CN111450813A - SnS2-g-C3N4Heterojunction photocatalytic degradation material and preparation method thereof - Google Patents

SnS2-g-C3N4Heterojunction photocatalytic degradation material and preparation method thereof Download PDF

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CN111450813A
CN111450813A CN202010395779.7A CN202010395779A CN111450813A CN 111450813 A CN111450813 A CN 111450813A CN 202010395779 A CN202010395779 A CN 202010395779A CN 111450813 A CN111450813 A CN 111450813A
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陈艮
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Abstract

The invention relates to the technical field of photocatalytic degradation and discloses SnS2‑g‑C3N4The heterojunction photocatalytic degradation material comprises the following formula raw materials and components: honeycomb Ag doped g-C3N4Carbon nano tube, stannic chloride, thioglycolic acid and hexadecyl trimethyl ammonium bromide. The SnS2‑g‑C3N4Heterojunction photocatalytic degradation material, honeycomb Ag doped g-C3N4Has rich pore structure and large specific surface area, and the doping of Ag makes g-C3N4The light absorption edge of the photocatalyst generates red shift, the responsiveness and the utilization rate of the photocatalyst to light energy are enhanced, and the nano SnS2Deposition of hollow microsphere modified carbon nanotube on Ag doped g-C3N4The carbon nano tube forms a heterojunction structure on the SnS2And Ag doped g-C3N4A three-dimensional conductive network is formed between the two layers, the separation of photo-generated electrons and holes is promoted under the synergistic effect, a large amount of photo-generated electrons and holes are generated, and superoxide radicals and hydroxyl radicals with extremely strong activity are generated to carry out the degradation process of organic pollutants.

Description

SnS2-g-C3N4Heterojunction photocatalytic degradation material and preparation method thereof
Technical Field
The invention relates to the technical field of photocatalytic degradation, in particular to SnS2-g-C3N4Heterojunction photocatalytic degradation material and its preparation method are provided.
Background
Water pollution becomes one of the most serious global environmental pollution problems at present, the water pollution sources mainly comprise untreated and discharged industrial wastewater, domestic sewage, farmland anhydrous and the like, and the pollutants mainly comprise inorganic pollutants, such as acid, alkali and inorganic salt, including heavy metal ions such as copper, cadmium, mercury and the like; the organic pollutants mainly comprise aromatic compounds, halides, carbohydrates, proteins and the like, dissolved oxygen in water is consumed when the organic pollutants are decomposed by microorganisms, the reproductive metabolic process of aquatic organisms is influenced, after the dissolved oxygen in water is exhausted, the organic matters are subjected to anaerobic decomposition to generate toxic gases such as hydrogen sulfide and mercaptan, the water quality is further deteriorated, and organic dye pollutants containing aromatic rings such as methylene blue, orange yellow I, rhodamine B and the like have high toxicity and are difficult to biodegrade in a water body environment, so that the aquatic organisms are seriously damaged, and the water body environment is polluted.
At present, the organic dye wastewater treatment methods mainly comprise a physical flocculation method, a chemical oxidation method, a membrane separation method, an ion exchange method, an adsorption method and the like, wherein photocatalytic degradation is a novel high-efficiency water pollution treatment method, and light is radiated on a photocatalyst to produce in a reaction systemThe generated photoproduction electrons, holes and free radicals with extremely strong activity are added and substituted with organic pollutants to degrade the pollutants into non-toxic and low-toxic micromolecules or inorganic substances, and the photocatalyst mainly comprises TiO2Semiconductor material, CdS, MoS2、SnS2Iso-transition metal sulfide, BiOBr, BiFeO3An equi-bismuth based metal catalyst, etc., wherein the graphite phase carbon nitride is g-C3N4The chemical property is stable, the preparation method is simple, the pollution is less, the electronic band structure is unique, the photochemical activity is certain, and the research on the aspects of photocatalytic water splitting hydrogen production, photocatalytic pollutant degradation and the like is wide, but g-C3N4Has a low specific surface area and a narrow light absorption range, has photochemical activity only in the range of 440-475nm visible light wave band, has low utilization rate of light energy, and has g-C3N4The generated photoproduction electrons and holes are easy to be combined, and the g-C is greatly reduced3N4Photochemical activity and degradation efficiency of the catalyst.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an SnS2-g-C3N4Heterojunction photocatalytic degradation material and preparation method thereof, solving the problem of g-C3N4Has low specific surface area and narrow light absorption range, and solves the problem of g-C3N4The problem of easy recombination of the photo-generated electrons and holes.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: SnS2-g-C3N4The heterojunction photocatalytic degradation material comprises the following formula raw materials and components: honeycomb Ag doped g-C3N4Carbon nano tube, stannic chloride, thioglycolic acid and hexadecyl trimethyl ammonium bromide.
