CN111450871A - Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material and the preparation method thereof - Google Patents
Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material and the preparation method thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910003119 ZnCo2O4 Inorganic materials 0.000 claims abstract description 39
- 239000011572 manganese Substances 0.000 claims abstract description 30
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 26
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 28
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- 238000001354 calcination Methods 0.000 claims description 23
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 16
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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 16
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 16
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- 238000001914 filtration Methods 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 12
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
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- 229910052797 bismuth Inorganic materials 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- B01J35/60—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to the technical field of photocatalysts and discloses Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material comprises the following formula raw materials and components: porous nano ZnCo2O4Modified carbon nanotube and Mn-doped porous g-C3N4. The Mn is doped with g-C3N4Loaded porous ZnCo2O4Mn doped porous g-C3N4Has ultra-high specific surface area, and the doping of manganese ions regulates g-C3N4Charge arrangements and electronic structures of, reducing charge inhibitionWidth of belt, porous nano ZnCo2O4Modified carbon nanotubes with Mn doped porous g-C3N4Composite, Mn-doped porous g-C3N4And porous nano ZnCo2O4A heterojunction structure is formed between the two, Mn is doped with g-C3N4Can trap ZnCo by delocalized pi bond2O4The carbon nano tube can be used as an electron acceptor to promote the migration of the photo-generated electrons to the carbon nano tube, accelerate the separation of the photo-generated electrons and the holes and ensure that Mn is doped with g-C3N4Loaded porous ZnCo2O4The photocatalytic material exhibits excellent photocatalytic degradation activity.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material and the method for producing the same.
Background
In recent years, the problem of water pollution in China is becoming more severe, pollutants mainly comprise inorganic pollutants and organic pollutants, wherein the pollutants such as phenol, tetracycline, methylene blue and the like have high toxicity and serious pollution degree to the water body environment, the existing treatment method for the organic pollutants mainly comprises a physical adsorption method, an oxidation reduction method and the like, photocatalytic degradation is a novel efficient pollutant degradation method, light is radiated on a photocatalytic material to generate photoproduction electrons and cavities, and the photoproduction electrons and the cavities further react with oxygen and water to obtain active oxygen radicals and hydroxyl radicals, so that the organic pollutants are degraded into non-toxic small molecules.
The existing photocatalytic degradation materials mainly comprise titanium dioxide, transition metal sulfides, bismuth-based compounds and the like, wherein graphite phase carbon nitride g-C3N4Has a narrow forbidden band width, has good optical activity under visible light, and has g-C3N4The preparation method is simple, cheap and easy to obtain, is a photocatalytic material with great development potential, but the g-C3N4Has a low specific surface area, a low utilization ratio of light energy, and g-C3N4The photoproduction electrons and holes are easy to recombine, and the g-C is greatly reduced3N4Photocatalytic activity of (1).
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Mn-doped g-C3N4The photocatalyst material of porous ZnCo2O4 and its preparation process solve the problem of g-C3N4The problem of low specific surface area of the catalyst is solved, and g-C is solved3N4The problem of recombination of the photo-generated electrons and holes is easy to occur.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material comprises the following raw materials and components: porous nano ZnCo2O4Modified carbon nanotube and Mn-doped porous g-C3N4The mass ratio of the two is 100: 5-30.
Preferably, the Mn is doped with g-C3N4Loaded porous ZnCo2O4The preparation method of the photocatalytic material comprises the following steps:
(1) adding distilled water solvent, carbon nano tube, ammonium fluoride and urea into a reaction bottle, adding zinc nitrate and cobalt nitrate after uniform ultrasonic dispersion, pouring the solution into a hydrothermal reaction kettle, heating to 140 ℃ for reaction for 5-10h, filtering the solution, washing a solid product with ethanol and distilled water, drying, placing the solid product in a muffle furnace, heating to 150 ℃ for heat preservation and calcination for 2-3h to prepare the porous nano ZnCo2O4And modifying the carbon nano tube.
