CN113101961A - Ag/C loaded3N4Nano particle active carbon composite material and preparation method thereof - Google Patents

Ag/C loaded3N4Nano particle active carbon composite material and preparation method thereof Download PDF

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CN113101961A
CN113101961A CN202110423207.XA CN202110423207A CN113101961A CN 113101961 A CN113101961 A CN 113101961A CN 202110423207 A CN202110423207 A CN 202110423207A CN 113101961 A CN113101961 A CN 113101961A
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active carbon
composite material
carbon composite
nano particles
temperature
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陈潘林
余晨义
包衎杰
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Gonggu Environmental Protection Technology Zhejiang Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01D2257/91—Bacteria; Microorganisms

Abstract

The invention relates to the technical field of new materials, and discloses a load Ag/C3N4Active carbon composite material of nano particles, melamine and silver nitrate are mixed and pyrolyzed to prepare Ag/g-C3N4The nano particles are then compounded with a porous activated carbon material to prepare the Ag/C load3N4The active carbon composite material of nano particles takes porous active carbon as a carrier and uniformly loads Ag/g-C3N4Nanoparticles, Ag/g-C3N4The nanoparticles have excellent photochemical activity, can generate more photogenerated carriers under light irradiation, and have g-C3N4The Ag doped in the matrix has excellent conductivity, and can promote the transfer of photo-generated electrons, promote the separation of the photo-generated electrons and holes and ensure that the Ag/g-C3N4The nano particles show better photocatalytic activity, and have good functions of adsorbing and photodegrading formaldehyde and excellent photocatalytic antibacterial activity on bacteria and microorganisms such as escherichia coli by being combined with the porous activated carbon.

Description

Ag/C loaded3N4Nano particle active carbon composite material and preparation method thereof
Technical Field
The invention relates to the technical field of new materials, in particular to a load Ag/C3N4An active carbon composite material of nano particles and a preparation method thereof.
Background
In 2020, the global new crown epidemic situation is greatly outbreak, which prompts people to pay more and more attention to the aspects of disinfection, antibiosis and sanitation, and particularly in indoor or environment-closed places, the problems of poor gas circulation, formaldehyde release and the like become one of the important daily concerns of people, and how to effectively purify and improve the respiratory air quality of people and maintain the healthy life of people becomes more and more urgent and important.
Among various gas adsorption and filtration treatment technologies, the activated carbon adsorption technology is the most common and effective, the activated carbon is very fine carbon particles and has a large surface area, and the carbon particles also have very fine pores, so that the activated carbon adsorption technology has very strong adsorption performance, however, the activated carbon adsorption technology also has the defects, for example, the huge specific surface area of the activated carbon also provides a hotbed for the propagation of microorganisms such as bacteria and the like, so that secondary pollution is caused, and in order to overcome the defect, the activated carbon can be loaded with substances with bactericidal activity, so that the adsorption capacity can be maintained, and the propagation of microorganisms such as bacteria, mold and the like can be effectively inhibited.
Research shows that many heavy metal elements have certain antibacterial activity, including mercury, lead, zinc, silver and copper, but mercury and lead have strong toxicity and are not suitable for being applied in daily life, zinc is an active metal element, the smelting industry is difficult, and the antibacterial performance of zinc is poor, so silver and copper are the most widely used antibacterial active metal elements at present, compared with copper, silver is expensive, but silver has good chemical stability and very high bactericidal activity, the antibacterial performance of nano silver below 25nm is increased to thousands of times, and trace silver is harmless to human bodies, so that the silver is widely applied to daily life.
