CN111097476A - Composite photocatalytic material with high-efficiency photocatalytic activity and preparation method thereof - Google Patents
Composite photocatalytic material with high-efficiency photocatalytic activity and preparation method thereof Download PDFInfo
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- CN111097476A CN111097476A CN201911411648.7A CN201911411648A CN111097476A CN 111097476 A CN111097476 A CN 111097476A CN 201911411648 A CN201911411648 A CN 201911411648A CN 111097476 A CN111097476 A CN 111097476A
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- 239000000463 material Substances 0.000 title claims abstract description 152
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 88
- 150000002829 nitrogen Chemical class 0.000 claims abstract description 62
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 44
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 21
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 21
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 49
- 238000001035 drying Methods 0.000 claims description 44
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 42
- 239000012153 distilled water Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 35
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 28
- 239000004005 microsphere Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 25
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 21
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 21
- 235000019800 disodium phosphate Nutrition 0.000 claims description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 21
- 235000011008 sodium phosphates Nutrition 0.000 claims description 20
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 108010024636 Glutathione Proteins 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229960003180 glutathione Drugs 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- VNWKTOKETHGBQD-YPZZEJLDSA-N carbane Chemical group [10CH4] VNWKTOKETHGBQD-YPZZEJLDSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 6
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 238000002715 modification method Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 229910000161 silver phosphate Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 59
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 26
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 26
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- -1 trithiocyanamide Chemical compound 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical group [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- GPWDPLKISXZVIE-UHFFFAOYSA-N cyclo[18]carbon Chemical group C1#CC#CC#CC#CC#CC#CC#CC#CC#C1 GPWDPLKISXZVIE-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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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- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, wherein the composite photocatalytic material comprises modified nitrogen carbide, a first catalytic material, a second catalytic material, carbon fiber, sodium phosphate and other components, the modified nitrogen carbide is prepared by a precursor self-assembly copolymerization modification method, and the adopted raw materials are melamine and melamine cyanurate; the first catalyst is Ag/Ag3PO4/BiPO4The second catalyst is CdS microsphere @ TiO2In the core-shell structure, the first catalytic material and the second catalytic material both have excellent photocatalytic activity and visible light utilization rate, and then the first catalytic material, the second catalytic material and the modified nitrogen carbide are compounded; hair brushThe photocatalytic material is prepared by compounding the first catalytic material, the second catalytic material and the modified nitrogen carbide, so that the visible light utilization rate of the photocatalytic material is effectively improved, and the photocatalytic material is excellent in reactivity and photocatalytic reaction efficiency and has high practicability.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof.
Background
The photocatalysis technology is a green technology with important application prospect in the field of energy and environment, and the photocatalysis principle is based on the oxidation-reduction capability of the photocatalyst under the condition of illumination, so that the aims of purifying pollutants, synthesizing and converting substances and the like can be fulfilled. Generally, a photocatalytic oxidation reaction takes a semiconductor as a catalyst and light as energy to degrade organic matters into carbon dioxide and water, so that a photocatalytic technology is an efficient and safe environment-friendly environmental purification technology.
At present, the photocatalysis technology is mostly used in the fields of environmental cleaning, wastewater treatment and the like, but the existing photocatalyst has high sunlight utilization rate, poor photocatalytic activity and low pollution degradation efficiency, which brings great inconvenience to people.
Aiming at the problems, a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof are designed, which are one of the problems to be solved urgently.
Disclosure of Invention
The invention aims to provide a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a composite photocatalytic material with high-efficiency photocatalytic activity comprises the following raw materials: 10-25 parts of modified nitrogen carbide, 10-15 parts of a first catalytic material, 10-15 parts of a second catalytic material, 3-7 parts of carbon fiber and 10-18 parts of sodium phosphate.
According to an optimized scheme, the first catalytic material comprises the following raw materials in parts by weight: 8-16 parts of bismuth nitrate pentahydrate, 5-12 parts of silver nitrate, 10-20 parts of ethylene glycol and 3-8 parts of sodium hydrogen phosphate.
According to an optimized scheme, the second catalytic material comprises the following raw materials: by weight, 6-13 parts of tetrabutyl titanate, 2-10 parts of CdS microspheres, 10-20 parts of absolute ethyl alcohol and 3-5 parts of ammonia water.