Preferably, the cellular Ag is doped with g-C3N4The preparation method comprises the following steps:
(1) adding distilled water solvent and nano SiO into a reaction bottle2Is placed in ultrasonic for dispersionPerforming ultrasonic dispersion in an instrument, adding polyethyleneimine, heating to 80-110 ℃, stirring at a constant speed for 4-6h, performing vacuum drying on the solution to remove the solvent, placing the solid product in an atmosphere furnace, introducing argon, heating at the rate of 3-8 ℃/min, and performing heat preservation and calcination at the temperature of 520-560 ℃ for 2-4 h.
(2) Placing the calcined product in a distilled water solvent, adding cyanamide and silver nitrate, after uniformly dispersing by ultrasonic, drying the solution in vacuum to remove the solvent and grinding the solution into fine powder, then placing the fine powder in an atmosphere furnace and introducing argon, wherein the heating rate is 1-5 ℃/min, carrying out heat preservation calcination at the temperature of 540-560 ℃ for 3-5h, placing the calcined product in a hydrofluoric acid solution to carry out etching to remove SiO2, and preparing the honeycomb-shaped Ag doped g-C3N4。
Preferably, the nano SiO in the step (1)2Has an average particle diameter of not more than 20nm and is made of nano SiO2The mass ratio of the polyethyleneimine to the polyethyleneimine is 1: 3-4.
Preferably, the mass ratio of the calcined product, the cyanamide and the silver nitrate in the step (2) is 0.3-0.6:1: 0.008-0.02.
Preferably, ultrasonic dispersion appearance includes instrument main part, the inside left side fixedly connected with ultrasonic emitter of instrument main part, the inside right side fixedly connected with heating ring of instrument main part, the inside below fixedly connected with agitating unit of instrument main part, agitating unit swing joint has the (mixing) shaft, (mixing) shaft and magnetic stirring fan piece fixed connection, the top swing joint of instrument main part has the apron, apron upper surface and nut fixed connection, the apron is inside and adjusts pole swing joint, adjust pole swing joint nut, the one end swing joint who adjusts the pole has the governing valve, governing valve and fixation clamp swing joint.
Preferably, the SnS2-g-C3N4The preparation method of the heterojunction photocatalytic degradation material comprises the following steps:
(1) adding polyvinyl alcohol solvent, carbon nano tube, hexadecyl trimethyl ammonium bromide, thioglycolic acid and stannic chloride into a reaction bottle, placing the reaction bottle in an ultrasonic dispersion instrument for ultrasonic dispersion, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating the reaction kettle to 190 plus materials for reaction at 220 ℃ for 10-15h, cooling the solution to room temperature, centrifugally separating to remove the impuritiesRemoving solvent, washing the solid product with distilled water and ethanol, and drying to obtain SnS2The hollow microspheres modify the carbon nanotubes.
(2) Distilled water and SnS were added to the reaction flask2Modifying carbon nano-tubes with hollow microspheres, adding honeycomb Ag doped g-C after uniformly dispersing by ultrasonic3N4Pouring the solution into a high-pressure hydrothermal reaction kettle after uniformly stirring, placing the solution into a reaction kettle heating box, heating the solution to the temperature of 120-160 ℃, reacting for 15-25h, carrying out vacuum drying on the solution to remove the solvent, grinding the solution into fine powder, and preparing to obtain SnS2-g-C3N4A heterojunction photocatalytic degradation material.
Preferably, the mass ratio of the carbon nano tube, the hexadecyl trimethyl ammonium bromide, the thioglycolic acid and the stannic chloride is 0.2-0.6:0.8-1.2:3.5-4: 1.
Preferably, the SnS2Hollow microsphere modified carbon nanotube and honeycomb Ag-doped g-C3N4The mass ratio of (A) to (B) is 0.04-0.1: 1.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the SnS2-g-C3N4The heterojunction photocatalytic degradation material is prepared by modifying nano SiO with polyethyleneimine2Preparing the honeycomb Ag doped g-C by using silver nitrate as a silver source as a pore-forming agent through high-temperature thermal cracking and hydrofluoric acid etching3N4Has rich honeycomb-coal-shaped pore structure, greatly increases the specific surface area, and Ag is doped into g-C3N4In the matrix of (2), the g-C is reduced3N4Intermolecular van der Waals forces, decrease g-C3N4Thereby promoting full contact of the catalyst with light radiation, while Ag doping makes g-C3N4The light absorption edge of (A) is red-shifted to make g-C3N4Has good photochemical activity in the wavelength range of 460-580nm, and enhances the response and utilization rate of the photocatalyst to light energy.
