CN105879890B - Magnetic composite photocatalyst and its preparation method and application - Google Patents
Magnetic composite photocatalyst and its preparation method and application Download PDFInfo
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- CN105879890B CN105879890B CN201610238572.2A CN201610238572A CN105879890B CN 105879890 B CN105879890 B CN 105879890B CN 201610238572 A CN201610238572 A CN 201610238572A CN 105879890 B CN105879890 B CN 105879890B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 70
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 70
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 70
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 65
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 44
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000003115 biocidal effect Effects 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 17
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 45
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 26
- 238000001291 vacuum drying Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000001509 sodium citrate Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 13
- 238000002955 isolation Methods 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 8
- -1 sodium citrate ethylene glycol Chemical compound 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 5
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229960003405 ciprofloxacin Drugs 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RRXWRHLYVPTSIF-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;silver Chemical compound [Ag].OC(=O)CC(O)(C(O)=O)CC(O)=O RRXWRHLYVPTSIF-UHFFFAOYSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/185—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
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/396—
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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
-
- 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
Abstract
The invention discloses a kind of magnetic composite photocatalysts and its preparation method and application, and the magnetic composite photocatalyst is with Fe3O4Nano particle is core, Fe3O4Nano grain surface is coated with SiO2Inert layer, SiO2Inert layer surface enrichment has Ag3PO4, Ag3PO4Surface modification has AgCl.Its preparation method includes：Prepare Fe3O4‑SiO2Carrier prepares Fe3O4‑SiO2@Ag3PO4With preparation Fe3O4‑SiO2@Ag3PO4/AgCl.The magnetic composite photocatalyst of the present invention can be applied to processing antibiotic waste water, have the advantages that visible light utilization efficiency is high, it is convenient to recycle, photocatalysis performance is stable and high to antibiotic degradation efficiency.
Description
Technical field
The invention belongs to antibiotic waste water process fields, and in particular to a kind of magnetic composite photocatalyst and preparation method thereof
And application.
Background technology
With the continuous improvement of social development and human material's demand, antibiotic be widely used in treating human body diseases and
Livestock and poultry, the bacterial disease of aquatic products are treated and prevented, causes it constantly long-pending in the environment in worldwide a large amount of uses
It is tired.Antibiotic pollution, which is likely to become, endangers one of factor of public health, it is necessary to cause the great attention of people, therefore explores
Effective repair has very important significance with control measures.
Due to the bacteriostasis of antibiotic, traditional biologic treating technique need to increase pretreatment when handling antibiotic waste water
Unit is to reduce bio-toxicity, and cost is larger and treatment effect is bad.And photocatalysis oxidation technique is due to its green, environmental protection, height
The advantages that effect, gets the attention in terms of environment pollution control.However, using nano-titanium dioxide as most of light of representative
Catalyst is only in ultraviolet light（Only account for solar radiation total amount 5%）Irradiation is lower could to generate photocatalytic activity.Relatively low solar energy profit
Application of the photochemical catalyst in the depollution of environment and new energy development etc. is greatly limited with rate.There is strong oxidizing property as one kind
Visible-light photocatalyst, silver orthophosphate（Ag3PO4）It is concerned in recent years, the sun of 520 nm can be less than with absorbing wavelength
Light.However separation of solid and liquid nanocatalyst is relatively difficult, Ag3PO4Stability difference in water causes photocatalysis performance easily to drop
It is low, so as to limit practical application of the photocatalysis technology in water process.
The content of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of visible light utilization efficiency height, return
Receive magnetic composite photocatalyst stable and high to antibiotic degradation efficiency using convenient, photocatalysis performance and preparation method thereof and
Using.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of magnetic composite photocatalyst, the magnetic composite photocatalyst is with Fe3O4Nano particle is core, the Fe3O4
Nano grain surface is coated with SiO2Inert layer, the SiO2Inert layer surface enrichment has Ag3PO4, the Ag3PO4Surface modification
There is AgCl.