According to an optimized scheme, the CdS microspheres are prepared from cadmium nitrate tetrahydrate, thiourea and glutathione.
According to an optimized scheme, the modified nitrogen carbide is prepared from melamine and melamine cyanurate.
The invention discloses a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, wherein the composite photocatalytic material comprises modified carbonized nitrogen, a first catalytic material, a second catalytic material, carbon fiber, sodium phosphate and the likeThe nitrogen is prepared by a precursor self-assembly copolymerization modification method, and the adopted raw materials are melamine and melamine cyanurate; the first catalyst is Ag/Ag3PO4/BiPO4The second catalytic material is a CdS microsphere @ TiO2 core-shell structure, the first catalytic material and the second catalytic material both have excellent photocatalytic activity and visible light utilization rate, and the first catalytic material, the second catalytic material and the modified nitrogen carbide are compounded to obtain the photocatalytic material which is high in visible light utilization rate, excellent in photocatalytic activity and excellent in stability.
The optimized scheme is that the preparation method of the composite photocatalytic material with high-efficiency photocatalytic activity comprises the following steps:
1) preparing materials;
2) preparing a first catalyst;
3) preparing a second catalytic material;
4) preparing modified nitrogen carbide;
5) and dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding a modified nitrogen carbide solution and a sodium phosphate solution, and reacting to obtain the photocatalytic material.
The optimized scheme comprises the following steps:
1) preparing materials;
2) preparation of a first catalyst: dissolving the pentahydrate bismuth nitrate and the silver nitrate prepared in the step 1) with ethylene glycol, stirring, adding sodium hydrogen phosphate, continuously stirring, placing in an oil bath for heat preservation at the temperature of 120-;
3) preparation of the second catalyst:
a) dissolving the cadmium nitrate tetrahydrate, thiourea and glutathione prepared in the step 1) in distilled water, stirring for reaction for 1-2h, then placing the solution in a high-pressure reaction kettle, reacting for 3-4h at the temperature of 250-260 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres;
b) taking tetrabutyl titanate prepared in the step 1) and absolute ethyl alcohol, and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving the CdS microspheres prepared in the step a) with ethanol, performing ultrasonic dispersion for 20-30min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at a constant temperature of 60-70 ℃ for 3-4h to obtain a second catalytic material;
4) preparing modified nitrogen carbide: dissolving the melamine prepared in the step 1) in distilled water, and performing ultrasonic dispersion to obtain a melamine solution; dissolving the melamine prepared in the step 1) with distilled water, and performing ultrasonic dispersion for 30-40min to obtain melamine solution, adding the prepared melamine solution and carbon fiber, mixing and stirring, standing, removing supernatant, alternately washing with deionized water and ethanol, drying in a drying oven, heating to 550-560 ℃, and preserving heat for 4-5h to obtain modified nitrogen carbide;
5) dissolving the modified nitrogen carbide prepared in the step 4) in distilled water, and performing ultrasonic dispersion to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring in the dark for reaction, adding the sodium phosphate solution, mixing and stirring, washing and drying to obtain the photocatalytic material.