The SnS2-g-C3N4A heterojunction photocatalytic degradation material is prepared from nano SnS by using hexadecyl trimethyl ammonium bromide as a template sacrificial agent and adopting a high-pressure hot solvent method2The hollow microsphere modified carbon nano tube has smaller particle size, larger specific surface area and nano SnS2Deposition on Ag doped g-C3N4The carbon nano tube with excellent conduction band performance is used as an electron acceptor, and the carbon nano tube is positioned on SnS2And Ag doped g-C3N4Form a three-dimensional conductive network between the catalyst and the SnS to promote the migration of photogenerated electrons when light is radiated on the catalyst2And g-C3N4The generated photogenerated electrons are transited from a valence band to a conduction band, holes are left in the valence band, and g-C is promoted by a heterojunction structure and a three-dimensional conductive network3N4Electron direction SnS on conduction band2Conduction band migration of, SnS2Hole direction of valence band g-C3N4The valence band migration promotes the separation of the photoproduction electrons and the holes, the recombination rate of the photoproduction electrons and the holes is reduced, a large amount of photoproduction electrons and holes are generated and further react with oxygen and water molecules to generate superoxide radicals and hydroxyl radicals with extremely strong activity, the superoxide radicals and organic pollutants such as methylene blue, rhodamine B and the like are subjected to redox reaction and degraded into non-toxic or low-toxic micromolecules, a xenon lamp is used as a light source, and after 72 hours of irradiation time, the degradation efficiency of the catalyst on the rhodamine B reaches 94.9-98.8%, and the degradation efficiency on the methylene blue reaches 94.7-97.5%.
Drawings
FIG. 1 is a schematic front view of an instrument body;
fig. 2 is a schematic view of adjustment lever adjustment.
1. An instrument body; 2. an ultrasonic transmitter; 3. heating a ring; 4. a stirring device; 5. a stirring shaft; 6. magnetic stirring fan blades; 7. a cover plate; 8. a nut; 9. adjusting a rod; 10. adjusting a valve; 11. and (4) fixing clips.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: SnS2-g-C3N4Heterogeneous natureThe light catalyzed degradable material comprises the following raw materials in formula and components: honeycomb Ag doped g-C3N4Carbon nano tube, stannic chloride, thioglycolic acid and hexadecyl trimethyl ammonium bromide.
Honeycomb Ag doped g-C3N4The preparation method comprises the following steps:
(1) adding distilled water solvent and nano SiO with average grain diameter less than or equal to 20nm into a reaction bottle2The ultrasonic dispersion device comprises an instrument main body, an ultrasonic emitter is fixedly connected to the left side inside the instrument main body, a heating ring is fixedly connected to the right side inside the instrument main body, a stirring device is fixedly connected to the lower portion inside the instrument main body, a stirring shaft is movably connected to the stirring device and is fixedly connected with a magnetic stirring fan blade, a cover plate is movably connected to the upper portion of the instrument main body, the upper surface of the cover plate is fixedly connected with a nut, the inner portion of the cover plate is movably connected with an adjusting rod, the adjusting rod is movably connected with the nut, one end of the adjusting rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a fixing clamp, polyethyleneimine is added, the mass ratio of the cover plate to the adjusting rod to the nut is 1:3-4, the cover plate is heated to 80-110 ℃, the solution is stirred at, the heating rate is 3-8 ℃/min, and the calcination is carried out for 2-4h at the temperature of 520-560 ℃.
(2) Placing the calcined product into a distilled water solvent, adding cyanamide and silver nitrate with the mass ratio of 0.3-0.6:1:0.008-0.02, after ultrasonic dispersion is uniform, drying the solution in vacuum to remove the solvent and grinding the solution into fine powder, then placing the fine powder into an atmosphere furnace and introducing argon, the heating rate is 1-5 ℃/min, carrying out heat preservation and calcination at the temperature of 540 plus 560 ℃ for 3-5h, placing the calcined product into a hydrofluoric acid solution for etching to remove SiO2Preparing the honeycomb Ag doped g-C3N4。
SnS2-g-C3N4The preparation method of the heterojunction photocatalytic degradation material comprises the following steps:
(1) adding polyvinyl alcohol solvent, carbon nano tube, hexadecyl trimethyl ammonium bromide, thioglycolic acid and stannic chloride into a reaction bottle, wherein the mass ratio of the four is 0.2-0.6:0.8-1.2:3.5-4:1, and placing the mixture in a super-solventPerforming ultrasonic dispersion in an acoustic dispersion instrument, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the solution into a reaction kettle heating box, heating the solution to 190-2The hollow microspheres modify the carbon nanotubes.