(2) Placing melamine in an atmosphere furnace, in the nitrogen atmosphere, heating up at a rate of 30-40 ℃/min, carrying out heat preservation treatment at 400 ℃ of 350-plus-one temperature for 20-30min, reducing the heating up rate to 2-4 ℃/min, heating up to 550-plus-one temperature, carrying out heat preservation calcination for 3-4h, and calcining the product g-C3N4Grinding into fine powder, placing in ethanol solvent, performing ultrasonic dispersion treatment for 3-6h, adding concentrated sulfuric acid, placing in an oil bath, stirring at 30-40 deg.C for 12-24h at uniform speed, heating to 75-85 deg.C, pre-activating for 3-5h, pouring the solution into a hydrothermal reaction kettle, heating to 140 deg.C and 170 deg.C, reacting for 15-25h, washing the solid product with distilled water and ethanol until it is neutral, and drying to obtain porous g-C3N4。
(3) Adding glycol solvent and porous g-C into a reaction bottle3N4And manganese chloride, adding aqueous solution of hydrazine hydrate after uniform ultrasonic dispersion, uniformly stirring for 10-30min at 80-100 ℃, then slowly adding aqueous solution of sodium hydroxide, adjusting the pH value of the solution to 11, uniformly stirring for 30-60min, then standing and aging for 1-3h, filtering the solution, washing a solid product by using distilled water and ethanol until the solid product is neutral and dried to prepare the Mn-doped porous g-C3N4。
(4) Adding distilled water solvent and porous nano ZnCo into a reaction bottle2O4Modified carbon nanotubes and Mn doped porous g-C3N4Uniformly dispersing by ultrasonic wave, drying the solution in vacuum to remove the solvent to prepare Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material of (1).
Preferably, the mass ratio of the carbon nanotubes, the ammonium fluoride, the urea, the zinc nitrate and the cobalt nitrate in the step (1) is 20-60:35-45:150-160:100: 190-200.
Preferably, the concentration of the sulfuric acid in the ethanol solution in the step (2) is 0.1-0.2 mol/L.
Preferably, the porous g-C in said step (3)3N4The mass ratio of the manganese chloride to the hydrazine hydrate is 200:35-60: 120-200.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the Mn is doped with g-C3N4Loaded porous ZnCo2O4By treating with a hot solvent of sulfuric acid system to promote g-C3N4The surface adsorbs a large amount of hydrogen ions, and the g-C is enhanced3N4Hydrogen bonding forces between the grains, thereby reducing interplanar spacings, and a portion of g-C by protonation of hydrogen ions3N4Can be decomposed into soluble condensed triazine ring with low polymerization degree, thereby forming rich mesoporous structure and increasing g-C3N4The manganese ions are doped into g-C by the reduction of hydrazine hydrate3N4In the crystal of (A), manganese ion regulates g-C3N4The charge arrangement and the electronic structure reduce the forbidden band width, thereby obviously improving the g-C3N4The utilization rate of light energy.
The Mn is doped with g-C3N4Loaded porous ZnCo2O4The porous nano ZnCo is prepared by using ammonium fluoride and urea as template for guiding2O4Modifying the carbon nanotubes further with Mn doped porous g-C3N4Composite, Mn-doped porous g-C3N4And porous nano ZnCo2O4A heterojunction structure is formed between the two, Mn is doped with g-C3N4Can trap ZnCo by delocalized pi bond2O4Of (2) a lightThe carbon nano tube with excellent conductivity can be used as an electron acceptor, promotes the migration of photo-generated electrons to the carbon nano tube, accelerates the separation of the photo-generated electrons and holes, and enables Mn to be doped with g-C3N4Loaded porous ZnCo2O4The photocatalytic material exhibits excellent photocatalytic degradation activity.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material comprises the following raw materials and components: porous nano ZnCo2O4Modified carbon nanotube and Mn-doped porous g-C3N4The mass ratio of the two is 100: 5-30.
Mn doped g-C3N4Loaded porous ZnCo2O4The preparation method of the photocatalytic material comprises the following steps:
(1) adding a distilled water solvent, a carbon nano tube, ammonium fluoride and urea into a reaction bottle, adding zinc nitrate and cobalt nitrate after uniformly dispersing by ultrasonic, wherein the mass ratio of the zinc nitrate to the cobalt nitrate is 20-60:35-45:150-2O4And modifying the carbon nano tube.