The magnetic composite photocatalyst of the present invention is that AgCl is loaded to magnetic core-shell material using the method for template in situ
Fe3O4-SiO2@Ag3PO4Surface is prepared, the Fe3O4-SiO2@Ag3PO4It is by silver-citric acid complex（Ag-C6H8O6）
With being enriched with PO4 3-The Fe of functional group3O4-SiO2Particle is prepared by ion exchange, Fe3O4-SiO2It is by SiO2Uniformly cladding
Fe3O4Nano-particle obtains.
The inventive concept total as one, the present invention also provides a kind of preparation method of magnetic composite photocatalyst, bags
Include following steps：
（1）By Fe3O4Nano particle is distributed in water, adds in polyethylene glycol 200 and isopropanol, adjusts gained mixed liquor
PH value adds ethyl orthosilicate and is reacted, obtain Fe more than 113O4-SiO2Carrier；
（2）By Fe3O4-SiO2Support dispersion adds in NaH into water2PO4Solution after vibration, obtains enrichment PO4 3-Functional group
Fe3O4-SiO2The dispersion liquid of carrier；To AgNO3Ethylene glycol solution in add in sodium citrate ethylene glycol solution, after stirring,
Obtain Ag-C6H8O6Complex solution；By the enrichment PO4 3-The Fe of functional group3O4-SiO2The dispersion liquid of carrier is added to described
Ag-C6H8O6In complex solution, after reaction, Fe is obtained3O4-SiO2@Ag3PO4；
（3）By step（2）Obtained Fe3O4-SiO2@Ag3PO4It is distributed in water, to Fe3O4-SiO2@Ag3PO4It is scattered
NaCl solution is added in liquid, after reaction, obtains Fe3O4-SiO2@Ag3PO4/AgCl。
In the preparation method of above-mentioned magnetic composite photocatalyst, it is preferred that the step（1）In, the Fe3O4Nanometer
The molar ratio of particle and the ethyl orthosilicate is 1: 3~5；The volume ratio of the water and the isopropanol is 1: 2~2.5；
The step（2）In, the Fe3O4-SiO2The quality of carrier and the NaH2PO4The ratio between mole for 0.5g~
1g: 0.0025mol~0.0075mol；The AgNO3Molar ratio with the sodium citrate is 2.5~3: 1；
The step（3）In, the Fe3O4-SiO2@Ag3PO4The ratio between the mole of quality and the NaCl for 1g~
1.2g: 0.0008mol~0.001mol.
In the preparation method of above-mentioned magnetic composite photocatalyst, it is preferred that the step（2）In, the NaH2PO4It is molten
The concentration of liquid is 0.1mol/L~0.15mol/L, the AgNO3Ethylene glycol solution in AgNO3Concentration for 0.3mol/L~
0.45mol/L, the concentration of sodium citrate is 0.1mol/L~0.15mol/L in the ethylene glycol solution of the sodium citrate；It is described
Step（3）In, the concentration of the NaCl solution is 0.1mol/L~0.15mol/L.
In the preparation method of above-mentioned magnetic composite photocatalyst, it is preferred that the step（1）In, before adjusting pH value
It first stands, time of repose is 40min~60min, and the feed postition of the ethyl orthosilicate carries out when being stirring at low speed mixed liquor
It is added dropwise, mixing speed is 60rpm~80rpm, and time of the reaction is 12h~for 24 hours；
And/or the step（2）In, the NaH2PO4To be added dropwise, the time of the vibration is the feed postition of solution
For 24 hours~30h；For the feed postition of the ethylene glycol solution of the sodium citrate to be added dropwise, the rate of addition is 30 drops/min~60
Drop/min（It is preferred that 1 drop/sec）, the speed of the stirring is 800rpm~1000rpm, time of the stirring for 45min~
60min；The enrichment PO4 3-The Fe of functional group3O4-SiO2The feed postition of the dispersion liquid of carrier is is added dropwise, the rate of addition
For 30 drops/min~60 drops/min（It is preferred that 1 drop/sec）, the time of the reaction is 30min~60min；
And/or the step（3）In, the feed postition of the NaCl solution to be added dropwise, the rate of addition for 30 drops/
Min~60 drops/min（It is preferred that 1 drop/sec）, the time of the reaction is 30min~45min.
