CN111701615A - Pr (Pr) powder3+Doping with Bi2MoO6-g-C3N4Heterojunction photocatalytic degradation material and preparation method thereof - Google Patents
Pr (Pr) powder3+Doping with Bi2MoO6-g-C3N4Heterojunction photocatalytic degradation material and preparation method thereof Download PDFInfo
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- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000002135 nanosheet Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 32
- 239000008103 glucose Substances 0.000 claims abstract description 32
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims abstract description 29
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 20
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 20
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000004005 microsphere Substances 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
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- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 229960000583 acetic acid Drugs 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000012362 glacial acetic acid Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000012265 solid product Substances 0.000 claims description 12
- 238000010257 thawing Methods 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims 3
- 230000008014 freezing Effects 0.000 claims 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 8
- 239000004098 Tetracycline Substances 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 229960002180 tetracycline Drugs 0.000 abstract description 6
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- 235000019364 tetracycline Nutrition 0.000 abstract description 6
- 150000003522 tetracyclines Chemical class 0.000 abstract description 6
- -1 oxygen anion Chemical class 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
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- 230000004043 responsiveness Effects 0.000 abstract description 3
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- 241000219094 Vitaceae Species 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
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- 239000000203 mixture Substances 0.000 description 28
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- 238000007664 blowing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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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
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Abstract
The invention relates to the technical field of photocatalytic degradation and discloses a Pr catalyst3+Doping with Bi2MoO6‑g‑C3N4The photocatalytic degradation material for the heterojunction comprises the following formula raw materials and components: three-dimensional porous g-C3N4Nano-sheets, polyvinylpyrrolidone, glucose, bismuth nitrate, sodium molybdate and praseodymium nitrate. Porous g-C3N4The nano-sheet has ultra-high specific surface area, can improve the responsiveness and the utilization rate to light energy, and is porous g-C3N4The nano-sheet is used as a substrate, and polyvinylpyrrolidone and grapes are added into a surfactantPreparing porous Pr in the system with carbon nanometer ball as template produced with sugar water3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, Pr3+Doping with Bi2MoO6And g-C3N4Forming a Z-type heterojunction, Pr when light is radiated at the Z-type heterojunction3+Doping with Bi2MoO6Hole sum g-C in the valence band3N4The photo-generated electrons on the conduction band can rapidly react with oxygen and water, and the generated oxygen anion free radicals and hydroxyl free radicals rapidly degrade organic pollutants such as tetracycline.
Description
Technical Field
The invention relates to the technical field of photocatalytic degradation, in particular to Pr3+Doping with Bi2MoO6-g-C3N4A photocatalytic degradation material of heterojunction and its preparation method are provided.
Background
Water pollution, noise pollution, air pollution and solid waste pollution are four pollution problems in the contemporary society, the pollution-free problem form of China is severe, the pollutants mainly comprise inorganic pollutants and organic pollutants, the organic pollutants such as phenol, methylene blue, tetracycline and the like, the pollution degree is large, the degradation is difficult, and the existing treatment methods for the organic pollutants mainly comprise a physical adsorption method, an oxidation-reduction method and the like.
The photocatalytic degradation is a new high-efficiency organic pollutant degradation method, and utilizes the light radiation and free radical with strong activity produced by photocatalyst in the reaction system, and utilizes the processes of addition, substitution and electron transfer between free radical and organic pollutant to degrade the pollutant into inorganic substance, and the existent photocatalytic degradation material mainly contains titanium dioxide, transition metal sulfide and bismuthate, etc. and graphite phase carbon nitride g-C3N4Has moderate band gap and good optical activity under visible light, is a photocatalytic degradation material with wide application, but 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 degradation activity of (1) g-C3N4And transition metal sulfide, bismuthate and the like with suitable band gaps form a heterojunction structure, so that the recombination of photogenerated electrons and holes can be effectively reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a Pr3+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of heterojunction and its preparation method solve the problem of common g-C3N4Is not high, and the photogenerated electrons and holes are easily recombined.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: pr (Pr) powder3+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction is characterized in that: comprises the following raw materials and components, three-dimensional porous g-C3N4Nano-sheets, polyvinylpyrrolidone, glucose, bismuth nitrate, sodium molybdate and praseodymium nitrate, wherein the mass ratio of the bismuth nitrate to the sodium molybdate to the praseodymium nitrate to the glucose is 97-99.5:50:0.5-3:120-3N4The mass ratio of the nano-sheets, the polyvinylpyrrolidone and the glucose is 150-300:100: 10-15.