(2) Placing melamine in an atmosphere furnace, in the nitrogen atmosphere, heating up at a rate of 30-40 ℃/min, carrying out heat preservation treatment at 400 ℃ of 350-plus-one temperature for 20-30min, reducing the heating up rate to 2-4 ℃/min, heating up to 550-plus-one temperature, carrying out heat preservation calcination for 3-4h, and calcining the product g-C3N4Grinding into fine powder, placing in ethanol solvent, performing ultrasonic dispersion treatment for 3-6h, adding concentrated sulfuric acid, controlling the mass concentration of sulfuric acid in the solution to be 0.1-0.2 mol/L, placing in an oil bath kettle, stirring at 30-40 deg.C for 12-24h at constant speed, heating to 75-85 deg.C, pre-activating for 3-5h, pouring the solution into a hydrothermal reaction kettle, heating to 140 deg.C and 170 deg.C, reacting for 15-25h, washing the solid product with distilled water and ethanolUntil neutral and dried to prepare porous g-C3N4。
(3) Adding glycol solvent and porous g-C into a reaction bottle3N4And manganese chloride, adding aqueous solution of hydrazine hydrate after uniform ultrasonic dispersion, wherein the porous g-C3N4Manganese chloride and hydrazine hydrate in the mass ratio of 200:35-60:120-200, stirring at 80-100 ℃ for 10-30min at a constant speed, slowly adding an aqueous solution of sodium hydroxide, adjusting the pH value of the solution to 11, stirring at a constant speed for 30-60min, standing and aging for 1-3h, filtering the solution, washing a solid product with distilled water and ethanol until the solid product is neutral and dried to prepare the Mn-doped porous g-C3N4。
(4) Adding distilled water solvent and porous nano ZnCo into a reaction bottle2O4Modified carbon nanotubes and Mn doped porous g-C3N4Uniformly dispersing by ultrasonic wave, drying the solution in vacuum to remove the solvent to prepare Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material of (1).
Example 1
(1) Adding distilled water solvent, carbon nano tube, ammonium fluoride and urea into a reaction bottle, adding zinc nitrate and cobalt nitrate after uniformly dispersing by ultrasonic, wherein the mass ratio of the zinc nitrate to the cobalt nitrate is 20:35:150:100:190, pouring the solution into a hydrothermal reaction kettle, heating to 120 ℃, reacting for 5 hours, filtering the solution, washing a solid product by using ethanol and distilled water, drying, putting the solid product into a muffle furnace, heating to 120 ℃, preserving heat and calcining for 2 hours to prepare the porous nano ZnCo2O4And modifying the carbon nano tube.
(2) Placing melamine in an atmosphere furnace, in the nitrogen atmosphere, heating at a rate of 30 ℃/min, carrying out heat preservation treatment at 350 ℃ for 20min, reducing the heating rate to 2 ℃/min, heating to 520 ℃, carrying out heat preservation calcination for 3h, and placing the calcination product g-C3N4Grinding into fine powder, placing in ethanol solvent, performing ultrasonic dispersion for 3h, adding concentrated sulfuric acid, controlling the concentration of sulfuric acid in the solution to be 0.1 mol/L, placing in an oil bath, stirring at 30 deg.C for 12h, heating to 75 deg.C, pre-activating for 3h, pouring the solution into a hydrothermal reaction kettle, heating to 140 deg.C, reacting for 15hWashing the solid product with distilled water and ethanol until neutral and drying to prepare porous g-C3N4。
(3) Adding glycol solvent and porous g-C into a reaction bottle3N4And manganese chloride, adding aqueous solution of hydrazine hydrate after uniform ultrasonic dispersion, wherein the porous g-C3N4Manganese chloride and hydrazine hydrate in a mass ratio of 200:35:120, stirring at a constant speed for 10min at 80 ℃, then slowly adding an aqueous solution of sodium hydroxide, adjusting the pH of the solution to 11, stirring at a constant speed for 30min, then standing and aging for 1h, filtering the solution, washing a solid product with distilled water and ethanol until the solid product is neutral and dried to prepare the Mn-doped porous g-C3N4。
(4) Adding distilled water solvent and porous nano ZnCo into a reaction bottle2O4Modified carbon nanotubes and Mn doped porous g-C3N4Uniformly dispersing the two components in a mass ratio of 100:5 by ultrasonic, and drying the solution in vacuum to remove the solvent to prepare the Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material 1 of (1).