(2) Distilled water and SnS were added to the reaction flask2The hollow microsphere modified carbon nano tube has the mass ratio of 0.04-0.1:1, and the honeycomb Ag is added to dope g-C after the ultrasonic dispersion is uniform3N4Pouring the solution into a high-pressure hydrothermal reaction kettle after uniformly stirring, placing the solution into a reaction kettle heating box, heating the solution to the temperature of 120-160 ℃, reacting for 15-25h, carrying out vacuum drying on the solution to remove the solvent, grinding the solution into fine powder, and preparing to obtain SnS2-g-C3N4A heterojunction photocatalytic degradation material.
Example 1
(1) Preparation of cellular Ag doped g-C3N4Component 1: adding distilled water solvent and nano SiO with average grain diameter less than or equal to 20nm into a reaction bottle2The ultrasonic dispersion instrument comprises an instrument main body, an ultrasonic emitter is fixedly connected to the left side inside the instrument main body, a heating ring is fixedly connected to the right side inside the instrument main body, a stirring device is fixedly connected to the lower portion inside the instrument main body, a stirring shaft is movably connected to the stirring device and is fixedly connected with a magnetic stirring fan blade, a cover plate is movably connected to the upper portion of the instrument main body, the upper surface of the cover plate is fixedly connected with a nut, the inner portion of the cover plate is movably connected with an adjusting rod, the adjusting rod is movably connected with the nut, one end of the adjusting rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a fixing clamp, polyethyleneimine is added, the mass ratio of the cover plate to the adjusting rod is 1:3, the cover plate is heated to 80 ℃, the solution is stirred at a constant speed for, calcining at 520 ℃ for 2h, placing the calcined product into a distilled water solvent, adding cyanamide and silver nitrate with the mass ratio of 0.3:1:0.008, ultrasonically dispersing uniformly, drying the solution in vacuum to remove the solvent, grinding into fine powder, placing into an atmosphere furnace, and introducingIntroducing argon, heating at a rate of 1 ℃/min, calcining at 540-560 ℃ for 3h, placing the calcined product in hydrofluoric acid solution for etching to remove SiO2, and preparing the honeycomb-shaped Ag doped g-C3N4And (3) component 1.
(2) Preparation of SnS2The hollow microsphere modified carbon nanotube comprises the following components in percentage by weight: adding polyvinyl alcohol solvent, carbon nano tube, hexadecyl trimethyl ammonium bromide, thioglycolic acid and stannic chloride into a reaction bottle, placing the mixture into an ultrasonic disperser for ultrasonic dispersion, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle into a reaction kettle heating box, heating to 190 ℃, reacting for 10 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the SnS2And (3) modifying the carbon nanotube component 1 by the hollow microspheres.
(3) Preparation of SnS2-g-C3N4Heterojunction photocatalytic degradation material 1: distilled water and SnS were added to the reaction flask2The component 1 of the hollow microsphere modified carbon nano tube is 0.04:1 in mass ratio, and the honeycomb-shaped Ag is added to be doped with g-C after the ultrasonic dispersion is uniform3N4Uniformly stirring the component 1, pouring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle in a heating box of the reaction kettle, heating to 120 ℃, reacting for 15 hours, drying the solution in vacuum to remove the solvent, grinding the solution into fine powder, and preparing the SnS2-g-C3N4The heterojunction photocatalytic degradation material 1.
Example 2
(1) Preparation of cellular Ag doped g-C3N4And (2) component: adding distilled water solvent and nano SiO with average grain diameter less than or equal to 20nm into a reaction bottle2The ultrasonic dispersion instrument comprises an instrument main body, an ultrasonic emitter fixedly connected to the left side inside the instrument main body, a heating ring fixedly connected to the right side inside the instrument main body, and a stirring device fixedly connected to the lower side inside the instrument main body, wherein the stirring device is movably connected with a stirring shaft, the stirring shaft is fixedly connected with a magnetic stirring fan blade, a cover plate is movably connected to the upper side of the instrument main body, the upper surface of the cover plate is fixedly connected with a nut, and the cover plate is movably connected with an adjusting rodConnecting, movably connecting an adjusting rod with a nut, movably connecting one end of the adjusting rod with an adjusting valve, movably connecting the adjusting valve with a fixing clamp, adding polyethyleneimine, heating to 110 ℃ with the mass ratio of 1:3, stirring at constant speed for 4-6h, vacuum drying the solution to remove the solvent, placing the solid product in an atmosphere furnace, introducing argon gas, heating at the rate of 8 ℃/min, calcining at 520 ℃ for 2h, placing the calcined product into a distilled water solvent, adding cyanamide and silver nitrate according to the mass ratio of 0.3:1:0.011, dispersing uniformly by ultrasonic, vacuum drying the solution to remove the solvent, grinding into fine powder, placing in an atmosphere furnace, introducing argon gas, heating at a rate of 5 deg.C/min, and (3) carrying out heat preservation and calcination at 540 ℃ for 3h, and placing the calcined product in a hydrofluoric acid solution for etching to remove SiO2 to prepare the honeycomb-shaped Ag doped g-C.3N4And (3) component 2.
