CN111437883A - Preparation method of porous magnetic semiconductor composite photocatalyst - Google Patents
Preparation method of porous magnetic semiconductor composite photocatalyst Download PDFInfo
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- CN111437883A CN111437883A CN202010277508.1A CN202010277508A CN111437883A CN 111437883 A CN111437883 A CN 111437883A CN 202010277508 A CN202010277508 A CN 202010277508A CN 111437883 A CN111437883 A CN 111437883A
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- composite photocatalyst
- semiconductor composite
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- magnetic semiconductor
- quantum dots
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 239000004065 semiconductor Substances 0.000 title claims abstract description 42
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 241000283973 Oryctolagus cuniculus Species 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002096 quantum dot Substances 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007966 viscous suspension Substances 0.000 claims abstract description 18
- AMHXQVUODFNFGR-UHFFFAOYSA-K [Ag+3].[O-]P([O-])([O-])=O Chemical class [Ag+3].[O-]P([O-])([O-])=O AMHXQVUODFNFGR-UHFFFAOYSA-K 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 9
- 229920000161 Locust bean gum Polymers 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 235000010420 locust bean gum Nutrition 0.000 claims abstract description 8
- 239000000711 locust bean gum Substances 0.000 claims abstract description 8
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 8
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 8
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 7
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229940019931 silver phosphate Drugs 0.000 claims abstract description 6
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 6
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 4
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical class O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 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
- 229940043267 rhodamine b Drugs 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000005293 ferrimagnetic effect Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J35/33—Electric or magnetic properties
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- 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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/51—Spheres
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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
- B01J35/61—Surface area
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- 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 discloses a preparation method of a porous magnetic semiconductor composite photocatalyst, which is characterized in that water-soluble zinc and sulfur-doped carbon quantum dots are prepared by a hydrothermal method by taking rabbit hair as a carbon source and zinc chloride and thiourea as solvents; modifying disodium hydrogen phosphate by adopting zinc and sulfur doped carbon quantum dots, and dropwise adding a silver nitrate solution to prepare quantum dot modified silver phosphate; in the reactor, deionized water: 60-66%, protein powder: 6-10%, locust bean gum: 3-6%, stirring and dissolving, and modifying the silver phosphate by the quantum dots: 18-22%, aminated iron sesquioxide magnetic nanoparticles: 4-6 percent of the porous magnetic semiconductor composite photocatalyst is ultrasonically dispersed for 20 min to obtain a viscous suspension, the viscous suspension is extruded into a sphere, the sphere is solidified in a 5 percent magnesium chloride solution for 12 h, and the porous magnetic semiconductor composite photocatalyst is prepared by solid-liquid separation, washing and freeze drying. The invention has the characteristics of simple preparation method, good stability, degradability and the like; the catalyst is easy to recover and has high catalytic activity.
Description
Technical Field
The invention relates to the technical field of preparation of supported catalysts, in particular to a preparation method of a porous magnetic semiconductor composite photocatalyst and application of the porous magnetic semiconductor composite photocatalyst in degradation of organic pollutants.
Background
The environmental pollution problem is one of the major problems to be solved urgently by human beings nowadays. The photocatalytic oxidation method has the advantages of low energy consumption, mild purification conditions, no secondary pollution and the like for treating environmental pollution, so the photocatalytic oxidation method is concerned as a green chemical process. Conventional semiconductor photocatalysts such as TiO2And ZnO, which has a wider forbidden band width and can only absorb 3% -5% of solar energy. Bi-based and Ag-based semiconductors have the problems of narrow visible light absorption range, strong light corrosivity and the like, and the recombination rate of photon-generated carriers of most semiconductors is high, so that the potential application of semiconductor photocatalysts is limited. Therefore, an increasing amount of research is being conducted to widen the visible light absorption range of the photocatalyst and to promote the separation efficiency of carriers to improve the photocatalytic activity and stability thereof.
