Preparation method of cobalt-loaded porous framework-shaped graphite phase carbon nitride catalytic material

Abstract

The invention discloses a preparation method of a cobalt-loaded porous skeleton-shaped graphite phase carbon nitride catalytic material, which comprises the following steps: (1) dissolving melamine in deionized water in an oil bath state to obtain a melamine solution; dissolving cyanuric acid in deionized water in an oil bath state to obtain a cyanuric acid solution; (2) slowly dropwise adding a cyanuric acid solution into a melamine solution, fully stirring, carrying out suction filtration, washing, drying, and pyrolyzing in a nitrogen atmosphere to obtain a g-C3N4 carrier; and (3) dispersing a divalent cobalt salt and the g-C3N4 carrier in deionized water, fully stirring, centrifuging, collecting a precipitate, freeze-drying, and pyrolyzing in a nitrogen atmosphere to obtain the Co-g-C3N4 catalytic material. The porous framework-shaped graphite phase carbon nitride prepared by the method is formed by tightly stacking a large amount of flaky and tubular graphite phase carbon nitride, the surface of the porous framework-shaped graphite phase carbon nitride is porous, the structure is loose, and abundant attachment sites are provided for attachment of cobalt atoms.

Description

Technical Field

[0001] The invention relates to a method for preparing a porous skeleton-shaped graphite phase carbon nitride catalytic material loaded with cobalt. Background Art

[0002] With the continuous development of industry, a large amount of organic pollutants are discharged into natural water bodies along with sewage, causing serious harm to the ecological environment. At present, physical adsorption and biodegradation methods are used to solve this problem. However, the above methods have insufficient removal capacity of organic pollutants and the problem of secondary pollution, which limits their application. Compared with physical adsorption and biodegradation, advanced oxidation processes (AOPs) are more environmentally friendly, will not release a large amount of harmful residues, can degrade organic pollutants and mineralize them into harmless intermediates as well as CO2 and H2O, thereby achieving water purification and environmental remediation.

[0003] As a metal-free conjugated polymer semiconductor, g-C3N4 has become a promising catalytic material in AOPs in recent years due to its advantages such as simple synthesis, low cost, stable structure and unique electronic structure, and has been widely used in sewage treatment. However, the existing g-C3N4-based catalytic materials have excessive metal doping, which will cause the metal to aggregate on the g-C3N4 matrix, resulting in reduced catalytic activity of the material and accompanied by the destruction of the g-C3N4 matrix. Moreover, with the increase of metal doping, the overflow rate of metal ions will also increase greatly, which will confuse whether it is the active sites of the metal in the catalyst or the overflowed metal ions that play a decisive role in the degradation of pollutants in the reaction. Summary of the invention

[0004] Purpose of the invention: The purpose of the present invention is to provide a method for preparing a porous skeleton-like graphite-phase carbon nitride catalytic material loaded with cobalt. The catalytic material carrier prepared by the method has a porous skeleton structure, which can provide abundant attachment sites for the attachment of cobalt atoms, so that the cobalt atoms are highly dispersed on the surface of the carrier. On the one hand, it can significantly enhance the activation efficiency of the catalytic material for PMS, thereby improving the removal efficiency of benzotriazole in water. On the other hand, it can also reduce the leaching of cobalt on the carrier, thereby reducing the probability of secondary pollution.

[0005] Technical solution: The method for preparing the porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt of the present invention comprises the following steps:

[0006] (1) dissolving melamine in deionized water in an oil bath to obtain a melamine solution; dissolving cyanuric acid in deionized water in an oil bath to obtain a cyanuric acid solution;

[0007] (2) slowly dripping the cyanuric acid solution into the melamine solution, stirring thoroughly, filtering, washing, drying, and then pyrolyzing under a nitrogen atmosphere to obtain a g-C3N4 carrier;

[0008] (3) The divalent cobalt salt and the g-C3N4 carrier are dispersed in deionized water, stirred thoroughly and then centrifuged to collect the precipitate, freeze-dried and then pyrolyzed in a nitrogen atmosphere to obtain the Co-g-C3N4 catalytic material.