In the preparation method of above-mentioned magnetic composite photocatalyst, it is preferred that the step（1）In, the reaction is completed
Afterwards, separated, cleaned and dried, obtain Fe3O4-SiO2Carrier；Described to be separated into Magnetic Isolation, the cleaning is clear for ethyl alcohol
It washes, wash number is 3 times~5 times, and the drying is vacuum drying, and vacuum drying temperature is 60 DEG C~80 DEG C, vacuum drying
Time be 12h~for 24 hours；
And/or the step（2）In, it after the completion of the reaction, separated, cleaned and is dried, obtain Fe3O4-SiO2@
Ag3PO4；Described to be separated into Magnetic Isolation, using washes of absolute alcohol after first washing, the number of washing is 3 times~5 for the cleaning
Secondary, the wash number of absolute ethyl alcohol is 3 times~5 times, and the drying is vacuum drying, and vacuum drying temperature is 60 DEG C~80
DEG C, the vacuum drying time is 12h~for 24 hours；
And/or the step（3）In, it after the completion of the reaction, separated, washed and is dried, obtain Fe3O4-SiO2@
Ag3PO4/AgCl；Described to be separated into Magnetic Isolation, the washing is washing, and washing times are 3 times~5 times, and the drying is true
Sky is dry, and vacuum drying temperature is 60 DEG C~80 DEG C, and the vacuum drying time is 12h~for 24 hours.
In the preparation method of above-mentioned magnetic composite photocatalyst, it is preferred that the Fe3O4Nano particle is mainly by molten
The hot method of agent is prepared：By FeCl3It is dissolved in NaAc in ethylene glycol, gained mixed solution reacts for 24 hours at 180 DEG C~200 DEG C
~36h after cooling, through separating, cleaning and dry, obtains Fe3O4Nano particle.
In the preparation method of above-mentioned magnetic composite photocatalyst, it is preferred that the Fe3O4The preparation process of nano particle
In, FeCl in the mixed solution3Initial concentration for 0.1mol/L~0.15mol/L, in the mixed solution NaAc just
Beginning concentration is 0.35mol/L~0.40mol/L, and described to be separated into Magnetic Isolation, the cleaning is water after first washes of absolute alcohol
Be washed till neutrality, the drying is vacuum drying, and vacuum drying temperature is 60 DEG C~80 DEG C, the vacuum drying time for 12h~
24h。
The inventive concept total as one, the present invention also provides a kind of above-mentioned magnetic composite photocatalysts or above-mentioned
Application of the magnetic composite photocatalyst made from preparation method in antibiotic waste water is handled.
In above-mentioned application, it is preferred that the application comprises the following steps：By the magnetic coupling light under illumination condition
Catalyst is for antibiotic waste water of degrading, and intensity control is in 30 W/m2~50 W/m2, in the antibiotic waste water antibiotic just
Beginning concentration is 5mg/L~20mg/L, and the additive amount of the magnetic composite photocatalyst is 1.0g/L~3.0g/L, the antibiotic
6~8, the time of the degradation is 60min~90min for the pH value control of waste water.
In above-mentioned application, it is preferred that the illumination condition is using xenon lamp as light source analogy sunlight.
In the present invention, the sodium citrate can be anhydrous citric acid sodium, Sodium Citrate, usp, Dihydrate Powder or five water citric acid sodium.
Compared with prior art, the advantage of the invention is that：
1st, the present invention provides a kind of magnetic composite photocatalyst, fixation support is by SiO2The magnetic Nano of cladding
Fe3O4What particle was formed, magnetic Fe3O4Nano particle imparts catalyst magnetism characteristic, under the conditions of existing for external magnetic field,
It can realize the quick separation of solid and liquid of catalysis material, the separation and recovery and recycling of magnetic composite photocatalyst are simple and convenient；
Secondly, in magnetic Fe3O4Nano grain surface coated Si O2Inert layer avoids Ag3PO4Cross reaction occurs with Ferrite Material,
Reduce the loss in light induced electron and hole, photocatalysis performance is not easy to reduce；Ag simultaneously3PO4Visible light photocatalysis performance it is strong,
It can be less than the sunlight of 520nm with absorbing wavelength；Finally, AgCl is modified in Ag3PO4Surface improves Ag3PO4In water
Stability, stablize photocatalysis performance, so as to improve the degradation efficiency of antibiotic.The magnetic composite photocatalyst of the present invention
Visible light utilization efficiency it is high, recycle convenient, and photocatalysis performance is stablized, and can greatly reduce being degraded into for antibiotic
This, has a good application prospect.