The optimized scheme comprises the following steps:
1) preparing materials:
a) weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate for later use;
b) weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, carbon fiber and sodium phosphate for later use; preparing raw materials of each component in step 1) of the method for subsequent production and preparation;
2) preparation of a first catalyst: dissolving the pentahydrate bismuth nitrate and the silver nitrate prepared in the step 1) with ethylene glycol, stirring for 20-30min, adding sodium hydrogen phosphate, continuing stirring for 30-40min, placing in an oil bath for heat preservation at the temperature of 120-130 ℃, for 2-3h, filtering, alternately washing with ionized water and ethanol for 2-3 times, and then placing in a drying box for drying at the temperature of 70-80 ℃ for 8-9h to obtain a first catalytic material; the inventionThe silver-silver alloy is prepared by adopting a one-step low-temperature chemical bath precipitation method in the step 2), and Ag/Ag is generated by reacting pentahydrate bismuth nitrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate and other components3PO4/BiPO4Composite materials, i.e. first catalytic materials;
3) preparation of the second catalyst:
a) dissolving the cadmium nitrate tetrahydrate, thiourea and glutathione prepared in the step 1) in distilled water, stirring for reaction for 1-2h, then placing the solution in a high-pressure reaction kettle, reacting for 3-4h at the temperature of 250-260 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres; in the step 3), the CdS microspheres are synthesized by a hydrothermal method, have obvious hollow structures, can enhance the reflection efficiency of absorbed light, and improve the utilization rate of solar energy;
b) taking tetrabutyl titanate prepared in the step 1) and absolute ethyl alcohol, and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving the CdS microspheres prepared in the step a) with ethanol, performing ultrasonic dispersion for 20-30min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at a constant temperature of 60-70 ℃ for 3-4h to obtain a second catalytic material; coating a layer of titanium dioxide sol on the surface of the CdS microsphere in the step b) of the invention to form the CdS microsphere @ TiO2A core-shell structure, i.e. a second catalytic material;
4) preparing modified nitrogen carbide: dissolving the melamine prepared in the step 1) in distilled water, and performing ultrasonic dispersion for 30-40min to obtain a melamine solution; dissolving the melamine prepared in the step 1) with distilled water, performing ultrasonic dispersion for 30-40min to obtain melamine solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 8-9h, standing, removing supernatant, alternately washing with deionized water and ethanol for 2-3 times, drying in a drying oven at 60-70 ℃ for 24-28h, drying in a nitrogen environment, heating to 550 ℃ and 560 ℃, heating at a rate of 2-3 ℃/min, and keeping the temperature for 4-5h to obtain modified nitrogen carbide; the modified nitrogen carbide is prepared by a precursor self-assembly copolymerization modification method, and a plurality of holes with different sizes are formed on the surface of the modified nitrogen carbide, so that the modified nitrogen carbide can receive radiation light sources to a greater extent;
5) dissolving the modified nitrogen carbide prepared in the step 4) in distilled water, and performing ultrasonic dispersion for 20-30min to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring for 10-12h in the dark, adding the sodium phosphate solution, mixing and stirring for 5-6h, washing and drying to obtain the photocatalytic material. In the step 5) of the invention, the modified nitrogen carbide is compounded with the first catalytic material and the second catalytic material, and the first catalytic material and the second catalytic material can enter the modified nitrogen carbide through the holes and can be adsorbed on the surface of the modified nitrogen carbide, so that the prepared photocatalytic material has high reactivity and photocatalytic reaction efficiency.
Compared with the prior art, the invention has the beneficial effects that:
when the silver/silver nitrate/sodium hydrogen phosphate/silver nitrate/ethylene glycol/sodium hydrogen phosphate/silver nitrate/sodium hydrogen phosphate mixed solution is prepared by a one-step low-temperature chemical bath precipitation method3PO4/BiPO4The composite material, namely the first catalyst, bismuth nitrate pentahydrate has excellent visible light absorption performance, and Ag is used in the preparation process3PO4、BiPO4Form Ag/Ag on the surface of3PO4A heterojunction structure, the heterojunction containing a plurality of defects, and the defects inhibiting recombination of electron-hole pairs; ag and Ag at the same time3PO4The surface of the alloy also forms Ag/Ag3PO4The heterojunction structure and the heterojunction structure have synergistic effect, and the first catalytic material prepared by the heterojunction structure and the heterojunction structure has excellent photocatalytic performance and stability.
TiO2Is an important semiconductor photocatalytic material, and has the characteristics of high activity of photocatalytic degradation of organic matters, stable photochemistry, chemical and photochemical corrosion resistance, no toxicity and the like, and TiO2Although the light is relatively stable, the band gap is wide, the light absorption is limited to an ultraviolet region, and the light absorption can not reach 10 percent of the solar spectrum irradiated to the ground, the utilization of sunlight is limited, and the preparation of the composite semiconductor improves the TiO at present2A common and very efficient approach to photocatalytic activity; CdS (cadmium sulfide) is an optical bandgapThe CdS microspheres have obvious hollow structures, and after being compounded with the semiconductors, the hollow structures can increase the specific surface area of the compound, enhance the reflection efficiency of light absorbed by the compound and improve the separation of photo-generated electrons and holes of the compound.
Therefore, the invention designs a second catalytic material which is CdS microsphere @ TiO2According to the core-shell structure, the CdS microspheres are synthesized by a hydrothermal method, a layer of titanium dioxide sol is coated on the surfaces of the CdS microspheres to form the CdS microsphere @ TiO2 core-shell structure, and the second catalytic material has excellent photocatalytic performance and high visible light utilization rate.