[0009] Wherein, in step (1), the temperature of the oil bath treatment is 90 to 120° C. and the time is 20 to 30 minutes.

[0010] Wherein, in step (2), solution B is mixed with solution A at a mass ratio of melamine to cyanuric acid of 1:1.01-1.02. The solution mixing is to obtain a melamine-cyanuric acid supramolecular polymer.

[0011] Wherein, in step (2), the drying temperature is 40 to 60° C., and the drying time is 12 to 24 hours.

[0012] Wherein, in step (2), the heat treatment temperature is 550°C to 600°C, and the heat treatment heating rate is 2.5°C min -1 , the heat treatment time is 1 to 3 hours.

[0013] Wherein, in step (3), the divalent cobalt salt is one of cobalt chloride hexahydrate (CoCl2·6H2O), CoSO4 (cobalt sulfate) or cobalt nitrate hexahydrate (Co(NO3)2·6H2O).

[0014] Wherein, in step (3), the mass ratio of the divalent cobalt salt to the g-C3N4 carrier is 1.5 to 4:1.

[0015] Wherein, in step (3), the heat treatment temperature is 500°C to 550°C, and the heating rate is 2.5°C min -1 The heat treatment time is 1 to 3 hours. The first heat treatment is to obtain a loose and porous carbon nitride morphology, and the second heat treatment is to dope metal.

[0016] Among them, in step (3), the catalytic material uses a porous skeleton-like graphite phase carbon nitride as a carrier, the carrier is composed of a large number of flaky and tubular graphite carbon nitride tightly stacked, and the active site Co is fixed on the carrier by means of coordination bonding with the carrier.

[0017] The loading amount of Co in the active site is 1.1% to 6.5% of the mass of the catalytic material.

[0018] The catalytic material prepared by the present invention is used to activate PMS to degrade organic pollutants in water. The specific application process is as follows: the catalytic oxidation reaction is carried out in a beaker, the reaction temperature is 15-35°C, the volume of the benzotriazole solution is 250mL, and the initial concentration is 20mg·L -1 , the amount of catalytic material is 0.0125g to 0.075g, the amount of PMS is 0.125g to 0.75g, and the initial pH value of the reaction solution is 3 to 9. The catalytic material activates PMS to produce a variety of active substances, especially high-valent metal cobalt oxide species that will produce non-free radicals in the reaction system. Its strong oxidizing ability can achieve rapid and efficient removal of benzotriazole, converting it into harmless intermediates, carbon dioxide and water.

[0019] Co(II)+HSO5 - →Co(IV)=O+SO4 2- +H + Divalent cobalt reacts with sulfoxylate ions to generate high-valent cobalt species; the reason why high-valent metal species have strong oxidizing properties is mainly related to their valence and electronic structure. The higher the valence, the easier it is to lose electrons, thus carrying a positive charge. Due to the attraction of the positive charge, it is easier to attract electrons in the reaction and exhibit a strong oxidizing effect.

[0020] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: the porous skeleton-like graphite phase carbon nitride prepared by the method of the present invention is composed of a large number of closely stacked flaky and tubular graphite phase carbon nitrides, and its surface is porous and the structure is loose, which provides abundant attachment sites for the attachment of cobalt atoms. On the one hand, it can reduce the agglomeration of cobalt atoms on the surface of the carrier and make the cobalt atoms highly dispersed on the surface of the carrier. On the other hand, it can make the carrier load more cobalt, thereby greatly enhancing the activation efficiency of the catalytic material for PMS and the number of non-radical high-valent metal cobalt oxygen species generated by the catalytic material during the catalytic reaction, thereby achieving efficient and rapid removal of benzotriazole, and the catalytic material of the present invention can also reduce the probability of leaching of cobalt active sites. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a SEM image of the catalytic material prepared in Comparative Example 1;

[0022] Figure 2 is a SEM image of the catalytic material prepared in Example 4;

[0023] Figure 3 The XRD patterns of the catalytic materials prepared in Comparative Example 1 and Example 4;