Example 2
(1) Adding distilled water solvent, carbon nano tube, ammonium fluoride and urea into a reaction bottle, adding zinc nitrate and cobalt nitrate after uniformly dispersing by ultrasonic, wherein the mass ratio of the zinc nitrate to the cobalt nitrate is 30:38:152:100:193, pouring the solution into a hydrothermal reaction kettle, heating to 130 ℃, reacting for 10h, filtering the solution, washing a solid product with ethanol and distilled water, drying, putting the solid product into a muffle furnace, heating to 140 ℃, preserving heat and calcining for 3h to prepare the porous nano ZnCo2O4And modifying the carbon nano tube.
(2) Placing melamine in an atmosphere furnace, in the nitrogen atmosphere, heating at a rate of 40 ℃/min, carrying out heat preservation treatment at 350 ℃ for 30min, reducing the heating rate to 3 ℃/min, heating to 550 ℃, carrying out heat preservation calcination for 4h, and placing the calcination product g-C3N4Grinding into fine powder, placing in ethanol solvent, performing ultrasonic dispersion for 4h, adding concentrated sulfuric acid, controlling the concentration of sulfuric acid in the solution to be 0.15 mol/L, placing in oil bath pan, stirring at 40 deg.C for 18h at uniform speed, heating to 85 deg.C, pre-activating for 4h, and mixing the solutionPouring into a hydrothermal reaction kettle, heating to 170 ℃, reacting for 25h, washing the solid product with distilled water and ethanol until the solid product is neutral and dried to obtain porous g-C3N4。
(3) Adding glycol solvent and porous g-C into a reaction bottle3N4And manganese chloride, adding aqueous solution of hydrazine hydrate after uniform ultrasonic dispersion, wherein the porous g-C3N4Manganese chloride and hydrazine hydrate in the mass ratio of 200:40:140, stirring at 100 ℃ for 10min at a constant speed, slowly adding an aqueous solution of sodium hydroxide, adjusting the pH of the solution to 11, stirring at a constant speed for 45min, standing and aging for 2h, filtering the solution, washing a solid product with distilled water and ethanol until the solid product is neutral and dried to prepare the Mn-doped porous g-C3N4。
(4) Adding distilled water solvent and porous nano ZnCo into a reaction bottle2O4Modified carbon nanotubes and Mn doped porous g-C3N4Uniformly dispersing the two components in a mass ratio of 100:10 by ultrasonic, and drying the solution in vacuum to remove the solvent to prepare the Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material 2.
Example 3
(1) Adding distilled water solvent, carbon nano tube, ammonium fluoride and urea into a reaction bottle, adding zinc nitrate and cobalt nitrate after uniformly dispersing by ultrasonic, wherein the mass ratio of the zinc nitrate to the cobalt nitrate is 45:40:156:100:197, pouring the solution into a hydrothermal reaction kettle, heating to 130 ℃, reacting for 8 hours, filtering the solution, washing a solid product with ethanol and distilled water, drying, placing in a muffle furnace, heating to 140 ℃, preserving heat and calcining for 2.5 hours to obtain the porous nano ZnCo2O4And modifying the carbon nano tube.