The modified nitrogen carbide is prepared by a precursor self-assembly copolymerization modification method, is in a thin tubular structure after being calcined at high temperature, is in a hollow transparent state at a thinner pipe wall, and is provided with holes with different pore diameters on the surface, wherein the holes are close to the wavelength of a solar spectrum, can receive incident photons to generate resonance, and can increase the absorption and utilization efficiency of light.
The carbon fiber is added, during the high-temperature roasting process, the carbon fiber can be carbonized and combusted, the formation of holes is further improved, the holes are mutually and tightly connected, the diffusion distance of current carriers can be effectively reduced, a system can receive a radiation light source to a greater extent, when the carbon fiber is subsequently compounded with the first catalytic material and the second catalytic material, the first catalytic material and the second catalytic material with smaller particle sizes can enter the modified nitrogen carbide tube, the first catalytic material and the second catalytic material with larger particle sizes can be adsorbed on the surface of the modified nitrogen carbide tube, and the first catalytic material and the second catalytic material have synergistic effect with each other, so that the reaction activity site of the composite photocatalytic material is increased, and the reaction activity and the photocatalytic reaction efficiency of the composite photocatalytic material are improved.
The invention discloses a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, the process design is reasonable, the operation is simple, the visible light utilization rate of the photocatalytic material is effectively improved by preparing the photocatalytic material by compounding a first catalytic material, a second catalytic material and modified nitrogen carbide, and the photocatalytic material has excellent reactivity and photocatalytic reaction efficiency and higher practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
s1: preparing materials: weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate, and weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, trithiocyanamide, carbon fiber and sodium phosphate for later use;
s2: preparation of a first catalyst: dissolving bismuth nitrate pentahydrate and silver nitrate in ethylene glycol, stirring for 20min, adding sodium hydrogen phosphate, continuously stirring for 30min, placing in an oil bath for heat preservation at the temperature of 120 ℃ for 3h, filtering, alternately washing with ionized water and ethanol for 2 times, and then placing in a drying oven for drying at the temperature of 70 ℃ for 9h to obtain a first catalytic material;
s3: preparation of the second catalyst:
dissolving cadmium nitrate tetrahydrate, thiourea and glutathione in distilled water, stirring for reaction for 1h, then placing the solution in a high-pressure reaction kettle, reacting for 4h at 250 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres;
taking tetrabutyl titanate and absolute ethyl alcohol, and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving CdS microspheres in ethanol, performing ultrasonic dispersion for 20min, adding ammonia water, and mixing to obtain solution B; mixing the solution A and the solution B, and reacting at a constant temperature of 60 ℃ for 4 hours to obtain a second catalytic material;
s4: preparing modified nitrogen carbide:
dissolving melamine in distilled water, and ultrasonically dispersing for 30min to obtain a melamine solution; dissolving melamine in distilled water, performing ultrasonic dispersion for 30min to obtain melamine solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 8h, standing, removing supernatant, alternately washing with deionized water and ethanol for 2 times, drying in a drying oven at 60 ℃ for 28h, heating to 550 ℃ in a nitrogen environment at a heating rate of 2 ℃/min, and keeping the temperature for 5h to obtain modified nitrogen carbide;
s5: dissolving modified nitrogen carbide in distilled water, and performing ultrasonic dispersion for 20min to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring for 10 hours in the dark, adding the sodium phosphate solution, mixing and stirring for 5 hours, washing and drying to obtain the photocatalytic material.
In this embodiment, the composite photocatalytic material includes the following raw materials: the catalyst comprises, by weight, 10 parts of modified nitrogen carbide, 10 parts of a first catalytic material, 10 parts of a second catalytic material, 3 parts of carbon fibers and 10 parts of sodium phosphate.
The first catalytic material comprises the following raw materials in parts by weight: by weight, 8 parts of pentahydrate bismuth nitrate, 5 parts of silver nitrate, 10 parts of ethylene glycol and 3 parts of sodium hydrogen phosphate; the second catalytic material comprises the following raw materials: by weight, 6 parts of tetrabutyl titanate, 2 parts of CdS microspheres, 10 parts of absolute ethyl alcohol and 3 parts of ammonia water.