[0024] Figure 4 The proton nuclear magnetic resonance spectra of the catalytic materials prepared in Comparative Example 1 and Example 4 are shown. DETAILED DESCRIPTION

[0025] Example 1

[0026] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0027] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water under 100°C oil bath conditions to obtain cyanuric acid solution and melamine solution, respectively; the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution and magnetically stirred for 20 minutes; the mixed solution was filtered and then washed with 150 mL of deionized water and then with 100 mL of ethanol; the precipitate was dried in an oven at 50°C for 18 h to obtain a yellow powder sample; and then the precipitate was pyrolyzed in a tube furnace at 600°C for 2 h under a nitrogen atmosphere at a heating rate of 2.5°C min -1 , obtaining a carbon nitride support;

[0028] (2) 0.1 g of carbon nitride support and 0.1505 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0029] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with an initial concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 62.8%.

[0030] Example 2

[0031] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0032] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1, obtaining a carbon nitride support;

[0033] (2) 0.1 g of the carrier and 0.2003 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was then pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0034] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiment, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 77.9%.

[0035] Example 3

[0036] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0037] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0038] (2) 0.1 g of the carrier and 0.2505 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0039] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 87.1%.

[0040] Example 4

[0041] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0042] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0043] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0044] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0045] Example 5

[0046] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0047] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0048] (2) 0.1 g of the carrier and 0.3506 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0049] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 99.5%.

[0050] Example 6

[0051] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0052] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0053] (2) 0.1 g of the carrier and 0.4002 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min-1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0054] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiment, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 95.2%.

[0055] Example 7

[0056] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0057] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 90 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0058] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0059] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0060] Example 8

[0061] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0062] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 110 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 minutes, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0063] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0064] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0065] Example 9

[0066] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0067] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 120 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0068] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0069] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0070] Example 10

[0071] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0072] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 minutes, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 40 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0073] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0074] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0075] Embodiment 11

[0076] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0077] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 60 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0078] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0079] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0080] Example 12

[0081] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0082] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0083] (2) 0.1 g of the carrier and 0.3015 g of CoSO4 were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0084] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0085] Embodiment 13

[0086] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0087] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0088] (2) 0.1 g of the carrier and 0.3015 g of Co(NO3)2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was then pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min-1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0089] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0090] Embodiment 14

[0091] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0092] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water under 100 °C oil bath conditions, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 minutes, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 500 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0093] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was then pyrolyzed in a tube furnace at 500 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0094] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 73.1%.

[0095] Embodiment 15

[0096] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0097] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0098] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0099] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 95.7%.

[0100] Example 16

[0101] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0102] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C oil bath conditions, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 minutes, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 1 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0103] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was then pyrolyzed in a tube furnace at 550 °C for 1 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0104] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 88.3%.

[0105] Embodiment 17

[0106] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0107] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 3 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0108] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was then pyrolyzed in a tube furnace at 550 °C for 3 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0109] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 85.9%.

[0110] By comparing Examples 4 with 14 to 17, it can be seen that the heat treatment temperature and heat treatment time have a great influence on the catalytic activity of the catalytic material. When the heat treatment temperature is 550°C and the heat treatment time is 2h, the catalytic material obtained has more pores on the surface and the catalytic activity is the best.

[0111] Embodiment 18

[0112] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0113] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0114] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0115] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 15°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 55.3% within 30 minutes.

[0116] Embodiment 19

[0117] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0118] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0119] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0120] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 35°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 20 minutes.

[0121] Embodiment 20

[0122] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0123] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0124] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0125] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.0125g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 37.1% within 30 minutes.

[0126] Embodiment 21

[0127] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0128] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0129] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0130] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.025g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 71.4%.

[0131] Embodiment 22

[0132] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0133] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0134] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0135] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.075g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 20 minutes.

[0136] Embodiment 23

[0137] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0138] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0139] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0140] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.125g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole within 30 minutes was 69.1%.

[0141] Embodiment 24

[0142] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0143] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0144] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0145] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.25g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0146] Embodiment 25

[0147] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0148] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0149] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0150] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.75g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 30 minutes.