(2) Preparation of SnS2The hollow microsphere modified carbon nanotube component 2: adding a polyvinyl alcohol solvent, a carbon nano tube, hexadecyl trimethyl ammonium bromide, thioglycolic acid and stannic chloride into a reaction bottle, placing the mixture into an ultrasonic disperser for ultrasonic dispersion, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle into a reaction kettle heating box, heating to 190 ℃, reacting for 10 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the SnS2And (3) modifying the carbon nano tube component 2 by using the hollow microspheres.
(3) Preparation of SnS2-g-C3N4Heterojunction photocatalytic degradation material 2: distilled water and SnS were added to the reaction flask2The component 2 of the hollow microsphere modified carbon nano tube is 0.06:1 in mass ratio, and the mixture is added with honeycomb Ag doped g-C after being uniformly dispersed by ultrasonic3N4And (2) uniformly stirring the components, pouring the solution into a high-pressure hydrothermal reaction kettle, placing the solution into a heating box of the reaction kettle, heating the solution to 160 ℃, reacting for 15 to 25 hours, drying the solution in vacuum to remove the solvent, grinding the solution into fine powder, and preparing the SnS2-g-C3N4The heterojunction photocatalytically degrades the material 2.
Example 3
(1) Preparation of cellular Ag doped g-C3N4And (3) component: adding distilled water solvent and nano SiO with average grain diameter less than or equal to 20nm into a reaction bottle2Placing the mixture in an ultrasonic disperser for ultrasonic dispersion, wherein the ultrasonic disperser comprises an instrument main body, an ultrasonic emitter is fixedly connected on the left side inside the instrument main body, a heating ring is fixedly connected on the right side inside the instrument main body, a stirring device is fixedly connected below the inside of the instrument main body, the stirring device is movably connected with a stirring shaft, the stirring shaft is fixedly connected with a magnetic stirring fan blade, a cover plate is movably connected above the instrument main body, the upper surface of the cover plate is fixedly connected with a nut, the inside of the cover plate is movably connected with an adjusting rod, the adjusting rod is movably connected with the nut, one end of the adjusting rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a fixing clamp, then polyethyleneimine is added, the mass ratio of the two is 1:3.5, heating is carried out to 100 ℃, stirring is carried out for 5 hours at constant speed, calcining at 540 ℃ for 3h in a heat preservation way, placing the calcined product into a distilled water solvent, adding cyanamide and silver nitrate with the mass ratio of 0.45:1:0.014, after ultrasonic dispersion is uniform, drying the solution in vacuum to remove the solvent and grinding the solution into fine powder, then placing the fine powder into an atmosphere furnace and introducing argon, heating the fine powder at the speed of 2 ℃/min, calcining at 550 ℃ for 4h in a heat preservation way, placing the calcined product into a hydrofluoric acid solution to etch and remove SiO2, and preparing the honeycomb-shaped Ag doped g-C3N4And (3) component.
(2) Preparation of SnS2The hollow microsphere modified carbon nanotube component 3: adding polyvinyl alcohol solvent, carbon nano tube, hexadecyl trimethyl ammonium bromide, thioglycolic acid and stannic chloride into a reaction bottle, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle into a reaction kettle heating box, heating the kettle to 200 ℃ for reaction for 12 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the SnS2And (3) modifying the carbon nano tube component 3 by using the hollow microspheres.
(3) Preparation of SnS2-g-C3N4Heterojunction photocatalytic degradation material 3: distilled water and SnS were added to the reaction flask2The component 3 of the hollow microsphere modified carbon nano tube is 0.07:1 in mass ratio, and after uniform ultrasonic dispersion, the mixture is added with honeycomb Ag doped g-C3N4And (3) uniformly stirring the components, pouring the solution into a high-pressure hydrothermal reaction kettle, placing the solution into a heating box of the reaction kettle, heating the solution to 140 ℃, reacting for 20 hours, carrying out vacuum drying on the solution to remove the solvent, grinding the solution into fine powder, and preparing the SnS2-g-C3N4The heterojunction photocatalytically degrades the material 3.