A Carbon Quantum Dot (CQDs) is a novel Carbon nano material with outstanding fluorescence recently discovered, consists of quasi-discrete spherical Carbon nano particles with the size less than 10 nm, and is an environment-friendly material with excellent water solubility, high biocompatibility and low toxicityElectron transport performance, can effectively transfer and store photoproduction electrons in the catalyst, achieves the effect of improving charge separation efficiency, and the photoproduction electrons and O adsorbed on the surface of the photoproduction electrons2The combination can form superoxide radical to realize multi-site catalysis, the ④ pi-pi conjugated structure is favorable for the adsorption of organic pollutants on the surface of the photocatalyst, ⑤ can prevent the catalyst from dissolving and effectively prevent the photo corrosion after forming a core-shell structure on the CQDs layer and the CQDs layer, and the like, so the CQDs is compounded with the semiconductor and is an important way for improving the performance of the photocatalyst.
According to the preparation method, rabbit hair is used as a carbon source, zinc oxide and thiourea are used as solvents to prepare zinc and sulfur doped carbon quantum dots, then the semiconductor photocatalyst silver phosphate is modified, protein powder and magnetic particles are added into locust bean gum, and the porous magnetic semiconductor composite photocatalyst is prepared by freeze drying.
Disclosure of Invention
The invention aims to provide a preparation method of a porous magnetic semiconductor composite photocatalyst.
A preparation method of a porous magnetic semiconductor composite photocatalyst is characterized by comprising the following process steps:
(1) preparing zinc and sulfur doped carbon quantum dots, namely adding 84-88 mass percent of 2.0 mol/L zinc chloride and 4-8 mass percent of thiourea into a reaction kettle with a polytetrafluoroethylene lining, stirring and dissolving, pretreating rabbit hair powder, covering a sealing cover, placing the rabbit hair powder into a constant temperature box, keeping the temperature at 120 +/-2 ℃, reacting for 8 hours to obtain colorless transparent liquid, dialyzing, and drying to obtain water-soluble zinc and sulfur doped carbon quantum dots, wherein the sum of the mass percent of the components is one hundred percent;
(2) preparing quantum dot modified silver phosphate, namely adding 83-88 mass percent of deionized water, 4-8 mass percent of disodium hydrogen phosphate and 0.5-2.0 mass percent of zinc and sulfur doped carbon quantum dots into a reactor, stirring and dissolving, dropwise adding 5-9 mass percent of 12 mol/L silver nitrate solution, keeping the sum of the mass percent of the components at one hundred percent, stirring and reacting for 18 hours in a dark place, carrying out solid-liquid separation, washing and drying to obtain the quantum dot modified silver phosphate;
(3) preparing a porous magnetic semiconductor composite photocatalyst: adding deionized water into a reactor according to the following composition by mass percent: 60-66%, protein powder: 6-10%, locust bean gum: 3-6%, stirring and dissolving, and modifying the silver phosphate by the quantum dots: 18-22%, aminated iron sesquioxide magnetic nanoparticles: 4-6 percent of the porous magnetic semiconductor composite photocatalyst is obtained by ultrasonic dispersion for 20 min, wherein the sum of the mass percentages of the components is one hundred percent, a viscous suspension is obtained, the viscous suspension is extruded into a sphere, the sphere is solidified in a 5 percent magnesium chloride solution for 12 hours, and the porous magnetic semiconductor composite photocatalyst is obtained by solid-liquid separation, washing and freeze drying.
The pre-treatment rabbit hair powder in the step (1) is prepared by washing rabbit hair with water to remove impurities, drying, crushing, sieving with a 100-mesh sieve, soaking the rabbit hair powder in a hydrogen peroxide solution with the mass percentage concentration of 10% according to the solid-to-liquid ratio of 1: 40m L for 6h, boiling for 5min, cooling, washing with deionized water, carrying out solid-liquid separation, and drying.
The molar ratio of the disodium hydrogen phosphate to the silver nitrate in the step (2) is 1: 3-3.2.
Extruding into a sphere in the step (3), wherein the particle size of the sphere is 0.5-2.0 mm.
The invention also aims to apply the porous magnetic semiconductor composite photocatalyst to analysis and evaluation of catalytic degradation of methyl orange, rhodamine B, azo dyes, bisphenol A, tetracycline, organic pollutants and the like in wastewater.
