CN-121669236-B - Co@C/FHP catalyst and preparation method and application thereof

Abstract

The invention belongs to the technical field of catalytic dye degradation, and particularly relates to a Co@C/FHP catalyst, a preparation method and application thereof. The preparation method comprises the following steps: co (NO 3 ) 2 ·6H 2 O and terephthalic acid are dissolved in DMF, and the two-ball sycamore fruit wool (Fruit hair of Platanus, FHP) is added, washed and dried by hydrothermal reaction, and then calcined under the atmosphere of N 2 to obtain the Co@C/FHP catalyst, the invention uses FHP as a carrier, co-MOF grows on the surface of the catalyst in situ, after pyrolysis, FHP is carbonized into a porous carbon carrier, co-MOF is converted into metal cobalt nano particles wrapped by a carbon layer, and the catalyst has the advantages of high dispersity of active sites, good stability and good conductivity, and can efficiently activate peroxymonosulfate to degrade organic pollutants.

Inventors

• DONG ZHE
• Shang Shubo
• WANG AILI
• Wang Dengtai
• NIU PING
• TANG QI
• LI XINZHENG

Assignees

• 德州学院

Dates

Publication Date

20260508

Application Date

20260206

Claims (2)

1. 1. A Co@C/FHP catalyst is characterized in that a FHP pyrolysis product is used for forming a carbon carrier, a Co-MOF is pyrolyzed, a ligand is carbonized to form a carbon shell layer which wraps cobalt nano particles, and metal center cobalt ions are reduced into metal cobalt nano particles; the preparation method of the Co@C/FHP catalyst comprises the following steps: S1, dissolving 0.6mmolCo (NO 3 ) 2 ·6H 2 O and 0.4mmol of terephthalic acid in DMF, stirring at room temperature for dissolution, adding 40mg of wool FHP of platycodon grandiflorum, stirring to uniformly disperse the wool FHP, and then transferring the mixture into a reaction kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 120 ℃ for 12 hours; S2, centrifuging the obtained product at 8000rpm for 10min, discarding the supernatant, washing once with DMF, washing twice with absolute ethyl alcohol, discarding the supernatant, and drying at 80 ℃ in a vacuum drying oven for 24h to obtain Co-MOF; And S3, placing the product in a tube furnace, and calcining under the atmosphere of N 2 , wherein the product is the Co@C/FHP catalyst, and the calcining condition is that the calcining is carried out at 800 ℃ for 3 hours, and the heating rate is 5 ℃ per minute.
2. 2. The method for degrading organic pollutants by using the Co@C/FHP catalyst according to claim 1, wherein the organic pollutant is one of ponceau 2R, tetracycline and rhodamine B.

Description

Co@C/FHP catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of catalytic dye degradation, and particularly relates to a Co@C/FHP catalyst, a preparation method and application thereof. Background Advanced Oxidation Processes (AOPs) are based on the generation of strongly oxidative radicals such as sulfate radicals SO 4- and hydroxyl radicals OH that are effective in degrading organic contaminants, with activation of the Peroxymonosulfate (PMS) being a hotspot of current research. Cobalt (Co) based catalysts are one of the most effective homogeneous catalysts for activating PMS, but have problems of easy leaching, secondary pollution, difficult recovery, and the like. Immobilization of cobalt species on a support to prepare a heterogeneous catalyst is an ideal solution. The Metal Organic Framework (MOF) material can be used as an ideal precursor due to the high specific surface area and the adjustable structure, and the carbon-coated metal nanoparticle material can be prepared through high-temperature pyrolysis, so that the leaching and agglomeration of cobalt particles can be effectively prevented, and the excellent conductivity of the carbon material can be utilized to promote the catalytic reaction. However, conventional MOF-derived carbon materials are susceptible to particle aggregation during pyrolysis, resulting in a reduction of active sites. Therefore, the development of a heterogeneous catalyst which can highly disperse and stabilize cobalt active sites, is simple to prepare and low in cost, and has important significance for promoting the practical application of PMS activation technology. Disclosure of Invention The first object of the invention is to provide a preparation method of a Co@C/FHP catalyst, which comprises the following steps: S1, dissolving Co (NO 3)2·6H2 O, 0.4mmol terephthalic acid in DMF, stirring at room temperature for dissolution, adding the hairs (Fruit hair of Platanus, FHP) of the platycodon grandiflorum, stirring for uniform dispersion, and then transferring to a reaction kettle for hydrothermal reaction; S2, centrifuging the obtained product at 8000rpm for 10min, discarding the supernatant, washing once with DMF, washing twice with absolute ethyl alcohol, discarding the supernatant, and drying at 80 ℃ in a vacuum drying oven for 24h to obtain Co-MOF; and S3, placing the product in a tube furnace, and calcining under the atmosphere of N 2 to obtain the product, namely the Co@C/FHP catalyst. Further, the molar ratio of Co (NO 3)2·6H2 O to terephthalic acid) was 1.5:1. Further, the hydrothermal reaction condition is 120 ℃ hydrothermal for 12 hours. Further, the calcination condition is that the calcination is carried out for 3 hours at 700-900 ℃, and the temperature rising rate is 5 ℃ per minute. At temperatures exceeding 900 ℃, disruption of the carbon support structure may impair its ability to fix and disperse cobalt particles. The second object of the invention is to provide a Co@C/FHP catalyst prepared by the preparation method. The catalyst forms a carbon carrier by FHP pyrolysis products, co-MOF is pyrolyzed, ligands in the carbon carrier are carbonized to form a carbon shell Co@C wrapping cobalt nano particles, and metal center cobalt ions are reduced into metal cobalt nano particles. It is a fourth object of the present invention to provide the use of said catalyst for activating PMS to degrade a variety of organic contaminants. Further, the organic pollutant is one of ponceau 2R, tetracycline and rhodamine B. The beneficial technical effects of the invention are as follows: The Co@C/FHP composite catalyst with a core-shell heterostructure is prepared by creatively growing a cobalt-based metal organic framework (Co-based MOF) on the surface of the fruit villus of the sycamore in situ and through a controllable calcination process. The dual action of FHP skeleton and MOF precursor effectively prevents the aggregation of cobalt nano particles in the high temperature treatment process, and exposes more active sites. The carbon shell and the carbon carrier act together to firmly fix cobalt particles and prevent the cobalt particles from losing in the reaction, so that the catalyst can still keep high activity after being recycled for 12 times. The whole material of the Co@C/FHP composite catalyst is a conductive carbon network, which is beneficial to the rapid transfer of electrons to cobalt active sites, thereby efficiently activating PMS. Namely FHP and MOF are "transformed" together into a synergistic, high performance catalytic system by pyrolysis at high temperatures. Thanks to the serial regulation effect of the fruit Fluff (FHP) of the sycamore, the catalyst can effectively modulate the d-band center position of cobalt species, obviously accelerate the directional transfer process of electrons to PMS, and has excellent catalytic performance in the degradation treatment of typical organic pollutants