Example 2:
s1: preparing materials: weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate, and weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, trithiocyanamide, carbon fiber and sodium phosphate for later use;
s2: preparation of a first catalyst: dissolving bismuth nitrate pentahydrate and silver nitrate in ethylene glycol, stirring for 25min, adding sodium hydrogen phosphate, continuously stirring for 35min, placing in an oil bath for heat preservation, wherein the oil bath temperature is 125 ℃, the heat preservation time is 2.5h, filtering, alternately washing with ionized water and ethanol for 2 times, placing in a drying oven for drying, and the drying temperature is 75 ℃, the drying time is 8.5h to obtain a first catalyst;
s3: preparation of the second catalyst:
dissolving cadmium nitrate tetrahydrate, thiourea and glutathione in distilled water, stirring for reaction for 1.5h, placing the solution in a high-pressure reaction kettle, reacting for 3.5h at 255 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres;
taking tetrabutyl titanate and absolute ethyl alcohol, and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving CdS microspheres in ethanol, performing ultrasonic dispersion for 25min, adding ammonia water, and mixing to obtain solution B; mixing the solution A and the solution B, and reacting at the constant temperature of 65 ℃ for 3.5 hours to obtain a second catalytic material;
s4: preparing modified nitrogen carbide:
dissolving melamine in distilled water, and ultrasonically dispersing for 35min to obtain a melamine solution; dissolving melamine in distilled water, performing ultrasonic dispersion for 35min to obtain melamine solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 8.5h, standing, removing supernatant, alternately washing with deionized water and ethanol for 2 times, drying in a drying oven at 65 ℃ for 26h, heating to 555 ℃ in a nitrogen environment after drying, heating at a heating rate of 2.5 ℃/min, and keeping the temperature for 4.5h to obtain modified nitrogen carbide;
s5: dissolving modified nitrogen carbide in distilled water, and performing ultrasonic dispersion for 25min to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring in a dark place for 11 hours, adding the sodium phosphate solution, mixing and stirring for 5.5 hours, washing and drying to obtain the photocatalytic material.
In this embodiment, the composite photocatalytic material includes the following raw materials: the catalyst comprises, by weight, 15 parts of modified nitrogen carbide, 12 parts of a first catalytic material, 12 parts of a second catalytic material, 5 parts of carbon fiber and 14 parts of sodium phosphate.
The first catalytic material comprises the following raw materials in parts by weight: 13 parts of pentahydrate bismuth nitrate, 8 parts of silver nitrate, 15 parts of ethylene glycol and 5 parts of sodium hydrogen phosphate by weight; the second catalytic material comprises the following raw materials: by weight, 8 parts of tetrabutyl titanate, 6 parts of CdS microspheres, 15 parts of absolute ethyl alcohol and 4 parts of ammonia water.
Example 3:
s1: preparing materials: weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate, and weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, trithiocyanamide, carbon fiber and sodium phosphate for later use;
s2: preparation of a first catalyst: dissolving bismuth nitrate pentahydrate and silver nitrate in ethylene glycol, stirring for 30min, adding sodium hydrogen phosphate, continuously stirring for 40min, placing in an oil bath for heat preservation at the temperature of 130 ℃ for 2h, filtering, alternately washing with ionized water and ethanol for 3 times, and then placing in a drying oven for drying at the temperature of 80 ℃ for 8h to obtain a first catalytic material;
s3: preparation of the second catalyst:
dissolving cadmium nitrate tetrahydrate, thiourea and glutathione in distilled water, stirring for reaction for 2 hours, putting the solution into a high-pressure reaction kettle, reacting for 3 hours at 260 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres;
taking tetrabutyl titanate and absolute ethyl alcohol, and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving CdS microspheres in ethanol, performing ultrasonic dispersion for 30min, adding ammonia water, and mixing to obtain solution B; mixing the solution A and the solution B, and reacting at a constant temperature of 70 ℃ for 3 hours to obtain a second catalytic material;
s4: preparing modified nitrogen carbide:
dissolving melamine in distilled water, and ultrasonically dispersing for 40min to obtain a melamine solution; dissolving melamine in distilled water, performing ultrasonic dispersion for 40min to obtain melamine solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 9h, standing, removing supernatant, alternately washing with deionized water and ethanol for 3 times, drying in a drying oven at 70 ℃ for 24h, drying, placing in a nitrogen environment, heating to 560 ℃, heating at a rate of 3 ℃/min, and keeping the temperature for 4h to obtain modified nitrogen carbide;
s5: dissolving modified nitrogen carbide in distilled water, and performing ultrasonic dispersion for 30min to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring for 12 hours in a dark place, adding the sodium phosphate solution, mixing and stirring for 6 hours, washing and drying to obtain the photocatalytic material.