(2) Placing melamine in an atmosphere furnace, in the nitrogen atmosphere, heating at a rate of 35 ℃/min, carrying out heat preservation treatment at 380 ℃ for 25min, reducing the heating rate to 3 ℃/min, heating to 530 ℃, carrying out heat preservation calcination for 3.5h, and placing the calcination product g-C3N4Grinding into fine powder, placing in ethanol solvent, performing ultrasonic dispersion treatment for 4 hr, adding concentrated sulfuric acid, controlling the concentration of sulfuric acid in the solution to be 0.16 mol/L, placing in oil bath pan at 35 deg.CStirring at uniform speed for 18h, heating to 80 deg.C, preactivating for 4h, pouring the solution into hydrothermal reaction kettle, heating to 160 deg.C, reacting for 20h, washing solid product with distilled water and ethanol until neutral, and drying to obtain porous g-C3N4。
(3) Adding glycol solvent and porous g-C into a reaction bottle3N4And manganese chloride, adding aqueous solution of hydrazine hydrate after uniform ultrasonic dispersion, wherein the porous g-C3N4Manganese chloride and hydrazine hydrate in a mass ratio of 200:50:180, stirring at a constant speed for 20min at 90 ℃, then slowly adding an aqueous solution of sodium hydroxide, adjusting the pH of the solution to 11, stirring at a constant speed for 50min, then standing and aging for 2h, filtering the solution, washing a solid product with distilled water and ethanol until the solid product is neutral and dried to prepare the Mn-doped porous g-C3N4。
(4) Adding distilled water solvent and porous nano ZnCo into a reaction bottle2O4Modified carbon nanotubes and Mn doped porous g-C3N4Uniformly dispersing the two components in a mass ratio of 100:20 by ultrasonic, and drying the solution in vacuum to remove the solvent to prepare the Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material 3.
Example 4
(1) Adding distilled water solvent, carbon nano tube, ammonium fluoride and urea into a reaction bottle, adding zinc nitrate and cobalt nitrate after uniformly dispersing by ultrasonic, wherein the mass ratio of the zinc nitrate to the cobalt nitrate is 60:45:160:100:200, pouring the solution into a hydrothermal reaction kettle, heating to 140 ℃, reacting for 10 hours, filtering the solution, washing a solid product by using ethanol and distilled water, drying, putting the solid product into a muffle furnace, heating to 150 ℃, preserving heat and calcining for 3 hours to prepare the porous nano ZnCo2O4And modifying the carbon nano tube.
(2) Placing melamine in an atmosphere furnace, in the nitrogen atmosphere, heating at a rate of 40 ℃/min, carrying out heat preservation treatment at 400 ℃ for 30min, reducing the heating rate to 4 ℃/min, heating to 550 ℃, carrying out heat preservation calcination for 4h, and placing the calcination product g-C3N4Grinding into fine powder, placing in ethanol solvent, ultrasonic dispersing for 6 hr, adding concentrated sulfuric acid, and controlling sulfuric acid content in the solutionThe amount concentration of 0.2 mol/L, placing in an oil bath, stirring at constant speed for 24h at 40 ℃, heating to 85 ℃, pre-activating for 5h, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃, reacting for 25h, washing the solid product with distilled water and ethanol until the solid product is neutral and dried to obtain the porous g-C3N4。
(3) Adding glycol solvent and porous g-C into a reaction bottle3N4And manganese chloride, adding aqueous solution of hydrazine hydrate after uniform ultrasonic dispersion, wherein the porous g-C3N4Manganese chloride and hydrazine hydrate in a mass ratio of 200:60:200, stirring at a constant speed for 30min at 100 ℃, then slowly adding an aqueous solution of sodium hydroxide, adjusting the pH of the solution to 11, stirring at a constant speed for 60min, then standing and aging for 3h, filtering the solution, washing a solid product with distilled water and ethanol until the solid product is neutral and dried to prepare the Mn-doped porous g-C3N4。
(4) Adding distilled water solvent and porous nano ZnCo into a reaction bottle2O4Modified carbon nanotubes and Mn doped porous g-C3N4Uniformly dispersing the two components in a mass ratio of 100:30 by ultrasonic, and drying the solution in vacuum to remove the solvent to prepare the Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material 4.