Preferably, the Pr is3+Doping with Bi2MoO6-g-C3N4The preparation method of the heterojunction photocatalytic degradation material comprises the following steps:
(1) adding distilled water solvent, melamine and nano SiO into a reaction bottle2Uniformly dispersing by ultrasonic wave, placing in an oil bath, heating to 75-85 deg.C, stirring at constant speed until the solvent is evaporated to dryness, fully grinding the mixed product, placing in a resistance furnace, heating to 530-2Template, filtering, washing to neutrality, ultrasonic peeling the solid product, cooling and thawing in a freeze drier to obtain three-dimensional porous g-C3N4Nanosheets.
(2) Adding a mixed solvent of distilled water and ethanol and three-dimensional porous g-C into a reaction bottle3N4Uniformly dispersing nanosheets, polyvinylpyrrolidone and glucose by ultrasonic, uniformly stirring at room temperature for 2-4h, adding bismuth nitrate, sodium molybdate, praseodymium nitrate and glacial acetic acid, uniformly stirring for 12-24h, pouring the solution into a polymerization reaction kettle, placing the polymerization reaction kettle in a reaction kettle heating box, heating to 190 ℃ at 170 ℃, reacting for 6-12h, filtering the solution to remove the solvent, washing the precipitated product by using distilled water and ethanol, drying, calcining in nitrogen atmosphere to remove a carbon sphere template, and preparing to obtain Pr3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, as Pr3+Doping with Bi2MoO6-g-C3N4A photocatalytic degradation material of a heterojunction.
Preferably, the nano SiO in the step (1)2Has an average particle diameter of 10-50nm and a mass ratio of 1:2-6 to melamine.
Preferably, the freeze-thaw treatment in the step (1) is freeze-drying at-25 to-45 ℃ for 8 to 12 hours, thawing at room temperature, freeze-drying at-25 to-45 ℃ for 4 to 6 hours, thawing at room temperature, freeze-drying at-25 to-45 ℃ for 1 to 3 hours, and thawing at room temperature.
Preferably, the volume ratio of the distilled water, the ethanol and the glacial acetic acid in the step (2) is 40-50:10:6-10, and the mass fraction of the glucose in the total solution is controlled to be 0.3-0.4%.
Preferably, the reation kettle heating cabinet in step (2) includes the air-blast heater, and air-blast heater swing joint has the air-blast fan piece, reation kettle heating bottom of the case portion fixedly connected with rotary device, and rotary device swing joint has the rotation axis, rotation axis upper end fixedly connected with base, and the base top is provided with polymerization kettle, base top fixedly connected with bracing piece, bracing piece swing joint has the governing valve, governing valve fixedly connected with carriage release lever, carriage release lever fixedly connected with annular cardboard.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the Pr3+Doping with Bi2MoO6-g-C3N4Heterojunction photocatalytic degradation material, regulation and control template agent nanometer SiO2The prepared porous g-C with rich nano-aperture3N4Then the porous g-C is prepared by ultrasonic stripping and freeze drying treatment3N4Nanosheets, comparable to ordinary g-C3N4Porous g-C3N4The nano-sheet has an ultra-high specific surface area, and can improve the responsiveness and the utilization rate to light energy.
The Pr3+Doping with Bi2MoO6-g-C3N4Photocatalytic degradation material of heterojunction with porous g-C3N4The nano sheet is taken as a substrate, and porous Pr is prepared in a system with a carbon nano sphere generated by hydrothermal reaction of surfactant polyvinylpyrrolidone and glucose as a template3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, Pr3+Substituted part of Bi3+Forms a new donor level, reduces the energy band gap, and enables Pr3+Doping with Bi2MoO6The light absorption edge of the film generates red shift, the visible light absorption waveband is widened, and meanwhile, the film is Pr3+Doping with Bi2MoO6And g-C3N4Forming a Z-type heterojunction when light is radiated at Pr3+Doping with Bi2MoO6And g-C3N4When in the heterojunction, Pr3+Doping with Bi2MoO6And g-C3N4Both the conduction and valence bands of (2) generate photogenerated electrons and holes, but Pr3 +Doping with Bi2MoO6Valence band ratio of g to C3N4Correction of valence band, g-C3N4Conduction band ratio Pr of3+Doping with Bi2MoO6The conduction band of (2) is more negative, so that Pr is3+Doping with Bi2MoO6Electron transition to g-C in the conduction band of3N4And recombines with the hole on its valence band to make Pr3+Doping with Bi2MoO6Hole sum g-C in the valence band3N4The photo-generated electrons on the conduction band can rapidly react with oxygen and water to generate a large amount of oxygen anion free radicals and hydroxyl free radicals with strong activity, organic pollutants such as tetracycline and the like are rapidly degraded, and a high-efficiency photocatalytic degradation process is realized through a Z-type heterojunction carrier transmission mechanism.