In this embodiment, the composite photocatalytic material includes the following raw materials: the catalyst comprises, by weight, 25 parts of modified nitrogen carbide, 15 parts of a first catalytic material, 15 parts of a second catalytic material, 7 parts of carbon fiber and 18 parts of sodium phosphate.
The first catalytic material comprises the following raw materials in parts by weight: 16 parts of pentahydrate bismuth nitrate, 12 parts of silver nitrate, 20 parts of ethylene glycol and 8 parts of sodium hydrogen phosphate by weight; the second catalytic material comprises the following raw materials: by weight, 13 parts of tetrabutyl titanate, 10 parts of CdS microspheres, 20 parts of absolute ethyl alcohol and 5 parts of ammonia water.
Experiment:
the composite photocatalytic materials prepared in the examples 1 to 3 are respectively used for degrading rhodamine under visible light at room temperature, wherein a 300WXe lamp with an ultraviolet filter is used as a light source, and the operation is as follows:
0.10g of the composite photocatalytic material sample prepared in the embodiment 1-3 is taken and mixed with 100ml of rhodamine in the dark, and the mixture is uniformly stirred, so that the dynamic balance of adsorption-desorption is established between the composite photocatalytic material and the rhodamine.
In the light, 5ml of the solution was removed at regular intervals, the composite photocatalytic material was removed by centrifugation, and the change in absorbance at 554nm was recorded using a UV-2102PC photometer.
And (4) conclusion: according to the ultraviolet-visible absorption spectrogram of the composite photocatalytic material for degrading rhodamine, which is obtained after experimental operation, it can be seen from the figure that the absorption peak at 554nm on the curve is reduced dramatically with the prolonging of the illumination time, which shows that the composite photocatalytic material has excellent photocatalytic degradation performance on rhodamine under visible light.
The illumination experiment is carried out for 60min, statistics shows that the degradation rate of the composite photocatalytic material to rhodamine can reach 99% at most and 98% at least within 60min of illumination, which indicates that the composite photocatalytic material has high activity and high catalytic efficiency to rhodamine in photocatalytic reaction.
The invention discloses a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, the process design is reasonable, the operation is simple, the visible light utilization rate of the photocatalytic material is effectively improved by preparing the photocatalytic material by compounding a first catalytic material, a second catalytic material and modified nitrogen carbide, and the photocatalytic material has excellent reactivity and photocatalytic reaction efficiency and higher practicability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. A composite photocatalytic material with high-efficiency photocatalytic activity is characterized in that: the composite photocatalytic material comprises the following raw materials: 10-25 parts of modified nitrogen carbide, 10-15 parts of a first catalytic material, 10-15 parts of a second catalytic material, 3-7 parts of carbon fiber and 10-18 parts of sodium phosphate.
2. The composite photocatalytic material with high photocatalytic activity according to claim 1, wherein: the first catalytic material comprises the following raw materials in parts by weight: 8-16 parts of bismuth nitrate pentahydrate, 5-12 parts of silver nitrate, 10-20 parts of ethylene glycol and 3-8 parts of sodium hydrogen phosphate.
3. The composite photocatalytic material with high photocatalytic activity according to claim 1, wherein: the second catalytic material comprises the following raw materials: by weight, 6-13 parts of tetrabutyl titanate, 2-10 parts of CdS microspheres, 10-20 parts of absolute ethyl alcohol and 3-5 parts of ammonia water.
4. The composite photocatalytic material with high photocatalytic activity according to claim 1, wherein: the modified nitrogen carbide is prepared from melamine and melamine cyanurate.
5. The composite photocatalytic material with high photocatalytic activity, according to claim 3, wherein: the CdS microspheres are prepared from cadmium nitrate tetrahydrate, thiourea and glutathione.