2nd, the present invention provides a kind of preparation method of magnetic composite photocatalyst, magnetic Fe is combined3O4Nano particle,
TEOS、NaH2PO4、Ag-C6H8O6Complex compound and AgCl each the characteristics of, first by magnetic Fe3O4Nano particle is dehydrated key with TEOS
Conjunction forms Fe3O4-SiO2Carrier, then make its surface enrichment PO in acid condition4 3-Functional group, then by itself and Ag-C6H8O6Complexing
Object reacts, and Fe is obtained by ion exchange3O4-SiO2@Ag3PO4, finally using the method for template in situ in its area load AgCl
Obtain Fe3O4-SiO2@Ag3PO4/ AgCl is the magnetic composite photocatalyst of the present invention.
3rd, magnetic composite photocatalyst of the invention can be used for antibiotic waste water of degrading, and can effectively improve antibiotic waste water
Degradation efficiency, degradation rate are up to more than 95%, can be recycled after being separated under magneticaction.The present invention solves photochemical catalyst
Unstable in water, visible light utilization efficiency is low, photocatalysis performance is easily reduced and is not easily recycled and the critical problems such as utilizes.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection domain.
Material and instrument employed in following embodiment are commercially available.
Embodiment 1
A kind of magnetic composite photocatalyst of the present invention, the magnetic composite photocatalyst is with Fe3O4Nano particle is core,
Fe3O4Nano grain surface is coated with SiO2Inert layer, SiO2Inert layer surface enrichment has Ag3PO4, Ag3PO4Surface modification has
AgCl。
A kind of preparation method of the magnetic composite photocatalyst of above-mentioned the present embodiment, comprises the following steps：
（1）Prepare Fe3O4Nano particle
（1.1）Weigh 2.7g FeCl3·6H2O and 4.1g NaAc3H2O is dissolved in the ethylene glycol of 80mL, is sufficiently stirred
Make its dissolving, obtain mixed solution.
（1.2）By step（1.1）In obtained mixed solution be put into 100mL hydrothermal reaction kettles, then in an oven plus
Heat keeps for 24 hours, being then cooled to room temperature to 180 DEG C.
（1.3）Reaction product in hydrothermal reaction kettle is poured into beaker, by Magnetic Isolation, removes supernatant, gained
Precipitation is washed 5 times with absolute ethyl alcohol, then is washed with distilled water 5 times, and then Magnetic Isolation, in 60 DEG C of vacuum drying for 24 hours, obtains
Fe3O4Nano particle.
（2）Prepare Fe3O4-SiO2Carrier
（2.1）By 0.5g steps（1）In Fe3O4Nano particle is dispersed in 50mL distilled water, adds in 2mL polyethylene glycol
200, make even particulate dispersion into solution, then add in 100mL isopropanols, gained mixed liquor stands 40 min.
（2.2）The pH value that above-mentioned mixed liquor is adjusted with concentrated ammonia liquor is 12, the stirring at low speed under the conditions of rotating speed is 60rpm, drop
Add 2mL ethyl orthosilicates（TEOS）, react 12h.
（2.3）By step（2.2）In reaction product by Magnetic Isolation after, remove supernatant, gained precipitation ethyl alcohol
Cleaning 3 times in 80 DEG C of vacuum drying for 24 hours, obtains Fe3O4-SiO2Carrier.
（3）Prepare Fe3O4-SiO2@Ag3PO4
（3.1）By 1.0g steps（2）Obtained Fe3O4-SiO2Support dispersion is into 25mL distilled water, in mechanical agitation item
The NaH of 50mL 0.1mol/L is added dropwise under part thereto2PO4Enrichment PO is prepared in solution, vibration for 24 hours4 3-Functional group
Fe3O4-SiO2The dispersion liquid of carrier.