Drawings
FIG. 1 is a schematic front view of a reactor heating box;
FIG. 2 is a schematic view of the adjustment of the ring clamp;
FIG. 3 is a schematic top view of a polymerization reactor.
1-a reaction kettle heating box; 2-a blast heater; 3-blast fan sheet; 4-a rotating device; 5-a rotating shaft; 6-a base; 7-a polymerization reaction kettle; 8-a support bar; 9-adjusting valve; 10-a moving bar; 11-ring catch plate.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: pr (Pr) powder3+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction is characterized in that: comprises the following raw materials and components, three-dimensional porous g-C3N4Nano-sheets, polyvinylpyrrolidone, glucose, bismuth nitrate, sodium molybdate and praseodymium nitrate, wherein the mass ratio of the bismuth nitrate to the sodium molybdate to the praseodymium nitrate to the glucose is 97-99.5:50:0.5-3:120-3N4The mass ratio of the nano-sheets, the polyvinylpyrrolidone and the glucose is 150-300:100: 10-15.
Pr3+Doping with Bi2MoO6-g-C3N4The preparation method of the heterojunction photocatalytic degradation material comprises the following steps:
(1) adding distilled water solvent, melamine and nano SiO with average grain diameter of 10-50nm into a reaction bottle2The mass ratio of the two is 2-6:1, the mixture is placed in an oil bath pot after being dispersed evenly by ultrasonic, the mixture is heated to 75-85 ℃, the mixture is stirred at a constant speed until the solvent is evaporated to dryness, the mixture is fully ground and then placed in a resistance furnace, the temperature is raised to 530 ℃ and 560 ℃, the mixture is calcined for 3-5h, the calcined product is placed in hydrofluoric acid solution, the mixture is stirred at a constant speed for 20-30h after being dispersed evenly by ultrasonic, and the nano SiO is removed by etching2Filtering, washing to neutrality, ultrasonically stripping solid product, cooling and thawing in a freeze drier at-25 deg.c to-45 deg.c for 8-12 hr, thawing at room temperature, freeze drying at-25 deg.c to-45 deg.c for 4-6 hr, thawing at room temperature, freeze drying at-25 deg.c to-45 deg.c for 1-3 hr, thawing at room temperature to obtain three-dimensional porous g-C3N4Nanosheets.
(2) Adding a mixed solvent of distilled water and ethanol and three-dimensional porous g-C into a reaction bottle3N4Uniformly dispersing the nanosheets, polyvinylpyrrolidone and glucose by ultrasonic, uniformly stirring at room temperature for 2-4h, adding bismuth nitrate, sodium molybdate, praseodymium nitrate and glacial acetic acid, and controlling distilled water, ethanol and glacial ethyl acetateThe volume ratio of the acid is 40-50:10:6-10, the mass fraction of the glucose in the total solution is controlled to be 0.3-0.4%, the solution is stirred at a constant speed for 12-24h, the solution is poured into a polymerization reaction kettle and placed in a reaction kettle heating box, the reaction kettle heating box comprises an air blowing heating machine, the air blowing heating machine is movably connected with an air blowing fan sheet, the bottom of the reaction kettle heating box is fixedly connected with a rotating device, the rotating device is movably connected with a rotating shaft, the upper end of the rotating shaft is fixedly connected with a base, the polymerization reaction kettle is arranged above the base, a supporting rod is fixedly connected above the base, the supporting rod is movably connected with an adjusting valve, the adjusting valve is fixedly connected with a moving rod, the moving rod is fixedly connected with an annular clamping plate, the temperature is 190 ℃ when the solution is heated to 170 ℃, calcining in nitrogen atmosphere to remove the carbon sphere template to prepare the Pr3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, as Pr3+Doping with Bi2MoO6-g-C3N4A photocatalytic degradation material of a heterojunction.