The invention has the beneficial effects that:
(1) according to the porous magnetic semiconductor composite photocatalyst provided by the application, water-soluble zinc and sulfur-doped carbon quantum dots are synthesized by a solvothermal method with rabbit hair as a carbon source and zinc chloride and thiourea as solvents, silver phosphate is modified by the quantum dots, and then the catalyst is immobilized in a biological magnetic porous material, so that the porous magnetic semiconductor composite photocatalyst is more green, economic and environment-friendly compared with the traditional process. The rabbit hair is widely distributed, has short growth cycle, and is cheap and easily available as a carbon source raw material.
(2) The porous magnetic semiconductor composite photocatalyst prepared by adopting a solvothermal method is simple to operate, adopts quantum dots to modify silver phosphate, then is immobilized in a biomagnetic porous material, has uniformly dispersed particles, has the characteristics of being porous, large in specific surface area, high in catalytic efficiency, light in weight, low in price, good in stability, degradable, environment-friendly and the like, is a renewable resource, has good physicochemical stability and excellent mechanical stability, and can widen the absorption range of the catalyst to sunlight; the material has up-conversion photoluminescence characteristics, and can excite a semiconductor to form more photo-generated electron-hole pairs; the visible light catalysis efficiency is high.
(3) The porous magnetic semiconductor composite photocatalyst prepared by the solvothermal method has magnetism and is easy to separate.
Detailed Description
Example 1
(1) Preparing zinc and sulfur doped carbon quantum dots, namely respectively adding 2.0 mol/L of 86m L of zinc chloride and 6g of thiourea into a reaction kettle with a polytetrafluoroethylene lining, stirring and dissolving, pretreating 8g of rabbit hair powder, covering a sealing cover, placing the rabbit hair powder into a constant temperature box, keeping the temperature at 120 +/-2 ℃, reacting for 8 hours to obtain colorless transparent liquid, dialyzing, and drying to obtain water-soluble zinc and sulfur doped carbon quantum dots;
(2) the preparation of the quantum dot modified silver phosphate comprises the steps of respectively adding 85 m L deionized water, 6g disodium hydrogen phosphate and 2g zinc and sulfur doped carbon quantum dots into a reactor, stirring for dissolving, dropwise adding 7 m L12 mol/L silver nitrate solution, stirring for reacting for 18 hours in a dark place, carrying out solid-liquid separation, washing and drying to obtain the quantum dot modified silver phosphate;
(3) the preparation method of the porous magnetic semiconductor composite photocatalyst comprises the steps of respectively adding 63 m L parts of deionized water, 8g of protein powder, 5g of locust bean gum, stirring for dissolving, 20g of quantum dot modified silver phosphate and 4g of aminated ferrimagnetic nanoparticles into a reactor, carrying out ultrasonic dispersion for 20 min to obtain a viscous suspension, extruding the viscous suspension into a sphere, solidifying the viscous suspension in a 5% magnesium chloride solution for 12 h, carrying out solid-liquid separation, washing, and freeze drying to obtain the porous magnetic semiconductor composite photocatalyst.
Example 2
(1) Preparing zinc and sulfur doped carbon quantum dots, namely respectively adding 2.0 mol/L of zinc chloride (880 m L) and 50g of thiourea into a reaction kettle with a polytetrafluoroethylene lining, stirring and dissolving, pretreating 70g of rabbit hair powder, covering a sealing cover, placing the rabbit hair powder into a constant temperature box, keeping the temperature at 120 +/-2 ℃, reacting for 8 hours to obtain colorless transparent liquid, dialyzing, and drying to obtain water-soluble zinc and sulfur doped carbon quantum dots;
(2) the preparation of the quantum dot modified silver phosphate comprises the steps of respectively adding 880m L deionized water, 45g disodium hydrogen phosphate and 15g zinc and sulfur doped carbon quantum dots into a reactor, stirring for dissolving, dropwise adding 60m L12 mol/L silver nitrate solution, stirring for reacting for 18 hours in a dark place, carrying out solid-liquid separation, washing and drying to obtain the quantum dot modified silver phosphate;
(3) the preparation method of the porous magnetic semiconductor composite photocatalyst comprises the steps of respectively adding 650 m of deionized water L, 60g of protein powder, 60g of locust bean gum, stirring for dissolving, 180g of quantum dot modified silver phosphate and 50g of aminated ferrimagnetic nanoparticles into a reactor, carrying out ultrasonic dispersion for 20 min to obtain a viscous suspension, extruding the viscous suspension into a sphere, solidifying the viscous suspension in a 5% magnesium chloride solution for 12 h, carrying out solid-liquid separation, washing, and freeze-drying to obtain the porous magnetic semiconductor composite photocatalyst.