6. A preparation method of a composite photocatalytic material with high-efficiency photocatalytic activity is characterized by comprising the following steps: the method comprises the following steps:
1) preparing materials;
2) preparing a first catalyst;
3) preparing a second catalytic material;
4) preparing modified nitrogen carbide;
5) and dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding a modified nitrogen carbide solution and a sodium phosphate solution, and reacting to obtain the photocatalytic material.
7. The method for preparing a composite photocatalytic material with high photocatalytic activity according to claim 6, wherein: the method comprises the following steps:
1) preparing materials;
2) preparation of a first catalyst: dissolving the pentahydrate bismuth nitrate and the silver nitrate prepared in the step 1) with ethylene glycol, stirring, adding sodium hydrogen phosphate, continuously stirring, placing in an oil bath for heat preservation at the temperature of 120-;
3) preparation of the second catalyst:
a) dissolving the cadmium nitrate tetrahydrate, thiourea and glutathione prepared in the step 1) in distilled water, stirring for reaction for 1-2h, then placing the solution in a high-pressure reaction kettle, reacting for 3-4h at the temperature of 250-260 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres;
b) taking tetrabutyl titanate prepared in the step 1) and absolute ethyl alcohol, and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving the CdS microspheres prepared in the step a) with ethanol, performing ultrasonic dispersion for 20-30min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at a constant temperature of 60-70 ℃ for 3-4h to obtain a second catalytic material;
4) preparing modified nitrogen carbide: dissolving the melamine prepared in the step 1) in distilled water, and performing ultrasonic dispersion to obtain a melamine solution; dissolving the melamine prepared in the step 1) with distilled water, and performing ultrasonic dispersion for 30-40min to obtain melamine solution, adding the prepared melamine solution and carbon fiber, mixing and stirring, standing, removing supernatant, alternately washing with deionized water and ethanol, drying in a drying oven, heating to 550-560 ℃, and preserving heat for 4-5h to obtain modified nitrogen carbide;
5) dissolving the modified nitrogen carbide prepared in the step 4) in distilled water, and performing ultrasonic dispersion to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring in the dark for reaction, adding the sodium phosphate solution, mixing and stirring, washing and drying to obtain the photocatalytic material.
8. The method for preparing a composite photocatalytic material with high photocatalytic activity according to claim 7, wherein: the method comprises the following steps:
1) preparing materials;
a) weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate for later use;
b) weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, carbon fiber and sodium phosphate for later use;
2) preparation of a first catalyst: dissolving the pentahydrate bismuth nitrate and the silver nitrate prepared in the step 1) with ethylene glycol, stirring for 20-30min, adding sodium hydrogen phosphate, continuing stirring for 30-40min, placing in an oil bath for heat preservation at the temperature of 120-130 ℃, for 2-3h, filtering, alternately washing with ionized water and ethanol for 2-3 times, and then placing in a drying box for drying at the temperature of 70-80 ℃ for 8-9h to obtain a first catalytic material;
3) preparation of the second catalyst:
a) dissolving the cadmium nitrate tetrahydrate, thiourea and glutathione prepared in the step 1) in distilled water, stirring for reaction for 1-2h, then placing the solution in a high-pressure reaction kettle, reacting for 3-4h at the temperature of 250-260 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres;
b) taking tetrabutyl titanate prepared in the step 1) and absolute ethyl alcohol, and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving the CdS microspheres prepared in the step a) with ethanol, performing ultrasonic dispersion for 20-30min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at a constant temperature of 60-70 ℃ for 3-4h to obtain a second catalytic material;
4) preparing modified nitrogen carbide: dissolving the melamine prepared in the step 1) in distilled water, and performing ultrasonic dispersion for 30-40min to obtain a melamine solution; dissolving the melamine prepared in the step 1) with distilled water, performing ultrasonic dispersion for 30-40min to obtain melamine solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 8-9h, standing, removing supernatant, alternately washing with deionized water and ethanol for 2-3 times, drying in a drying oven at 60-70 ℃ for 24-28h, drying in a nitrogen environment, heating to 550 ℃ and 560 ℃, heating at a rate of 2-3 ℃/min, and keeping the temperature for 4-5h to obtain modified nitrogen carbide;
5) dissolving the modified nitrogen carbide prepared in the step 4) in distilled water, and performing ultrasonic dispersion for 20-30min to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring for 10-12h in the dark, adding the sodium phosphate solution, mixing and stirring for 5-6h, washing and drying to obtain the photocatalytic material.
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