Example 1
(1) Adding distilled water solvent, melamine and SiO with average particle diameter of 50nm into a reaction bottle2The mass ratio of the two is 2:1, the mixture is placed in an oil bath pot after being dispersed evenly by ultrasonic waves, the mixture is heated to 75 ℃, the mixture is stirred at a constant speed until the solvent is evaporated to dryness, the mixed product is fully ground and then placed in a resistance furnace, the temperature is raised to 530 ℃, the mixture is calcined for 3 hours, the calcined product is placed in hydrofluoric acid solution, the mixture is stirred at a constant speed for 20 hours after being dispersed evenly by ultrasonic waves, and the nano SiO is removed by etching2Filtering and washing a template to be neutral, ultrasonically stripping a solid product, placing the solid product in a freeze dryer, performing cooling-unfreezing treatment, performing freeze drying at the temperature of minus 25 ℃ for 8 hours, unfreezing at room temperature, performing freeze drying at the temperature of minus 25 ℃ for 4 hours, unfreezing at room temperature, performing freeze drying at the temperature of minus 25 ℃ for 1 hour, and unfreezing at room temperature to prepare the three-dimensional porous g-C3N4Nanosheets.
(2) Adding a mixed solvent of distilled water and ethanol and three-dimensional porous g-C into a reaction bottle3N4Dispersing nanosheets, polyvinylpyrrolidone and glucose uniformly by ultrasonic, and then carrying out ultrasonic dispersion at room temperatureStirring at a constant speed for 2 hours, adding bismuth nitrate, sodium molybdate, praseodymium nitrate and glacial acetic acid, controlling the volume ratio of distilled water, ethanol and glacial acetic acid to be 40:10:6, controlling the mass fraction of glucose in the total solution to be 0.3%, controlling the mass ratio of bismuth nitrate, sodium molybdate, praseodymium nitrate and glucose to be 99.5:50:0.5:120, and controlling the three-dimensional porous g-C3N4Stirring at a constant speed for 12 hours, pouring the solution into a polymerization reaction kettle, placing the solution into a reaction kettle heating box, wherein the reaction kettle heating box comprises a blast heater, the blast heater is movably connected with a blast fan, the bottom of the reaction kettle heating box is fixedly connected with a rotating device, the rotating device is movably connected with a rotating shaft, the upper end of the rotating shaft is fixedly connected with a base, the polymerization reaction kettle is arranged above the base, a supporting rod is fixedly connected above the base, the supporting rod is movably connected with an adjusting valve, the adjusting valve is fixedly connected with a moving rod, the moving rod is fixedly connected with an annular clamping plate, heating is carried out to 170 ℃, reacting for 6 hours, filtering the solution to remove a solvent, washing and drying a precipitation product by using distilled water and ethanol, calcining in a nitrogen atmosphere to remove a carbon sphere template, and preparing the Pr-containing graphene3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, as Pr3+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction 1.
Example 2
(1) Adding distilled water solvent, melamine and SiO with average particle diameter of 30nm into a reaction bottle2The mass ratio of the two is 3:1, the mixture is placed in an oil bath pot after being dispersed uniformly by ultrasonic waves, the mixture is heated to 85 ℃, the mixture is stirred at a constant speed until the solvent is evaporated to dryness, the mixed product is fully ground and placed in a resistance furnace, the temperature is raised to 550 ℃, the mixture is calcined for 5 hours, the calcined product is placed in hydrofluoric acid solution, the mixture is stirred at a constant speed for 30 hours after being dispersed uniformly by ultrasonic waves, and the nano SiO is removed by etching2Filtering template, washing to neutrality, ultrasonic peeling solid product, freeze drying at-35 deg.C for 12 hr, thawing at room temperature, freeze drying at-35 deg.C for 6 hr, thawing at room temperature, and freeze drying at-35 deg.C for 1 hrThawing at room temperature to prepare three-dimensional porous g-C3N4Nanosheets.