Comparative example 1
(1) Adding distilled water solvent, carbon nano tube, ammonium fluoride and urea into a reaction bottle, adding zinc nitrate and cobalt nitrate after uniformly dispersing by ultrasonic, wherein the mass ratio of the zinc nitrate to the cobalt nitrate is 12:30:145:100:180, pouring the solution into a hydrothermal reaction kettle, heating to 140 ℃, reacting for 5h, filtering the solution, washing a solid product with ethanol and distilled water, drying, placing in a muffle furnace, heating to 150 ℃, preserving heat and calcining for 1h to prepare the porous nano ZnCo2O4And modifying the carbon nano tube.
(2) Placing melamine in an atmosphere furnace, in the nitrogen atmosphere, heating at a rate of 35 ℃/min, carrying out heat preservation treatment at 380 ℃ for 30min, reducing the heating rate to 10 ℃/min, heating to 550 ℃, carrying out heat preservation calcination for 4h, and placing the calcination product g-C3N4Grinding into fine powder, adding into ethanol solvent, and ultrasonic dispersing4h, adding concentrated sulfuric acid, controlling the mass concentration of sulfuric acid in the solution to be 0.05 mol/L, placing the solution in an oil bath kettle, stirring at a constant speed for 20h at 40 ℃, heating to 75 ℃, pre-activating for 5h, pouring the solution into a hydrothermal reaction kettle, heating to 150 ℃, reacting for 25h, washing a solid product by using distilled water and ethanol until the solid product is neutral and dried, and preparing the porous g-C3N4。
(3) Adding glycol solvent and porous g-C into a reaction bottle3N4And manganese chloride, adding aqueous solution of hydrazine hydrate after uniform ultrasonic dispersion, wherein the porous g-C3N4Manganese chloride and hydrazine hydrate in a mass ratio of 200:25:220, stirring at a constant speed for 30min at 100 ℃, then slowly adding an aqueous solution of sodium hydroxide, adjusting the pH of the solution to 11, stirring at a constant speed for 60min, then standing and aging for 3h, filtering the solution, washing a solid product with distilled water and ethanol until the solid product is neutral and dried to prepare the Mn-doped porous g-C3N4。
(4) Adding distilled water solvent and porous nano ZnCo into a reaction bottle2O4Modified carbon nanotubes and Mn doped porous g-C3N4Uniformly dispersing the two components in a mass ratio of 100:2 by ultrasonic, and drying the solution in vacuum to remove the solvent to prepare Mn-doped g-C3N4Loaded porous ZnCo2O4Photocatalytic comparative material 1.
Adding a methylene blue solution with the mass fraction of 2% into a reaction bottle, and adding Mn doped g-C in each of the examples and the comparative examples3N4Loaded porous ZnCo2O4The photocatalytic material is irradiated for 6 hours under a 300W xenon lamp with the mass fraction of 5%, a 760CRT double-beam ultraviolet-visible spectrophotometer is used for detecting the absorbance and the residual concentration of methylene blue, and the degradation rate is calculated, wherein the test standard is GB/T23762-.
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Degradation Rate (%) | 94.8 | 98.9 | 97.2 | 98.6 | 65.9 |
In summary, the Mn is doped with g-C3N4Loaded porous ZnCo2O4By treating with a hot solvent of sulfuric acid system to promote g-C3N4The surface adsorbs a large amount of hydrogen ions, and the g-C is enhanced3N4Hydrogen bonding forces between the grains, thereby reducing interplanar spacings, and a portion of g-C by protonation of hydrogen ions3N4Can be decomposed into soluble condensed triazine ring with low polymerization degree, thereby forming rich mesoporous structure and increasing g-C3N4The manganese ions are doped into g-C by the reduction of hydrazine hydrate3N4In the crystal of (A), manganese ion regulates g-C3N4The charge arrangement and the electronic structure reduce the forbidden band width, thereby obviously improving the g-C3N4The utilization rate of light energy.