[0151] During the catalytic oxidation experiments of Examples 1 to 25, the initial pH of the reaction system was 7.3.

[0152] Embodiment 26

[0153] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0154] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0155] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0156] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments. Before the experiment, 0.2M H2SO4 was added to the solution to adjust the initial pH value of the solution to 3, followed by stirring for 30 minutes, and then 0.5g PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of benzotriazole by the catalytic material within 30 minutes was 83.1%, and 100% removal within 45 minutes.

[0157] Embodiment 27

[0158] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0159] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0160] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0161] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments. Before the experiment, 0.2M H2SO4 was added to the solution to adjust the initial pH value of the solution to 5, followed by stirring for 30 minutes, and then 0.5g PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of benzotriazole by the catalytic material within 30 minutes was 95.7%, and 100% removal within 45 minutes.

[0162] Embodiment 28

[0163] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0164] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0165] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0166] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments. Before the experiment, 0.2M H2SO4 was added to the solution to adjust the initial pH value of the solution to 7, followed by stirring for 30 minutes, and then 0.5g PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of benzotriazole by the catalytic material within 30 minutes was 99.3%, and 100% removal within 45 minutes.

[0167] Embodiment 29

[0168] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0169] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0170] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0171] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments. Before the experiment began, 0.2M H2SO4 was added to the solution to adjust the initial pH value of the solution to 9, followed by stirring for 30 minutes, and then 0.5g PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of benzotriazole by the catalytic material within 30 minutes was 95.1%, and 100% removal within 45 minutes.

[0172] Embodiment 30

[0173] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0174] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0175] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0176] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments. The solution was stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. At the same time, 0.2M H2SO4 was added to adjust the pH of the solution and keep it constant at 3. The test results showed that the degradation rate of the catalytic material for benzotriazole was 68.2% within 30 minutes, and 100% removal within 60 minutes.

[0177] Embodiment 31

[0178] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0179] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0180] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0181] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments. Stir for 30 minutes, then add 0.5g of PMS to start the catalytic oxidation experiment. At the same time, add 0.2M H2SO4 to adjust the solution pH and keep it constant at 5. The test results showed that the degradation rate of the catalytic material for benzotriazole was 90.1% within 30 minutes, and 100% removal within 45 minutes.

[0182] Embodiment 32

[0183] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0184] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0185] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0186] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments. The solution was stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. At the same time, 0.2M H2SO4 was added to adjust the solution pH to a constant 7. The test results showed that the degradation rate of the catalytic material for benzotriazole was 90.0% within 30 minutes, and 100% removal within 45 minutes.

[0187] Embodiment 33

[0188] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0189] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1, obtaining a carbon nitride support;

[0190] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0191] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments. The solution was stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. At the same time, 0.2M H2SO4 was added to adjust the solution pH to a constant 9. The test results showed that the degradation rate of the catalytic material for benzotriazole was 80.4% within 30 minutes, and 100% removal within 60 minutes.

[0192] By comparing Examples 4 with 26 to 33, it can be seen that the constant pH value of the reaction solution has a relatively obvious effect on the catalytic activity of the catalytic material, and the catalytic performance will be reduced under strong alkaline or strong alkaline conditions. In general, the catalytic materials have high adaptability in the range of pH = 3 to 9, and can achieve a 100% removal rate of benzotriazole within 60 minutes; Examples 26-29, adjusting different initial pH values ​​of the reaction solution (3, 5, 7, 9) and Examples 30-33, adjusting the reaction solution to be constant at 3, 5, 7, 9. By adjusting the initial pH value and constant pH value of the reaction solution, the catalytic material can achieve a 100% removal rate of benzotriazole within 60 minutes.

[0193] Embodiment 34

[0194] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0195] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0196] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0197] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL benzotriazole solution with a concentration of 10mg / L for degradation experiments. The solution was stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material to benzotriazole was 100% within 10 minutes.

[0198] Embodiment 35

[0199] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0200] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0201] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0202] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was as follows: at 25°C, 0.05g of catalytic material was added to a 250mL benzotriazole solution with a concentration of 30mg / L for degradation experiments. The mixture was stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of benzotriazole by the catalytic material within 30 minutes was 92.6%, and 100% removal within 45 minutes.