(2) Adding a mixed solvent of distilled water and ethanol and three-dimensional porous g-C into a reaction bottle3N4Uniformly dispersing nanosheets, polyvinylpyrrolidone and glucose by ultrasonic, uniformly stirring at room temperature for 4 hours, adding bismuth nitrate, sodium molybdate, praseodymium nitrate and glacial acetic acid, controlling the volume ratio of distilled water to ethanol to glacial acetic acid to be 44:10:7, controlling the mass fraction of glucose in the total solution to be 0.33%, controlling the mass ratio of the bismuth nitrate to the sodium molybdate to the praseodymium nitrate to be 99:50:1:140, and controlling the three-dimensional porous g-C3N4Stirring at a constant speed for 18 hours, pouring the solution into a polymerization reaction kettle, placing the solution into a reaction kettle heating box, wherein the reaction kettle heating box comprises a blast heater, the blast heater is movably connected with a blast fan, the bottom of the reaction kettle heating box is fixedly connected with a rotating device, the rotating device is movably connected with a rotating shaft, the upper end of the rotating shaft is fixedly connected with a base, the polymerization reaction kettle is arranged above the base, a supporting rod is fixedly connected above the base, the supporting rod is movably connected with an adjusting valve, the adjusting valve is fixedly connected with a moving rod, the moving rod is fixedly connected with an annular clamping plate, heating is carried out to 180 ℃, reacting for 12 hours, filtering the solution to remove a solvent, washing and drying a precipitation product by using distilled water and ethanol, calcining in a nitrogen atmosphere to remove a carbon sphere template, and preparing the Pr-containing carbon3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, as Pr3+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation of the heterojunction material 2.
Example 3
(1) Adding distilled water solvent, melamine and SiO with average particle diameter of 30nm into a reaction bottle2The mass ratio of the two is 4.5:1, the mixture is placed in an oil bath pot after being dispersed evenly by ultrasonic, the mixture is heated to 80 ℃, stirred at a constant speed until the solvent is evaporated to dryness, the mixed product is fully ground and then placed in a resistance furnace, the temperature is raised to 540 ℃, the mixture is calcined for 4 hours, the calcined product is placed in hydrofluoric acid solution, and the mixture is dispersed evenly by ultrasonic and then is calcined evenlyStirring for 25h at a high speed, and etching to remove nano SiO2Filtering and washing a template to be neutral, ultrasonically stripping a solid product, placing the solid product in a freeze dryer, performing cooling-unfreezing treatment, performing freeze drying at the temperature of minus 30 ℃ for 10 hours, unfreezing at room temperature, performing freeze drying at the temperature of minus 30 ℃ for 5 hours, unfreezing at room temperature, performing freeze drying at the temperature of minus 30 ℃ for 2 hours, and unfreezing at room temperature to prepare the three-dimensional porous g-C3N4Nanosheets.
(2) Adding a mixed solvent of distilled water and ethanol and three-dimensional porous g-C into a reaction bottle3N4Uniformly dispersing nanosheets, polyvinylpyrrolidone and glucose by ultrasonic, uniformly stirring at room temperature for 3 hours, adding bismuth nitrate, sodium molybdate, praseodymium nitrate and glacial acetic acid, controlling the volume ratio of distilled water, ethanol and glacial acetic acid to be 47:10:8.5, controlling the mass fraction of glucose in the total solution to be 0.38%, controlling the mass ratio of the bismuth nitrate, the sodium molybdate, the praseodymium nitrate and the glucose to be 98:50:2:160, and controlling the three-dimensional porous g-C3N4Stirring at a constant speed for 18 hours, pouring the solution into a polymerization reaction kettle, placing the solution into a reaction kettle heating box, wherein the reaction kettle heating box comprises a blast heater, the blast heater is movably connected with a blast fan, the bottom of the reaction kettle heating box is fixedly connected with a rotating device, the rotating device is movably connected with a rotating shaft, the upper end of the rotating shaft is fixedly connected with a base, the polymerization reaction kettle is arranged above the base, a supporting rod is fixedly connected above the base, the supporting rod is movably connected with an adjusting valve, the adjusting valve is fixedly connected with a moving rod, the moving rod is fixedly connected with an annular clamping plate, heating is carried out to 180 ℃, reacting for 10 hours, filtering the solution to remove a solvent, washing and drying a precipitation product by using distilled water and ethanol, calcining in a nitrogen atmosphere to remove a carbon sphere template, and preparing the Pr-containing graphene3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, as Pr3+Doping with Bi2MoO6-g-C3N4The heterojunction photocatalytic degradation material 3.
Example 4
(1) Adding distilled water solvent, melamine and average into a reaction bottleThe grain diameter is 10nm nano SiO2Uniformly dispersing the two components in a mass ratio of 6:1 by ultrasonic, placing the mixture in an oil bath, heating the mixture to 85 ℃, uniformly stirring the mixture until the solvent is evaporated to dryness, fully grinding the mixed product, placing the mixed product in a resistance furnace, heating the mixed product to 560 ℃, calcining the mixed product for 5 hours, placing the calcined product in a hydrofluoric acid solution, uniformly stirring the mixed product for 30 hours after uniformly dispersing the mixed product by ultrasonic, and etching the mixed product to remove nano SiO2Filtering and washing a template to be neutral, ultrasonically stripping a solid product, placing the solid product in a freeze dryer, performing cooling-unfreezing treatment, performing freeze drying at the temperature of minus 45 ℃ for 12 hours, unfreezing at room temperature, performing freeze drying at the temperature of minus 45 ℃ for 6 hours, unfreezing at room temperature, performing freeze drying at the temperature of minus 45 ℃ for 1 to 3 hours, and unfreezing at room temperature to prepare the three-dimensional porous g-C3N4Nanosheets.