However, the degradation function of nano-silver to formaldehyde is weak at normal temperature, and in order to obtain high-efficiency formaldehyde degradation performance, adsorption, sterilization and degradation are innovatively combined, and Ag and g-C are considered3N4Combined, unlike conventional photocatalysts corresponding only to ultraviolet light, g-C3N4Can also be driven by visible light, g-C3N4Can effectively activate molecular oxygen, generate superoxide radical for photocatalytic degradation of organic pollutants, is suitable for treating indoor air pollution, and is prepared by mixing silver and g-C3N4Combined, the antibacterial agent has antibacterial activity and can degrade gas pollutants such as formaldehyde, TVOC and the like.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a load Ag/C3N4The active carbon composite material of the nano particles and the preparation method thereof have the double functions of adsorption and bacteriostasis and formaldehyde degradation.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: Ag/C loaded3N4Nanoparticle-loaded activated carbon composite material, Ag/C3N4The preparation method of the active carbon composite material of the nano particles comprises the following steps:
(1) adding a solvent and a cosolvent into a reaction bottle, adding 1,3, 5-tri (4-bromophenyl) benzene and 1, 4-benzene diboronic acid, stirring for dissolving, adding an accelerator potassium carbonate and a catalyst tetrakis (triphenylphosphine) palladium, heating to 160 ℃, carrying out reflux reaction for 48-96h, filtering to remove the solvent, extracting and purifying by using distilled water, dichloromethane and acetone in sequence through a Soxhlet extractor, and drying to obtain the biphenyl microporous polymer.
(2) And (3) adding the biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 2-8 ℃/min, carrying out thermal oxidation pretreatment, and then carrying out high-temperature carbonization treatment to obtain the porous activated carbon material.
(3) Adding ethylene glycol and melamine into a reaction bottle, stirring and dissolving, adding a nitric acid solution, adjusting the pH value of the solution to 4-5, and then dropwise adding AgNO3The aqueous solution is placed in a drying oven after being dispersed uniformly by ultrasonic waves, the solution is dried for 10 to 20 hours at the temperature of between 70 and 100 ℃, then the mixed product is placed in an atmosphere tube furnace, the heating rate is controlled to be between 5 and 10 ℃/min, the temperature is raised to between 520 ℃ and 580 ℃, the heat preservation treatment is carried out for 1 to 2 hours, then distilled water and ethanol are used for centrifugal washing and drying, and the Ag/g-C is prepared3N4Nanoparticles.
(4) Adding ethanol and distilled water into a reaction bottle, adding a porous activated carbon material and Ag/g-C3N4The nano particles are stirred for 5 to 10 hours after ultrasonic dispersion, and then the solvent is removed by vacuum drying to obtain the load Ag/C3N4An active carbon composite material of nano particles.
Preferably, in the step (1), the solvent is N, N-dimethylformamide, the cosolvent is toluene, and the volume ratio of the two is 100: 15-40.
Preferably, the mass ratio of the 1,3, 5-tri (4-bromophenyl) benzene, the 1, 4-benzenediboronic acid, the potassium carbonate and the tetrakis (triphenylphosphine) palladium in the step (1) is 100:115-130:650-850: 28-35.
Preferably, the thermal oxidation pretreatment in the step (2) is carried out for 1-2h in an air atmosphere at 180-250 ℃; high-temperature carbonization is carried out for 2-3h at the temperature of 750-850 ℃ in the argon atmosphere.
Preferably, the melamine and AgNO in the step (3)3The mass ratio of (A) to (B) is 100: 0.4-4.5.
Preferably, it is characterized in that: Ag/C in the step (3)3N4The grain diameter of the nano particles is 5-500nm, and the mass fraction of Ag is 0.4% -0.7%.
Preferably, the porous activated carbon material in the step (4) andAg/g-C3N4the mass ratio of the nano particles is 100: 1.5-10.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the Ag/C load3N4The nanometer particle active carbon composite material is prepared by taking 1,3, 5-tri (4-bromophenyl) benzene and 1, 4-benzene diboronic acid as polymerization monomers under the catalysis of potassium carbonate and tetra (triphenylphosphine) palladium, polymerizing and crosslinking to generate a microporous polymer containing biphenyl structural units, wherein the microporous polymer has rich pore channel structures, then taking rigid biphenyl structural units of the microporous polymer as a carbon skeleton, generating a porous active carbon material through pre-oxidation and high-temperature carbonization, and the active carbon material prepared by taking the biphenyl microporous polymer as a carbon precursor has higher specific surface area, richer pore structure, more adsorption sites and excellent adsorption performance on gases such as formaldehyde.
