generated electron transmission of FeOOH quantum dots so as to promote the generation of oxygen-containing active species. The synergistic effect of the two structural features improves the photo Fenton capability of the synthesized material to the greatest extent. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: The FeOOH quantum dot modified amino-rich porous ultrathin g-C 3N4 photo Fenton water purification material is prepared by directly performing thermal polymerization on a nitrogen-rich precursor with the assistance of a high molecular structure guiding agent, and then the porous ultrathin carbon nitride (HUCN) material is obtained by performing chemical etching treatment to obtain the amino-functionalized modified porous ultrathin g-C 3N4 material, and the FeOOH quantum dot is further loaded in situ by a coprecipitation method. The preparation method of the FeOOH quantum dot modified amino-rich porous ultrathin g-C 3N4 photo Fent