[0203] Embodiment 36

[0204] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0205] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0206] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0207] The adsorption degradation process was carried out in a 500mL beaker, with carbamazepine as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The specific process was as follows: at 25°C, 0.05g of catalytic material was added to a 250mL carbamazepine solution with a concentration of 20mg / L for degradation experiment. The solution was stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of carbamazepine by the catalytic material within 10 minutes was 100%.

[0208] Embodiment 37

[0209] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0210] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0211] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0212] The adsorption degradation process was carried out in a 500mL beaker, with trichlorophenol as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade trichlorophenol. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL trichlorophenol solution with a concentration of 20mg / L for degradation experiments. The mixture was stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material for trichlorophenol was 100% within 10 minutes.

[0213] Embodiment 38

[0214] The method for preparing the porous skeleton-like graphite phase carbon nitride catalyst material loaded with cobalt of the present invention comprises the following steps:

[0215] (1) 0.504 g of melamine and 0.513 g of cyanuric acid were dissolved in deionized water at 100 °C in an oil bath, and the dissolved cyanuric acid solution was slowly dripped into the dissolved melamine solution, magnetically stirred for 20 min, filtered, washed with 150 mL of deionized water and 100 mL of ethanol, and then dried in an oven at 50 °C for 18 h to obtain a yellow powder sample, which was then pyrolyzed in a tube furnace at 600 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C min -1 , obtaining a carbon nitride support;

[0216] (2) 0.1 g of the carrier and 0.3015 g of CoCl2·6H2O were dispersed in deionized water and magnetically stirred for 12 h. The precipitate was collected by centrifugation and freeze-dried for 18 h. The precipitate was pyrolyzed in a tube furnace at 550 °C for 2 h under a nitrogen atmosphere at a heating rate of 2.5 °C·min -1 , a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt is obtained.

[0217] The adsorption degradation process was carried out in a 500mL beaker, with neutral red as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material in activating PMS to degrade neutral red. The specific process was as follows: at 25°C, 0.05g of the catalytic material was added to a 250mL neutral red solution with a concentration of 20mg / L for degradation experiments. The solution was stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of the catalytic material for neutral red was 100% within 10 minutes.

[0218] By comparing Examples 4 with 34 to 38, it can be seen that the catalytic material also has great advantages in degrading other pollutants such as drugs (carbamazepine), phenols (trichlorophenol), dyes (neutral red), etc., and can completely remove pollutants within 10 minutes.

[0219] Comparative Example 1

[0220] A method for preparing a porous skeleton-like graphite phase carbon nitride catalytic material, specifically comprising: dissolving 0.504 g of melamine and 0.513 g of cyanuric acid in deionized water under 100° C. oil bath conditions, slowly dripping the dissolved cyanuric acid solution into the dissolved melamine solution, magnetically stirring for 20 minutes, filtering and washing with 150 mL of deionized water and 100 mL of ethanol, and then drying the precipitate in an oven at 50° C. for 18 hours to obtain a yellow powder sample, and then pyrolyzing it in a 600° C. tube furnace under a nitrogen atmosphere for 2 hours at a heating rate of 2.5° C. min -1 , and obtain a porous skeleton-like graphite phase carbon nitride catalytic material.

[0221] The adsorption degradation process was carried out in a 500mL beaker, with benzotriazole as the target pollutant and PMS as the oxidant. High performance liquid chromatography was used to test the performance of the catalytic material activating PMS to degrade benzotriazole. The specific process was: at 25°C, 0.05g of carbon nitride was added to a 250mL benzotriazole solution with a concentration of 20mg / L for degradation experiments, stirred for 30 minutes, and then 0.5g of PMS was added to start the catalytic oxidation experiment. The test results showed that the degradation rate of benzotriazole by the catalytic material within 30 minutes was 9.7%.