The Ag/C load3N4Active carbon composite material of nano particles, melamine and silver nitrate are mixed and pyrolyzed to prepare Ag/g-C3N4The nano particles are then compounded with a porous activated carbon material to prepare the Ag/C load3N4The active carbon composite material of nano particles takes porous active carbon as a carrier and uniformly loads Ag/g-C3N4Nanoparticles, Ag/g-C3N4The nanoparticles have excellent photochemical activity, can generate more photogenerated carriers under light irradiation, and have g-C3N4The Ag doped in the matrix has excellent conductivity, and can promote the transfer of photo-generated electrons, promote the separation of the photo-generated electrons and holes and ensure that the Ag/g-C3N4The nano particles show better photocatalytic activity, and have good functions of adsorbing and photodegrading formaldehyde and excellent photocatalytic antibacterial activity on bacteria and microorganisms such as escherichia coli by being combined with the porous activated carbon.
Drawings
FIG. 1 is a reaction scheme for the preparation of biphenyl microporous polymers.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: Ag/C loaded3N4The preparation method of the active carbon composite material of the nano particles comprises the following steps:
(1) adding an N, N-dimethylformamide solvent and a toluene cosolvent in a volume ratio of 100:15-40 into a reaction bottle, adding 1,3, 5-tris (4-bromophenyl) benzene and 1, 4-phenyl diboronic acid, stirring for dissolving, adding a promoter potassium carbonate and a catalyst tetrakis (triphenylphosphine) palladium in a mass ratio of 100:115-130:650-850:28-35, heating to 120-160 ℃, performing reflux reaction for 48-96h, filtering to remove the solvent, extracting and purifying by using distilled water, dichloromethane and acetone in sequence through a Soxhlet extractor, and drying to obtain the biphenyl microporous polymer.
(2) Adding the biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 2-8 ℃/min, firstly carrying out thermal oxidation pretreatment for 1-2h at the temperature of 180-850 ℃ in the air atmosphere, and then carrying out high-temperature carbonization for 2-3h at the temperature of 750-850 ℃ in the argon atmosphere to prepare the porous activated carbon material.
(3) Adding ethylene glycol and melamine into a reaction bottle, stirring and dissolving, adding a nitric acid solution, adjusting the pH value of the solution to 4-5, and then dropwise adding AgNO3Controlling melamine and AgNO3The mass ratio of the components is 100:0.4-4.5, the solution is placed in a drying oven after being dispersed evenly by ultrasonic, the solution is dried for 10-20h at 70-100 ℃, then the mixed product is placed in an atmosphere tube furnace, the heating rate is controlled to be 5-10 ℃/min, the temperature is raised to 520 ℃ and 580 ℃, the heat preservation treatment is carried out for 1-2h, then distilled water and ethanol are used for centrifugal washing and drying, and the Ag/g-C is prepared3N4The nano particles have the particle size range of 5-500nm, wherein the mass fraction of Ag is 0.4-0.7%.
(4) Adding ethanol and distilled water into a reaction bottle, and adding a porous activated carbon material and Ag/g-C in a mass ratio of 100:1.5-103N4The nano particles are stirred for 5 to 10 hours after ultrasonic dispersion, and then the solvent is removed by vacuum drying to obtain the load Ag/C3N4An active carbon composite material of nano particles.
Example 1
(1) Adding 400mL of N, N-dimethylformamide solvent and 60mL of toluene cosolvent in volume ratio into a reaction bottle, adding 200mg of 1,3, 5-tri (4-bromophenyl) benzene and 230mg of 1, 4-phenyl diboronic acid, stirring to dissolve, adding 1300mg of promoter potassium carbonate and 56mg of catalyst tetrakis (triphenylphosphine) palladium, heating to 120 ℃, refluxing for 48h, filtering to remove the solvent, passing through a Soxhlet extractor, sequentially extracting and purifying by using distilled water, dichloromethane and acetone, and drying to obtain the biphenyl microporous polymer.
(2) Adding 5g of biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 2 ℃/min, firstly carrying out thermal oxidation pretreatment for 1h at 180 ℃ in the air atmosphere, and then carrying out high-temperature carbonization for 2h at 750 ℃ in the argon atmosphere to obtain the porous activated carbon material.