(2) Adding a mixed solvent of distilled water and ethanol and three-dimensional porous g-C into a reaction bottle3N4Uniformly dispersing nanosheets, polyvinylpyrrolidone and glucose by ultrasonic, uniformly stirring at room temperature for 4 hours, adding bismuth nitrate, sodium molybdate, praseodymium nitrate and glacial acetic acid, controlling the volume ratio of distilled water, ethanol and glacial acetic acid to be 50:10:10, controlling the mass fraction of glucose in the total solution to be 0.4%, controlling the mass ratio of the substances of bismuth nitrate, sodium molybdate, praseodymium nitrate and glucose to be 97:50:3:180, and controlling the three-dimensional porous g-C3N4Stirring at a constant speed for 24 hours, pouring the solution into a polymerization reaction kettle, placing the solution into a reaction kettle heating box, wherein the reaction kettle heating box comprises a blast heater, the blast heater is movably connected with a blast fan, the bottom of the reaction kettle heating box is fixedly connected with a rotating device, the rotating device is movably connected with a rotating shaft, the upper end of the rotating shaft is fixedly connected with a base, the polymerization reaction kettle is arranged above the base, a supporting rod is fixedly connected above the base, the supporting rod is movably connected with an adjusting valve, the adjusting valve is fixedly connected with a moving rod, the moving rod is fixedly connected with an annular clamping plate, heating is carried out to 190 ℃, reacting for 12 hours, filtering the solution to remove a solvent, washing and drying a precipitation product by using distilled water and ethanol, calcining in a nitrogen atmosphere to remove a carbon sphere template, and preparing the Pr (Pr)3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, as Pr3+Doping with Bi2MoO6-g-C3N4The heterojunction photocatalytic degradation material 4.
Comparative example 1
(1) Adding distilled water solvent, melamine and SiO with average particle diameter of 100nm into a reaction bottle2The mass ratio of the two is 1:1, the mixture is placed in an oil bath pot after being dispersed uniformly by ultrasonic waves, the mixture is heated to 85 ℃, the mixture is stirred at a constant speed until the solvent is evaporated to dryness, the mixed product is fully ground and placed in a resistance furnace, the temperature is raised to 530 ℃, the mixture is calcined for 4 hours, the calcined product is placed in hydrofluoric acid solution, the mixture is stirred at a constant speed for 20 hours after being dispersed uniformly by ultrasonic waves, and the nano SiO is removed by etching2Filtering and washing a template to be neutral, ultrasonically stripping a solid product, placing the solid product in a freeze dryer, performing cooling-unfreezing treatment, performing freeze drying at the temperature of-15 ℃ for 12 hours, unfreezing at room temperature, performing freeze drying at the temperature of-15 ℃ for 6 hours, unfreezing at room temperature, performing freeze drying at the temperature of-15 ℃ for 2 hours, and unfreezing at room temperature to prepare the three-dimensional porous g-C3N4Nanosheets.
(2) Adding a mixed solvent of distilled water and ethanol and three-dimensional porous g-C into a reaction bottle3N4Uniformly dispersing nanosheets, polyvinylpyrrolidone and glucose by ultrasonic, uniformly stirring at room temperature for 4 hours, adding bismuth nitrate, sodium molybdate, praseodymium nitrate and glacial acetic acid, controlling the volume ratio of distilled water to ethanol to glacial acetic acid to be 55:10:4, controlling the mass fraction of glucose in the total solution to be 0.25%, controlling the mass ratio of the bismuth nitrate to the sodium molybdate to the praseodymium nitrate to be 99.8:50:0.2:200, and controlling three-dimensional porous g-C3N4The mass ratio of the nanosheets to the polyvinylpyrrolidone to the glucose is 120:100:18, stirring is carried out at a constant speed for 24 hours, the solution is poured into a polymerization reaction kettle and is placed in a reaction kettle heating box, the reaction kettle heating box comprises a blast heater, the blast heater is movably connected with a blast fan, the bottom of the reaction kettle heating box is fixedly connected with a rotating device, the rotating device is movably connected with a rotating shaft, the upper end of the rotating shaft is fixedly connected with a base, the polymerization reaction kettle is arranged above the base, a supporting rod is fixedly connected above the base, the supporting rod is movably connected with an adjusting valve, and the adjusting valve is fixedlyThe method comprises the steps of heating an annular clamping plate fixedly connected with a moving rod to 180 ℃, reacting for 12 hours, filtering a solution to remove a solvent, washing a precipitate product by using distilled water and ethanol, drying, calcining in a nitrogen atmosphere to remove a carbon sphere template, and preparing to obtain the Pr3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, as Pr3+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction 1.