[0222] The porous skeleton-like graphite-phase carbon nitride catalytic material prepared in Comparative Example 1 does not contain metal cobalt active sites and cannot effectively activate PMS, so it cannot produce a large amount of active substances, resulting in a very low degradation efficiency.

[0223] like Figure 1 As shown, the SEM image of the g-C3N4 carrier shows that it has a porous skeleton-like morphology, and the surface is composed of stacked broken nanosheets; Figure 2 As shown, the morphology of the Co-g-C3N4 catalytic material prepared in Example 4 also presents a porous skeleton structure, but its surface pores are more, indicating that the introduction of Co atoms makes the g-C3N4 carrier looser, thereby providing more attachment sites; Figure 3 As shown, no characteristic peaks related to Co were detected in the XRD spectrum of the catalytic material prepared in Example 4, indicating that the Co atoms on the carrier are highly dispersed and not agglomerated. Since DMSO can be oxidized to DMSO2 by high-valent metals through the transfer of oxygen atoms, 1 H NMR is used to detect the catalytic oxidation products after adding DMSO (high-valent metals can oxidize DMSO into DMSO2, and both DMSO and the generated DMSO2 can be detected by NMR (nuclear magnetic resonance) with their corresponding characteristic peaks. Therefore, DMSO is added during the reaction, and then NMR is used to detect whether there is a DMSO2 characteristic peak. If so, it proves that high-valent metal species are generated). Figure 4 As shown, only the signal peak of DMSO was detected in Comparative Example 1, while in Example 4, not only the signal peak of DMSO but also the signal peak of DMSO2 was detected; this indicates that the porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt prepared in Example 4 produced non-radical high-valent metal cobalt oxide species (Co(IV)=O) during the activation of PMS as a catalyst.

Claims

1. A method for preparing a porous skeleton-like graphite phase carbon nitride catalytic material loaded with cobalt, characterized in that: The steps include: (1) dissolving melamine in deionized water in an oil bath to obtain a melamine solution; dissolving cyanuric acid in deionized water in an oil bath to obtain a cyanuric acid solution; (2) slowly dripping the cyanuric acid solution into the melamine solution, stirring thoroughly, filtering, washing, drying, and then pyrolyzing under a nitrogen atmosphere to obtain a g-C3N4 carrier; (3) The divalent cobalt salt and the g-C3N4 carrier are dispersed in deionized water, stirred thoroughly and then centrifuged to collect the precipitate, freeze-dried and then pyrolyzed in a nitrogen atmosphere to obtain the Co-g-C3N4 catalytic material.

2. The preparation method according to claim 1, characterized in that: In step (1), the temperature of the oil bath treatment is 90 to 120° C. and the time is 20 to 30 minutes.

3. The preparation method according to claim 1, characterized in that: In step (2), solution B is mixed with solution A at a mass ratio of melamine to cyanuric acid of 1:1.01-1.

02.

4. The preparation method according to claim 1, characterized in that: In step (2), the drying temperature is 40 to 60° C. and the drying time is 12 to 24 hours.

5. The preparation method according to claim 1, characterized in that: In step (2), the heat treatment temperature is 500°C to 600°C, and the heat treatment heating rate is 2.5°C min -1 , the heat treatment time is 1 to 3 hours.

6. The preparation method according to claim 1, characterized in that: In step (3), the divalent cobalt salt is one of cobalt chloride hexahydrate, cobalt sulfate or cobalt nitrate hexahydrate.

7. The preparation method according to claim 1, characterized in that: In step (3), the mass ratio of the divalent cobalt salt to the g-C3N4 carrier is 1.5 to 4:

1.

8. The preparation method according to claim 1, characterized in that: In step (3), the heat treatment temperature is 500°C to 600°C, and the heating rate is 2.5°C min -1 , the heat treatment time is 1 to 3 hours.

9. The preparation method according to claim 1, characterized in that: In step (3), the catalytic material uses porous skeleton-like graphite phase carbon nitride as a carrier, and the active site Co is fixed on the carrier by means of coordination bonding with the carrier.

10. The preparation method according to claim 9, characterized in that: The loading amount of Co in the active site is 1.1% to 6.5% of the mass of the catalytic material.

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