Example 3
(1) Preparing zinc and sulfur doped carbon quantum dots, namely respectively adding 336m L of 2.0 mol/L of zinc chloride and 28g of thiourea into a reaction kettle with a polytetrafluoroethylene lining, stirring for dissolving, pretreating 36g of rabbit hair powder, covering a sealing cover, placing the rabbit hair powder into a constant temperature box, keeping the temperature at 120 +/-2 ℃, reacting for 8 hours to obtain colorless transparent liquid, dialyzing, and drying to obtain the water-soluble zinc and sulfur doped carbon quantum dots;
(2) the preparation of the quantum dot modified silver phosphate comprises the steps of respectively adding 332 m L deionized water, 32g disodium hydrogen phosphate and 2g zinc and sulfur doped carbon quantum dots into a reactor, stirring for dissolving, dropwise adding 36m L12 mol/L silver nitrate solution, stirring for reacting for 18 hours in a dark place, carrying out solid-liquid separation, washing and drying to obtain the quantum dot modified silver phosphate;
(3) the preparation method of the porous magnetic semiconductor composite photocatalyst comprises the steps of respectively adding 240 m L parts of deionized water, 40g of protein powder, 12g of locust bean gum, stirring for dissolving, 88g of quantum dot modified silver phosphate and 20g of aminated ferrimagnetic nanoparticles into a reactor, carrying out ultrasonic dispersion for 20 min to obtain a viscous suspension, extruding the viscous suspension into a sphere, solidifying the viscous suspension in a 5% magnesium chloride solution for 12 h, carrying out solid-liquid separation, washing, and freeze drying to obtain the porous magnetic semiconductor composite photocatalyst.
Example 4
(1) Preparing zinc and sulfur doped carbon quantum dots, namely respectively adding 170m L of 2.0 mol/L of zinc chloride and 8g of thiourea into a reaction kettle with a polytetrafluoroethylene lining, stirring and dissolving, pretreating 20g of rabbit hair powder, covering a sealing cover, placing the rabbit hair powder into a constant temperature box, keeping the temperature at 120 +/-2 ℃, reacting for 8 hours to obtain colorless transparent liquid, dialyzing, and drying to obtain water-soluble zinc and sulfur doped carbon quantum dots;
(2) preparing quantum dot modified silver phosphate, namely adding 168 m L deionized water, 14g disodium hydrogen phosphate and 2g zinc and sulfur doped carbon quantum dots into a reactor respectively, stirring for dissolving, dropwise adding 16 m L12 mol/L silver nitrate solution, stirring for reacting for 18 hours in a dark place, carrying out solid-liquid separation, washing and drying to obtain the quantum dot modified silver phosphate;
(3) the preparation method of the porous magnetic semiconductor composite photocatalyst comprises the steps of respectively adding 124 m of deionized water L, 18g of protein powder and 8g of locust bean gum into a reactor, stirring and dissolving, 38g of quantum dot modified silver phosphate and 12g of amino ferric oxide magnetic nanoparticles, performing ultrasonic dispersion for 20 min to obtain a viscous suspension, extruding the viscous suspension into a sphere, curing the viscous suspension in a 5% magnesium chloride solution for 12 h, performing solid-liquid separation, washing, and freeze drying to obtain the porous magnetic semiconductor composite photocatalyst.