(3) Adding 15mL of ethylene glycol and 1g of melamine into a reaction bottle, stirring to dissolve, adding a nitric acid solution, adjusting the pH value of the solution to 4, and then dropwise adding AgNO containing 0.4g of the solution3The volume of the aqueous solution is 2mL, the solution is placed in a drying oven after being dispersed uniformly by ultrasonic waves, the solution is dried for 10 hours at 70 ℃, then the mixed product is placed in an atmosphere tube furnace, the temperature rising rate is controlled to be 5 ℃/min, the temperature is raised to 520 ℃, the heat preservation treatment is carried out for 1 hour, then distilled water and ethanol are used for centrifugal washing and drying, and the Ag/g-C is prepared3N4Nanoparticles.
(4) 60mL of ethanol and 8mL of distilled water were added to the reaction flask, and 30g of the porous activated carbon material and 0.45g of Ag/g-C were added3N4The nano particles are stirred for 5 hours after ultrasonic dispersion, and then the solvent is removed by vacuum drying to obtain the load Ag/C3N4An active carbon composite material of nano particles.
Example 2
(1) Adding 400mL of N, N-dimethylformamide solvent and 80mL of toluene cosolvent in volume ratio into a reaction bottle, adding 200mg of 1,3, 5-tri (4-bromophenyl) benzene and 235mg of 1, 4-phenyl diboronic acid, stirring to dissolve, adding 1400mg of promoter potassium carbonate and 58mg of catalyst tetrakis (triphenylphosphine) palladium, heating to 120 ℃, refluxing for 48h, filtering to remove the solvent, passing through a Soxhlet extractor, sequentially extracting and purifying by using distilled water, dichloromethane and acetone, and drying to obtain the biphenyl microporous polymer.
(2) Adding 5g of biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 5 ℃/min, firstly carrying out thermal oxidation pretreatment for 1h at 200 ℃ in the air atmosphere, and then carrying out high-temperature carbonization for 2h at 800 ℃ in the argon atmosphere to obtain the porous activated carbon material.
(3) Adding 20mL of ethylene glycol and 1g of melamine into a reaction bottle, stirring to dissolve, adding a nitric acid solution, adjusting the pH value of the solution to 5, and then dropwise adding AgNO containing 1g of the solution3The volume of the aqueous solution is 4mL, the solution is placed in a drying oven after being dispersed uniformly by ultrasonic waves, the solution is dried for 12 hours at the temperature of 100 ℃, then the mixed product is placed in an atmosphere tube furnace, the temperature rising rate is controlled to be 5 ℃/min, the temperature is raised to 550 ℃, the heat preservation treatment is carried out for 1 hour, then distilled water and ethanol are used for centrifugal washing and drying, and the Ag/g-C is prepared3N4Nanoparticles.
(4) 80mL of ethanol and 10mL of distilled water were added to a reaction flask, and 30g of a porous activated carbon material and 1g of Ag/g-C were added3N4The nano particles are stirred for 8 hours after ultrasonic dispersion, and then the solvent is removed by vacuum drying to obtain the load Ag/C3N4An active carbon composite material of nano particles.
Example 3
(1) Adding 400mL of N, N-dimethylformamide solvent and 120mL of toluene cosolvent in volume ratio into a reaction bottle, adding 200mg of 1,3, 5-tri (4-bromophenyl) benzene and 245mg of 1, 4-phenyl diboronic acid, stirring to dissolve, adding 1500mg of promoter potassium carbonate and 62mg of catalyst tetrakis (triphenylphosphine) palladium, heating to 150 ℃, refluxing for 72 hours, filtering to remove the solvent, passing through a Soxhlet extractor, sequentially extracting and purifying by using distilled water, dichloromethane and acetone, and drying to obtain the biphenyl microporous polymer.
(2) Adding 5g of biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 5 ℃/min, firstly carrying out thermal oxidation pretreatment for 1.5h at 200 ℃ in the air atmosphere, and then carrying out high-temperature carbonization for 2.5h at 800 ℃ in the argon atmosphere to obtain the porous activated carbon material.