Example 4
(1) Preparation of cellular Ag doped g-C3N4And (4) component: adding distilled water solvent and nano SiO with average grain diameter less than or equal to 20nm into a reaction bottle2Placing the mixture in an ultrasonic disperser for ultrasonic dispersion, wherein the ultrasonic disperser comprises an instrument main body, an ultrasonic emitter is fixedly connected on the left side inside the instrument main body, a heating ring is fixedly connected on the right side inside the instrument main body, a stirring device is fixedly connected below the inside of the instrument main body, the stirring device is movably connected with a stirring shaft, the stirring shaft is fixedly connected with a magnetic stirring fan blade, a cover plate is movably connected above the instrument main body, the upper surface of the cover plate is fixedly connected with a nut, the inside of the cover plate is movably connected with an adjusting rod, the adjusting rod is movably connected with the nut, one end of the adjusting rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a fixing clamp, then polyethyleneimine is added, the mass ratio of the two components is 1:4, heating is carried out to 80 ℃, stirring is carried out at constant speed for 4-6, calcining at 520 ℃ for 4h in a heat preservation manner, placing the calcined product into a distilled water solvent, adding cyanamide and silver nitrate in a mass ratio of 0.6:1:0.017, performing ultrasonic dispersion uniformly, then drying the solution in vacuum to remove the solvent and grinding the solution into fine powder, then placing the fine powder into an atmosphere furnace, introducing argon, heating at a rate of 5 ℃/min, calcining at 560 ℃ for 3h in a heat preservation manner, placing the calcined product into a hydrofluoric acid solution for etching to remove SiO2, and preparing the honeycomb-shaped Ag doped g-C3N4And (4) component.
(2) Preparation of SnS2The hollow microsphere modified carbon nanotube component 4: adding polyvinyl alcohol solvent, carbon nano tube, hexadecyl trimethyl ammonium bromide and mercaptoethane into a reaction bottleAcid and stannic chloride with the mass ratio of 0.6:0.8:3.5:1, placing the mixture into an ultrasonic disperser for ultrasonic dispersion, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle in a heating box of the reaction kettle, heating the kettle to 220 ℃ for reaction for 15 hours, cooling the solution to room temperature, centrifugally separating the solution to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying the solid product, and preparing the SnS2And (4) modifying the carbon nano tube component by the hollow microspheres.
(3) Preparation of SnS2-g-C3N4Heterojunction photocatalytic degradation material 4: distilled water and SnS were added to the reaction flask2The component 4 of the hollow microsphere modified carbon nano tube is 0.09:1 in mass ratio, and the honeycomb Ag is added to be doped with g-C after the ultrasonic dispersion is uniform3N4And (4) uniformly stirring the component 4, pouring the solution into a high-pressure hydrothermal reaction kettle, placing the solution into a heating box of the reaction kettle, heating the solution to 160 ℃, reacting for 15 hours, carrying out vacuum drying on the solution to remove the solvent, grinding the solution into fine powder, and preparing the SnS2-g-C3N4The heterojunction photocatalytically degrades the material 4.
Example 5
(1) Preparation of cellular Ag doped g-C3N4And (5) component: adding distilled water solvent and nano SiO with average grain diameter less than or equal to 20nm into a reaction bottle2The ultrasonic dispersion instrument comprises an instrument main body, an ultrasonic emitter is fixedly connected to the left side inside the instrument main body, a heating ring is fixedly connected to the right side inside the instrument main body, a stirring device is fixedly connected to the lower portion inside the instrument main body, a stirring shaft is movably connected to the stirring device and is fixedly connected with a magnetic stirring fan blade, a cover plate is movably connected to the upper portion of the instrument main body, the upper surface of the cover plate is fixedly connected with a nut, the inner portion of the cover plate is movably connected with an adjusting rod, the adjusting rod is movably connected with the nut, one end of the adjusting rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a fixing clamp, polyethyleneimine is added, the mass ratio of the cover plate to the adjusting rod is 1:4, the solution is heated to 110 ℃, the solution is stirred at a constant speed for 6, calcining at 560 deg.C for 4 hr, adding the calcined product to distilled water solvent, adding cyanamide and waterSilver nitrate, the mass ratio of the three is 0.6:1:0.02, after the three are dispersed evenly by ultrasonic, the solution is dried in vacuum to remove the solvent and ground into fine powder, then the fine powder is placed in an atmosphere furnace and is introduced with argon, the temperature rise rate is 5 ℃/min, the fine powder is calcined for 5 hours at 560 ℃, the calcined product is placed in hydrofluoric acid solution to be etched to remove SiO2, and the honeycomb-shaped Ag doped g-C is prepared3N4And (5) component.
(2) Preparation of SnS2The hollow microsphere modified carbon nanotube component 5: adding a polyvinyl alcohol solvent, a carbon nano tube, hexadecyl trimethyl ammonium bromide, thioglycolic acid and stannic chloride into a reaction bottle, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle into a reaction kettle heating box, heating to 220 ℃ for reaction for 15 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the SnS2And (3) modifying the carbon nano tube component 5 by the hollow microspheres.