Pr in the examples and the comparative examples are respectively3+Doping with Bi2MoO6-g-C3N4The heterojunction photocatalytic degradation material is placed in a tetracycline solution with the mass fraction of 3%, the mass fraction of the photocatalytic degradation material is 1%, a 300W xenon lamp is used as a light source, the light source is irradiated for 6 hours, an ND5000 ultraviolet visible light spectrophotometer is used for testing the absorbance and the residual concentration of the tetracycline, the degradation rate is calculated, and the test standard is GB/T23762 one-wall 2009.
| Item | Residual concentration (%) | Degradation Rate (%) |
| Example 1 | 0.0216 | 97.84 |
| Example 2 | 0.0094 | 99.06 |
| Example 3 | 0.0035 | 99.65 |
| Example 4 | 0.0171 | 98.29 |
| Comparative example 1 | 0.3480 | 65.20 |
In summary, the Pr3+Doping with Bi2MoO6-g-C3N4Heterojunction photocatalytic degradation material, regulation and control template agent nanometer SiO2The prepared porous g-C with rich nano-aperture3N4Then the porous g-C is prepared by ultrasonic stripping and freeze drying treatment3N4Nanosheets, comparable to ordinary g-C3N4Porous g-C3N4The nano-sheet has an ultra-high specific surface area, and can improve the responsiveness and the utilization rate to light energy.
With multiple pores g-C3N4The nano sheet is taken as a substrate, and porous Pr is prepared in a system with a carbon nano sphere generated by hydrothermal reaction of surfactant polyvinylpyrrolidone and glucose as a template3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, Pr3+Substituted part of Bi3+Forms a new donor level, reduces the energy band gap, and enables Pr3+Doping with Bi2MoO6The light absorption edge of the film generates red shift, the visible light absorption waveband is widened, and meanwhile, the film is Pr3+Doping with Bi2MoO6And g-C3N4Forming a Z-type heterojunction when light is radiated at Pr3+Doping with Bi2MoO6And g-C3N4When in the heterojunction, Pr3+Doping with Bi2MoO6And g-C3N4Both the conduction band and the valence band of (A) generate photogenerated electrons and vacanciesPoints, however, Pr3+Doping with Bi2MoO6Valence band ratio of g to C3N4Correction of valence band, g-C3N4Conduction band ratio Pr of3+Doping with Bi2MoO6The conduction band of (2) is more negative, so that Pr is3+Doping with Bi2MoO6Electron transition to g-C in the conduction band of3N4And recombines with the hole on its valence band to make Pr3+Doping with Bi2MoO6Hole sum g-C in the valence band3N4The photo-generated electrons on the conduction band can rapidly react with oxygen and water to generate a large amount of oxygen anion free radicals and hydroxyl free radicals with strong activity, organic pollutants such as tetracycline and the like are rapidly degraded, and a high-efficiency photocatalytic degradation process is realized through a Z-type heterojunction carrier transmission mechanism.
Claims (6)
1. Pr (Pr) powder3+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction is characterized in that: comprises the following raw materials and components, three-dimensional porous g-C3N4Nano-sheets, polyvinylpyrrolidone, glucose, bismuth nitrate, sodium molybdate and praseodymium nitrate, wherein the mass ratio of the bismuth nitrate to the sodium molybdate to the praseodymium nitrate to the glucose is 97-99.5:50:0.5-3:120-3N4The mass ratio of the nano-sheets, the polyvinylpyrrolidone and the glucose is 150-300:100: 10-15.