Example 5
The activity of the catalyst is evaluated by taking a 300W xenon lamp and a filter with the lambda of more than or equal to 420 nm as a light source, and immersing all test tubes in a constant-temperature water bath (25℃)In conducting the photocatalytic activity test experiment, 10 mg of the photocatalyst prepared in the examples of the present application was dispersed in 100 m L of rhodamine B (RhB) (10 mg/L) before the light irradiation, all the solutions were magnetically stirred in the dark for 30 minutes in order to achieve the adsorption/desorption equilibriummaxThe absorbance of the supernatant was measured at 553 nm. The ratio of the absorbance of the supernatant to the absorbance of the initial solution at different times is the ratio of the concentrations thereof (c/c 0) And is used for characterizing the degradation rate of the photocatalyst. The reaction is carried out for 2 hours, the degradation rate of rhodamine B reaches 75%, the reaction is carried out for 6 hours, the degradation rate of rhodamine B reaches more than 95%, and the degradation rate is highest and stable when the pH value of degradation is 5.5-7.5. And the solution of rhodamine B with the same concentration and volume is adopted without adding a catalyst, the catalytic reaction is carried out under the same conditions, and the degradation rate of the rhodamine B is 2.65 percent.
Claims (5)
1. A preparation method of a porous magnetic semiconductor composite photocatalyst is characterized by comprising the following process steps:
(1) preparing zinc and sulfur doped carbon quantum dots, namely adding 84-88 mass percent of 2.0 mol/L zinc chloride and 4-8 mass percent of thiourea into a reaction kettle with a polytetrafluoroethylene lining, stirring and dissolving, pretreating rabbit hair powder, covering a sealing cover, placing the rabbit hair powder into a constant temperature box, keeping the temperature at 120 +/-2 ℃, reacting for 8 hours to obtain colorless transparent liquid, dialyzing, and drying to obtain water-soluble zinc and sulfur doped carbon quantum dots, wherein the sum of the mass percent of the components is one hundred percent;
(2) preparing quantum dot modified silver phosphate, namely adding 83-88 mass percent of deionized water, 4-8 mass percent of disodium hydrogen phosphate and 0.5-2.0 mass percent of zinc and sulfur doped carbon quantum dots into a reactor, stirring and dissolving, dropwise adding 5-9 mass percent of 12 mol/L silver nitrate solution, keeping the sum of the mass percent of the components at one hundred percent, stirring and reacting for 18 hours in a dark place, carrying out solid-liquid separation, washing and drying to obtain the quantum dot modified silver phosphate;
(3) preparing a porous magnetic semiconductor composite photocatalyst: adding deionized water into a reactor according to the following composition by mass percent: 60-66%, protein powder: 6-10%, locust bean gum: 3-6%, stirring and dissolving, and modifying the silver phosphate by the quantum dots: 18-22%, aminated iron sesquioxide magnetic nanoparticles: 4-6 percent of the porous magnetic semiconductor composite photocatalyst is obtained by ultrasonic dispersion for 20 min, wherein the sum of the mass percentages of the components is one hundred percent, a viscous suspension is obtained, the viscous suspension is extruded into a sphere, the sphere is solidified in a 5 percent magnesium chloride solution for 12 hours, and the porous magnetic semiconductor composite photocatalyst is obtained by solid-liquid separation, washing and freeze drying.
2. The preparation method of the porous magnetic semiconductor composite photocatalyst according to claim 1, wherein the pre-treated rabbit hair powder in step (1) is prepared by washing rabbit hair with water to remove impurities, drying, pulverizing, sieving with a 100-mesh sieve, soaking the rabbit hair powder in 10% hydrogen peroxide solution by mass for 6h according to a solid-to-liquid ratio of 1: 40m L, boiling for 5min, cooling, washing with deionized water, performing solid-liquid separation, and drying.
3. The method for preparing the porous magnetic semiconductor composite photocatalyst according to claim 1, wherein the molar ratio of disodium hydrogen phosphate to silver nitrate in step (2) is 1: 3-3.2.
4. The method for preparing the porous magnetic semiconductor composite photocatalyst according to claim 1, wherein in the step (3), the extruded sphere has a particle size of 0.5-2.0 mm.
5. The porous magnetic semiconductor composite photocatalyst prepared by the method for preparing the porous magnetic semiconductor composite photocatalyst according to claim 1.
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