(3) Adding 20mL of ethylene glycol and 1g of melamine into a reaction bottle, stirring to dissolve, adding a nitric acid solution, adjusting the pH value of the solution to 4, and then dropwise addingContaining 2.5g of AgNO3The volume of the aqueous solution is 5mL, the solution is placed in a drying oven after being dispersed uniformly by ultrasonic waves, the solution is dried for 12 hours at the temperature of 80 ℃, then the mixed product is placed in an atmosphere tube furnace, the temperature rising rate is controlled to be 8 ℃/min, the temperature is raised to 550 ℃, the heat preservation treatment is carried out for 1.5 hours, then distilled water and ethanol are used for centrifugal washing and drying, and the Ag/g-C is prepared3N4Nanoparticles.
(4) To a reaction flask, 90mL of ethanol and 12mL of distilled water were added, and 30g of a porous activated carbon material and 1.5g of Ag/g-C were added3N4The nano particles are stirred for 8 hours after ultrasonic dispersion, and then the solvent is removed by vacuum drying to obtain the load Ag/C3N4An active carbon composite material of nano particles.
Example 4
(1) Adding 400mL of N, N-dimethylformamide solvent and 160mL of toluene cosolvent in volume ratio into a reaction bottle, adding 200mg of 1,3, 5-tri (4-bromophenyl) benzene and 250mg of 1, 4-phenyl diboronic acid, stirring to dissolve, adding 1600mg of promoter potassium carbonate and 65mg of catalyst tetrakis (triphenylphosphine) palladium, heating to 160 ℃, refluxing for 72 hours, filtering to remove the solvent, passing through a Soxhlet extractor, sequentially extracting and purifying by using distilled water, dichloromethane and acetone, and drying to obtain the biphenyl microporous polymer.
(2) Adding 5g of biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 5 ℃/min, firstly carrying out thermal oxidation pretreatment for 2h at 250 ℃ in the air atmosphere, and then carrying out high-temperature carbonization for 2h at 850 ℃ in the argon atmosphere to obtain the porous activated carbon material.
(3) Adding 25mL of ethylene glycol and 1g of melamine into a reaction bottle, stirring to dissolve, adding a nitric acid solution, adjusting the pH value of the solution to 5, and then dropwise adding AgNO containing 3.5g of the solution3The volume of the aqueous solution is 6mL, the solution is placed in a drying oven after being dispersed uniformly by ultrasonic waves, the solution is dried for 20 hours at the temperature of 80 ℃, then the mixed product is placed in an atmosphere tube furnace, the temperature rising rate is controlled to be 10 ℃/min, the temperature is raised to 550 ℃, the heat preservation treatment is carried out for 1 hour, then distilled water and ethanol are used for centrifugal washing and drying, and the Ag/g-C is prepared3N4Nanoparticles.
(4) Adding 100m into a reaction bottleL of ethanol and 14mL of distilled water, 30g of a porous activated carbon material and 2.5g of Ag/g-C were added3N4The nano particles are stirred for 10 hours after ultrasonic dispersion, and then the solvent is removed by vacuum drying to obtain the load Ag/C3N4An active carbon composite material of nano particles.
Example 5
(1) Adding 400mL of N, N-dimethylformamide solvent and 180mL of toluene cosolvent in volume ratio into a reaction bottle, adding 200mg of 1,3, 5-tri (4-bromophenyl) benzene and 260mg of 1, 4-phenyl diboronic acid, stirring to dissolve, adding 1700mg of promoter potassium carbonate and 70mg of catalyst tetrakis (triphenylphosphine) palladium, heating to 160 ℃, refluxing for 96h, filtering to remove the solvent, passing through a Soxhlet extractor, sequentially extracting and purifying by using distilled water, dichloromethane and acetone, and drying to obtain the biphenyl microporous polymer.
(2) Adding 5g of biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 8 ℃/min, firstly carrying out thermal oxidation pretreatment for 2h at 250 ℃ in the air atmosphere, and then carrying out high-temperature carbonization for 3h at 850 ℃ in the argon atmosphere to obtain the porous activated carbon material.