(3) Preparation of SnS2-g-C3N4Heterojunction photocatalytic degradation material 5: distilled water and SnS were added to the reaction flask2The component 5 of the hollow microsphere modified carbon nano tube is 0.1:1 in mass ratio, and the honeycomb-shaped Ag is added to be doped with g-C after the ultrasonic dispersion is uniform3N4And (5) uniformly stirring the components, pouring the solution into a high-pressure hydrothermal reaction kettle, placing the solution into a heating box of the reaction kettle, heating the solution to 160 ℃, reacting for 25 hours, drying the solution in vacuum to remove the solvent, grinding the solution into fine powder, and preparing the SnS2-g-C3N4The heterojunction photocatalytically degrades the material 5.
1000m L of distilled water and 20mg of rhodamine B were added to six groups of reaction flasks, respectively, and 10mg of SnS prepared in examples 1 to 5 was added to five groups of reaction flasks, respectively2-g-C3N41-5 of heterojunction photocatalytic degradation material, and taking the other group without adding a catalyst as a blank control experiment, placing six groups of reaction bottles in a dark place for standing for 24h, irradiating for 24h and 72h by taking a 480W xenon lamp as a light source, and detecting the residual concentration of rhodamine B by using a liquid chromatography-mass spectrometer.
Figure BDA0002487474310000111
1000m L distilled water and 20mg of methylene blue were added to six reaction flasks, respectively, and 10mg of SnS obtained in examples 1 to 5 was added to five reaction flasks, respectively2-g-C3N41-5 of heterojunction photocatalytic degradation material, and the other group of reaction bottles without catalysts as blank control experiments, standing the six groups of reaction bottles for 24h in a dark place, irradiating the reaction bottles for 24h and 72h under a 480W xenon lamp as a light source, and detecting the residual concentration of methylene blue by using a liquid chromatography-mass spectrometer.
Figure BDA0002487474310000121
In summary, the SnS2-g-C3N4The heterojunction photocatalytic degradation material is prepared by modifying nano SiO with polyethyleneimine2Preparing the honeycomb Ag doped g-C by using silver nitrate as a silver source as a pore-forming agent through high-temperature thermal cracking and hydrofluoric acid etching3N4Has rich honeycomb-coal-shaped pore structure, greatly increases the specific surface area, and Ag is doped into g-C3N4In the matrix of (2), the g-C is reduced3N4Intermolecular van der Waals forces, decrease g-C3N4Thereby promoting full contact of the catalyst with light radiation, while Ag doping makes g-C3N4The light absorption edge of (A) is red-shifted to make g-C3N4Has good photochemical activity in the wavelength range of 460-580nm, and enhances the response and utilization rate of the photocatalyst to light energy.
The nano SnS is prepared by taking hexadecyl trimethyl ammonium bromide as a template sacrificial agent through a high-pressure hot solvent method2The hollow microsphere modified carbon nano tube has smaller particle size, larger specific surface area and nano SnS2Deposition on Ag doped g-C3N4The carbon nano tube with excellent conduction band performance is used as an electron acceptor, and the carbon nano tube is positioned on SnS2And Ag doped g-C3N4Form a three-dimensional conductive network between the catalyst and the SnS to promote the migration of photogenerated electrons when light is radiated on the catalyst2And g-C3N4The generated photogenerated electrons are transited from a valence band to a conduction band, holes are left in the valence band, and g-C is promoted by a heterojunction structure and a three-dimensional conductive network3N4Electron direction SnS on conduction band2Conduction band migration of, SnS2Hole direction of valence band g-C3N4The valence band migration promotes the separation of the photoproduction electrons and the holes, the recombination rate of the photoproduction electrons and the holes is reduced, a large amount of photoproduction electrons and holes are generated and further react with oxygen and water molecules to generate superoxide radicals and hydroxyl radicals with extremely strong activity, the superoxide radicals and organic pollutants such as methylene blue, rhodamine B and the like are subjected to redox reaction and degraded into non-toxic or low-toxic micromolecules, a xenon lamp is used as a light source, and after 72 hours of irradiation time, the degradation efficiency of the catalyst on the rhodamine B reaches 94.9-98.8%, and the degradation efficiency on the methylene blue reaches 94.7-97.5%.

Claims (8)

1. SnS2-g-C3N4The heterojunction photocatalytic degradation material comprises the following formula raw materials and components, and is characterized in that: honeycomb Ag doped g-C3N4Carbon nano tube, stannic chloride, thioglycolic acid and hexadecyl trimethyl ammonium bromide.