The porous nano ZnCo is prepared by using ammonium fluoride and urea as template guide2O4Modifying the carbon nanotubes further with Mn doped porous g-C3N4Composite, Mn-doped porous g-C3N4And porous nano ZnCo2O4A heterojunction structure is formed between the two, Mn is doped with g-C3N4Can trap ZnCo by delocalized pi bond2O4The carbon nano tube with excellent conductivity can be used as an electron acceptor, promotes the migration of photo-generated electrons to the carbon nano tube, accelerates the separation of the photo-generated electrons and holes, and enables Mn to be doped with g-C3N4Loaded porous ZnCo2O4The photocatalytic material exhibits excellent photocatalytic degradation activity.
Claims (5)
1. Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material comprises the following raw materials and components, and is characterized in that: porous nano ZnCo2O4Modified carbon nanotube and Mn-doped porous g-C3N4The mass ratio of the two is 100: 5-30.
2. An Mn doped g-C according to claim 13N4Loaded porous ZnCo2O4The photocatalytic material of (1), characterized in that: the Mn is doped with g-C3N4Loaded porous ZnCo2O4The preparation method of the photocatalytic material comprises the following steps:
(1) adding distilled water solvent, carbon nano tube, ammonium fluoride and urea into a reaction bottle, adding zinc nitrate and cobalt nitrate after uniform ultrasonic dispersion, pouring the solution into a hydrothermal reaction kettle, heating to 140 ℃ for reaction for 5-10h, filtering the solution, washing a solid product with ethanol and distilled water, drying, placing the solid product in a muffle furnace, heating to 150 ℃ for heat preservation and calcination for 2-3h to prepare the porous nano ZnCo2O4Modifying the carbon nano tube;
(2) placing melamine in an atmosphere furnace, in the nitrogen atmosphere, heating up at a rate of 30-40 ℃/min, carrying out heat preservation treatment at 400 ℃ of 350-plus-one temperature for 20-30min, reducing the heating up rate to 2-4 ℃/min, heating up to 550-plus-one temperature, carrying out heat preservation calcination for 3-4h, and calcining the product g-C3N4Grinding into fine powder, dissolving in ethanolIn the agent, ultrasonic dispersion treatment is carried out for 3-6h, concentrated sulfuric acid is added, the mixture is placed in an oil bath pot, the mixture is stirred at a constant speed for 12-24h at the temperature of 30-40 ℃, the temperature is raised to 75-85 ℃, pre-activation is carried out for 3-5h, the solution is poured into a hydrothermal reaction kettle, the mixture is heated to 140 ℃ and 170 ℃, reaction is carried out for 15-25h, distilled water and ethanol are used for washing a solid product until the solid product is neutral and dried, and porous g-C is prepared3N4；
(3) Adding glycol solvent and porous g-C into a reaction bottle3N4And manganese chloride, adding aqueous solution of hydrazine hydrate after uniform ultrasonic dispersion, uniformly stirring for 10-30min at 80-100 ℃, then slowly adding aqueous solution of sodium hydroxide, adjusting the pH value of the solution to 11, uniformly stirring for 30-60min, then standing and aging for 1-3h, filtering the solution, washing a solid product by using distilled water and ethanol until the solid product is neutral and dried to prepare the Mn-doped porous g-C3N4；
(4) Adding distilled water solvent and porous nano ZnCo into a reaction bottle2O4Modified carbon nanotubes and Mn doped porous g-C3N4Uniformly dispersing by ultrasonic wave, drying the solution in vacuum to remove the solvent to prepare Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material of (1).
3. An Mn doped g-C according to claim 23N4Loaded porous ZnCo2O4The photocatalytic material of (1), characterized in that: the mass ratio of the carbon nano tube, the ammonium fluoride, the urea, the zinc nitrate and the cobalt nitrate in the step (1) is 20-60:35-45:150-160:100: 190-200.
4. An Mn doped g-C according to claim 23N4Loaded porous ZnCo2O4The photocatalytic material of (2) is characterized in that the mass concentration of the sulfuric acid in the ethanol solution in the step (2) is 0.1-0.2 mol/L.
5. An Mn doped g-C according to claim 23N4Loaded porous ZnCo2O4Of a photocatalytic materialThe method is characterized in that: porous g-C in the step (3)3N4The mass ratio of the manganese chloride to the hydrazine hydrate is 200:35-60: 120-200.
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