(3) Adding 25mL of ethylene glycol and 1g of melamine into a reaction bottle, stirring to dissolve, adding a nitric acid solution, adjusting the pH value of the solution to 5, and then dropwise adding AgNO containing 4.5g of the solution3The volume of the aqueous solution is 8mL, the solution is placed in a drying oven after being dispersed uniformly by ultrasonic waves, the solution is dried for 20 hours at the temperature of 100 ℃, then the mixed product is placed in an atmosphere tube furnace, the heating rate is controlled to be 10 ℃/min, the temperature is raised to 580 ℃, the heat preservation treatment is carried out for 2 hours, then distilled water and ethanol are used for centrifugal washing and drying, and the Ag/g-C is prepared3N4Nanoparticles.
(4) 120mL of ethanol and 15mL of distilled water were added to a reaction flask, and 30g of a porous activated carbon material and 3g of Ag/g-C were added3N4The nano particles are stirred for 10 hours after ultrasonic dispersion, and then the solvent is removed by vacuum drying to obtain the load Ag/C3N4An active carbon composite material of nano particles.
Comparative example 1
(1) Adding 400mL of N, N-dimethylformamide solvent and 150mL of toluene cosolvent in volume ratio into a reaction bottle, adding 200mg of 1,3, 5-tri (4-bromophenyl) benzene and 250mg of 1, 4-phenyl diboronic acid, stirring to dissolve, adding 1600mg of promoter potassium carbonate and 65mg of catalyst tetrakis (triphenylphosphine) palladium, heating to 140 ℃, refluxing for 72 hours, filtering to remove the solvent, passing through a Soxhlet extractor, sequentially extracting and purifying by using distilled water, dichloromethane and acetone, and drying to obtain the biphenyl microporous polymer.
(2) Adding 5g of biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 8 ℃/min, firstly carrying out thermal oxidation pretreatment for 1.5h at 250 ℃ in the air atmosphere, and then carrying out high-temperature carbonization for 3h at 750 ℃ in the argon atmosphere to obtain the porous activated carbon material.
Ag/C loading in the examples was tested using a BET fully automatic specific surface area and porosity analyzer3N4The total pore volume and specific surface area of the activated carbon composite material of nanoparticles, and the porous activated carbon material of the comparative example.
Figure BDA0003028490390000091
Adding agar culture medium into a sterile culture dish, dropwise adding pH buffer solution, and transferring 2mL of Escherichia coli suspension liquid with concentration of 5 × 10 by using a liquid transfer gun6After the CFU/mL is vibrated uniformly, the Ag/C load in 0.2g of the embodiment is added3N4The nano particle active carbon composite material is used as an experimental group, the porous active carbon material added in the comparative example is used as a control group, after the nano particle active carbon composite material is uniformly dispersed, each culture dish is placed in a constant temperature incubator and is cultured for 6 hours under a 5W xenon lamp, and the antibacterial performance is tested by adopting a bacteriostatic ring method.
Figure BDA0003028490390000092

Claims (7)

1. Ag/C loaded3N4The active carbon composite material of the nanometer particle is characterized in that: the load Ag/C3N4Of nanoparticlesThe preparation method of the active carbon composite material comprises the following steps:
(1) adding a solvent and a cosolvent into a reaction bottle, adding 1,3, 5-tri (4-bromophenyl) benzene and 1, 4-benzene diboronic acid, stirring for dissolving, adding an accelerator potassium carbonate and a catalyst tetrakis (triphenylphosphine) palladium, heating to 160 ℃, carrying out reflux reaction for 48-96h, filtering to remove the solvent, extracting and purifying by using distilled water, dichloromethane and acetone in sequence through a Soxhlet extractor, and drying to obtain a biphenyl microporous polymer;
(2) adding the biphenyl microporous polymer into an atmosphere tube furnace, controlling the heating rate to be 2-8 ℃/min, carrying out thermal oxidation pretreatment, and then carrying out high-temperature carbonization treatment to obtain a porous activated carbon material;
(3) adding ethylene glycol and melamine into a reaction bottle, stirring and dissolving, adding a nitric acid solution, adjusting the pH value of the solution to 4-5, and then dropwise adding AgNO3The aqueous solution is placed in a drying oven after being dispersed uniformly by ultrasonic waves, the solution is dried for 10 to 20 hours at the temperature of between 70 and 100 ℃, then the mixed product is placed in an atmosphere tube furnace, the heating rate is controlled to be between 5 and 10 ℃/min, the temperature is raised to between 520 ℃ and 580 ℃, the heat preservation treatment is carried out for 1 to 2 hours, then distilled water and ethanol are used for centrifugal washing and drying, and the Ag/g-C is prepared3N4Nanoparticles;
(4) adding ethanol and distilled water into a reaction bottle, adding a porous activated carbon material and Ag/g-C3N4The nano particles are stirred for 5 to 10 hours after ultrasonic dispersion, and then the solvent is removed by vacuum drying to obtain the load Ag/C3N4An active carbon composite material of nano particles.