2. An SnS according to claim 12-g-C3N4The heterojunction photocatalytic degradation material is characterized in that: the cellular Ag is doped with g-C3N4The preparation method comprises the following steps:
(1) adding nano SiO into distilled water solvent2Placing the mixture in an ultrasonic dispersion instrument for ultrasonic dispersion, adding polyethyleneimine, heating to 80-110 ℃, stirring at a constant speed for 4-6h, removing the solvent, placing the solid product in an atmosphere furnace, introducing argon, heating at the rate of 3-8 ℃/min, and carrying out heat preservation and calcination at the temperature of 520-560 ℃ for 2-4 h;
(2) placing the calcined product in distilled water solvent, adding cyanamide and silver nitrate, and addingAfter the sound is dispersed evenly, removing the solvent and grinding into fine powder, then placing the fine powder in an atmosphere furnace and introducing argon, the heating rate is 1-5 ℃/min, carrying out heat preservation and calcination at 540-3N4。
3. An SnS according to claim 22-g-C3N4The heterojunction photocatalytic degradation material is characterized in that: the nano SiO in the step (1)2Has an average particle diameter of not more than 20nm and is made of nano SiO2The mass ratio of the polyethyleneimine to the polyethyleneimine is 1: 3-4.
4. An SnS according to claim 22-g-C3N4The heterojunction photocatalytic degradation material is characterized in that: the mass ratio of the calcined product, the cyanamide and the silver nitrate in the step (2) is 0.3-0.6:1: 0.008-0.02.
5. An SnS according to claim 22-g-C3N4The heterojunction photocatalytic degradation material is characterized in that: ultrasonic dispersion appearance includes instrument main part, the inside left side fixedly connected with ultrasonic emitter of instrument main part, the inside right side fixedly connected with heating ring of instrument main part, the inside below fixedly connected with agitating unit of instrument main part, agitating unit swing joint has the (mixing) shaft, (mixing) shaft and magnetic stirring fan piece fixed connection, the top swing joint of instrument main part has the apron, apron upper surface and nut fixed connection, the apron is inside and adjusts pole swing joint, adjust pole swing joint nut, the one end swing joint who adjusts the pole has the governing valve, governing valve and fixation clamp swing joint.
6. An SnS according to claim 12-g-C3N4The heterojunction photocatalytic degradation material is characterized in that: the SnS2-g-C3N4The preparation method of the heterojunction photocatalytic degradation material comprises the following steps:
(1) to polyvinyl alcoholAdding carbon nano tube, hexadecyl trimethyl ammonium bromide, thioglycollic acid and stannic chloride into a solvent, after uniform ultrasonic dispersion, transferring the solution into a reaction kettle, heating to 190-2Modifying the carbon nano tube by the hollow microsphere;
(2) adding SnS to distilled water2Modifying carbon nano-tubes with hollow microspheres, adding honeycomb Ag doped g-C after uniformly dispersing by ultrasonic3N4Pouring the solution into a reaction kettle, heating to 160 ℃ for reaction for 15-25h, removing the solvent and grinding into fine powder to prepare the SnS2-g-C3N4A heterojunction photocatalytic degradation material.
7. An SnS according to claim 62-g-C3N4The heterojunction photocatalytic degradation material is characterized in that: the mass ratio of the carbon nano tube, the hexadecyl trimethyl ammonium bromide, the thioglycolic acid and the stannic chloride is 0.2-0.6:0.8-1.2:3.5-4: 1.
8. An SnS according to claim 62-g-C3N4The heterojunction photocatalytic degradation material is characterized in that: the SnS2Hollow microsphere modified carbon nanotube and honeycomb Ag-doped g-C3N4The mass ratio of (A) to (B) is 0.04-0.1: 1.
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CN113278948A (en) * 2021-04-16 2021-08-20 中国计量大学 Tin sulfide/tin disulfide heterojunction material and preparation method thereof
CN113333012A (en) * 2021-06-02 2021-09-03 成都理工大学 Bi-doped porous carbon nitrogen compound and preparation method thereof
CN114808009A (en) * 2021-11-18 2022-07-29 青岛科技大学 Preparation of N, O CO-regulated Ni/N doped porous carbon tube and CO thereof 2 Application of electroreduction

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Publication number Priority date Publication date Assignee Title
CN113278948A (en) * 2021-04-16 2021-08-20 中国计量大学 Tin sulfide/tin disulfide heterojunction material and preparation method thereof
CN113333012A (en) * 2021-06-02 2021-09-03 成都理工大学 Bi-doped porous carbon nitrogen compound and preparation method thereof
CN113333012B (en) * 2021-06-02 2022-08-19 成都理工大学 Bi-doped porous carbon nitrogen compound and preparation method thereof
CN114808009A (en) * 2021-11-18 2022-07-29 青岛科技大学 Preparation of N, O CO-regulated Ni/N doped porous carbon tube and CO thereof 2 Application of electroreduction
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