2. A Pr according to claim 13+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction is characterized in that: the Pr3+Doping with Bi2MoO6-g-C3N4The preparation method of the heterojunction photocatalytic degradation material comprises the following steps:
(1) adding melamine and nano SiO into distilled water solvent2After ultrasonic dispersion is uniform, heating to 75-85 ℃, stirring until the solvent is evaporated to dryness, fully grinding the mixed product, placing the mixed product in a resistance furnace, heating to 530-In the process, stirring for 20-30h after ultrasonic dispersion is uniform, and etching to remove nano SiO2Template, filtering, washing to neutrality, ultrasonic peeling the solid product, cooling and thawing in a freeze drier to obtain three-dimensional porous g-C3N4Nanosheets;
(2) adding three-dimensional porous g-C into a mixed solvent of distilled water and ethanol3N4Uniformly dispersing nanosheets, polyvinylpyrrolidone and glucose by ultrasonic, stirring at room temperature for 2-4h, adding bismuth nitrate, sodium molybdate, praseodymium nitrate and glacial acetic acid, stirring for 12-24h, pouring the solution into a polymerization reaction kettle, placing the polymerization reaction kettle in a reaction kettle heating box, heating to 170-190 ℃, reacting for 6-12h, filtering, washing and drying, calcining in a nitrogen atmosphere to remove a carbon sphere template, and preparing to obtain Pr3+Doping with Bi2MoO6Hollow microsphere loaded porous g-C3N4Nanosheets, as Pr3+Doping with Bi2MoO6-g-C3N4A photocatalytic degradation material of a heterojunction.
3. A Pr according to claim 23+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction is characterized in that: the nano SiO in the step (1)2Has an average particle diameter of 10-50nm and a mass ratio of 1:2-6 to melamine.
4. A Pr according to claim 23+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction is characterized in that: the freezing-unfreezing treatment in the step (1) comprises the steps of freezing and drying for 8-12h at-25 to-45 ℃, unfreezing at room temperature, freezing and drying for 4-6h at-25 to-45 ℃, unfreezing at room temperature, freezing and drying for 1-3h at-25 to-45 ℃, and unfreezing at room temperature.
5. A Pr according to claim 23+Doping with Bi2MoO6-g-C3N4Photocatalytic degradation material of heterojunctionThe method is characterized in that: the volume ratio of the distilled water, the ethanol and the glacial acetic acid in the step (2) is 40-50:10:6-10, and the mass fraction of the glucose in the total solution is controlled to be 0.3-0.4%.
6. A Pr according to claim 23+Doping with Bi2MoO6-g-C3N4The photocatalytic degradation material of the heterojunction is characterized in that: the reation kettle heating cabinet in step (2) includes the air-blast heater, air-blast heater swing joint has the air-blast fan piece, reation kettle heating cabinet bottom fixedly connected with rotary device, rotary device swing joint has the rotation axis, rotation axis upper end fixedly connected with base, the base top is provided with polymerization reaction kettle, base top fixedly connected with bracing piece, bracing piece swing joint has the governing valve, governing valve fixedly connected with carriage release lever, carriage release lever fixedly connected with annular cardboard.
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| CN114471653A (en) * | 2021-12-31 | 2022-05-13 | 山东华夏神舟新材料有限公司 | Catalyst for preparing 1, 1-difluoroethylene by catalytic cracking of chlorodifluoroethane and preparation method and application thereof |
| CN115093683A (en) * | 2022-06-08 | 2022-09-23 | 青岛普诺恩生物科技有限公司 | Modified degradable material with controllable degradation rate and preparation method thereof |
| CN117210080A (en) * | 2023-10-19 | 2023-12-12 | 青岛中氟氟碳材料有限公司 | Preparation method and application of anti-pollution water-based paint for inner wall of high-speed rail |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114471653A (en) * | 2021-12-31 | 2022-05-13 | 山东华夏神舟新材料有限公司 | Catalyst for preparing 1, 1-difluoroethylene by catalytic cracking of chlorodifluoroethane and preparation method and application thereof |
| CN114471653B (en) * | 2021-12-31 | 2024-03-26 | 山东华夏神舟新材料有限公司 | Catalyst for preparing 1, 1-difluoroethylene by catalytic pyrolysis of chlorodifluoroethane and preparation method and application thereof |
| CN115093683A (en) * | 2022-06-08 | 2022-09-23 | 青岛普诺恩生物科技有限公司 | Modified degradable material with controllable degradation rate and preparation method thereof |
| CN117210080A (en) * | 2023-10-19 | 2023-12-12 | 青岛中氟氟碳材料有限公司 | Preparation method and application of anti-pollution water-based paint for inner wall of high-speed rail |
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