2. Ag/C-loaded carrier according to claim 13N4The active carbon composite material of the nanometer particle is characterized in that: in the step (1), the solvent is N, N-dimethylformamide, the cosolvent is toluene, and the volume ratio of the N, N-dimethylformamide to the cosolvent is 100: 15-40.
3. Ag/C-loaded carrier according to claim 13N4The active carbon composite material of the nanometer particle is characterized in that: 1,3,5-The mass ratio of the tri (4-bromophenyl) benzene to the 1, 4-benzenediboronic acid to the potassium carbonate to the tetrakis (triphenylphosphine) palladium is 100:115-130:650-850: 28-35.
4. Ag/C-loaded carrier according to claim 13N4The active carbon composite material of the nanometer particle is characterized in that: the thermal oxidation pretreatment in the step (2) is carried out in the air atmosphere at the temperature of 180 ℃ and 250 ℃ for 1-2 h; high-temperature carbonization is carried out for 2-3h at the temperature of 750-850 ℃ in the argon atmosphere.
5. Ag/C-loaded carrier according to claim 13N4The active carbon composite material of the nanometer particle is characterized in that: the melamine and AgNO in the step (3)3The mass ratio of (A) to (B) is 100: 0.4-4.5.
6. Ag/C-loaded carrier according to claim 13N4The active carbon composite material of the nanometer particle is characterized in that: Ag/C in the step (2)3N4The grain diameter of the nano particles is 5-500nm, and the mass fraction of Ag is 0.4% -0.7%.
7. Ag/C-loaded carrier according to claim 13N4The active carbon composite material of the nanometer particle is characterized in that: the porous activated carbon material and Ag/g-C in the step (4)3N4The mass ratio of the nano particles is 100: 1.5-10.
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CN113578300A (en) * 2021-07-15 2021-11-02 华南理工大学 Ag-g-C3N4Biological carbon composite material and preparation method and application thereof
CN113755031A (en) * 2021-10-22 2021-12-07 安徽锦华氧化锌有限公司 Dispersing and activating treatment method for zinc oxide
CN114717690A (en) * 2022-03-31 2022-07-08 中国科学院赣江创新研究院 Preparation method and application of biomass carbon-based material
CN115463654A (en) * 2022-08-31 2022-12-13 广东工业大学 Pd-Ag loaded g-C3N4 nanosheet photocatalyst as well as preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113578300A (en) * 2021-07-15 2021-11-02 华南理工大学 Ag-g-C3N4Biological carbon composite material and preparation method and application thereof
CN113755031A (en) * 2021-10-22 2021-12-07 安徽锦华氧化锌有限公司 Dispersing and activating treatment method for zinc oxide
CN114717690A (en) * 2022-03-31 2022-07-08 中国科学院赣江创新研究院 Preparation method and application of biomass carbon-based material
CN115463654A (en) * 2022-08-31 2022-12-13 广东工业大学 Pd-Ag loaded g-C3N4 nanosheet photocatalyst as well as preparation method and application thereof
CN115463654B (en) * 2022-08-31 2024-02-20 广东工业大学 Pd-Ag loaded g-C 3 N 4 Nanosheet photocatalyst, preparation method and application

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