（3.2）By 2.55g AgNO3It is distributed in 50mL ethylene glycol and obtains AgNO3Ethylene glycol solution；By 1.47g lemons
Sour sodium（Na3C6H5O7·2H2O）It is distributed in 50mL ethylene glycol and obtains the ethylene glycol solution of sodium citrate；It is 1 by rate of addition
Drop/sec, the ethylene glycol solution of sodium citrate is added dropwise to AgNO3Ethylene glycol solution in, and rotating speed be 800rpm items
45 min are vigorously stirred under part, obtain Ag-C6H8O6Complex solution.
（3.3）It it is 1 drop/sec by rate of addition, by step（3.1）In enrichment PO4 3-The Fe of functional group3O4-SiO2Carrier
Dispersant liquid drop be added to step（3.2）Ag-C6H8O6In complex solution, after reacting 30min, Magnetic Isolation goes out sample, first uses
Deionized water is cleaned 4 times, then with washes of absolute alcohol 4 times, sample is then put into 80 DEG C of vacuum drying chambers dry 12h, is obtained
To Fe3O4-SiO2@Ag3PO4。
（4）Prepare Fe3O4-SiO2@Ag3PO4/AgCl
（4.1）Take 1g steps（3）Obtained Fe3O4-SiO2@Ag3PO4It is distributed in 50mL distilled water, obtains Fe3O4-
SiO2@Ag3PO4Dispersion liquid.
（4.2）It is 1 drop/sec by rate of addition, 10mL, 0.1mol/L NaCl solution is added dropwise to Fe3O4-SiO2@
Ag3PO4Dispersion liquid in, in rotating speed be oscillating reactions 30min under the conditions of 120rpm.
（4.3）It will（4.2）Reaction product separated under magneticaction, gained precipitation be washed with distilled water 3 times, then will
Sample is put into 60 DEG C of vacuum drying chambers after drying for 24 hours, obtains Fe3O4-SiO2@Ag3PO4/ AgCl is that magnetism of the invention is answered
Closing light catalyst.
A kind of application of above-mentioned magnetic composite photocatalyst manufactured in the present embodiment in antibiotic waste water is handled, including with
Lower step：
Using xenon lamp as light source analogy sunlight, intensity control is in 30W/m2, initial concentration of the Ciprofloxacin in waste water
For 10 mg/L, dosage of the magnetic composite photocatalyst into waste water is 2.0 g/L, during the pH of waste water=7, reacts 90 min
The degradation rate of Ciprofloxacin afterwards is up to 95%.Photochemical catalyst separates Posterior circle after use under magneticaction and uses, and recycles
5 times, catalytic activity does not reduce significantly.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications without departing from the principle of the present invention, also should be regarded as the present invention guarantor
Protect scope.
Claims (8)
1. a kind of magnetic composite photocatalyst, which is characterized in that the magnetic composite photocatalyst is with Fe3O4Nano particle is core,
The Fe3O4Nano grain surface is coated with SiO2Inert layer, the SiO2Inert layer surface enrichment has Ag3PO4, the Ag3PO4
Surface modification has AgCl；
The preparation method of the magnetic composite photocatalyst comprises the following steps：
（1）By Fe3O4Nano particle is distributed in water, adds in polyethylene glycol 200 and isopropanol, adjusts the pH value of gained mixed liquor
More than 11, add ethyl orthosilicate and reacted, obtain Fe3O4-SiO2Carrier；
（2）By Fe3O4-SiO2Support dispersion adds in NaH into water2PO4Solution after vibration, obtains enrichment PO4 3-Functional group
Fe3O4-SiO2The dispersion liquid of carrier；To AgNO3Ethylene glycol solution in add in sodium citrate ethylene glycol solution, after stirring, obtain
To Ag-C6H8O6Complex solution；By the enrichment PO4 3-The Fe of functional group3O4-SiO2The dispersion liquid of carrier is added to the Ag-
C6H8O6In complex solution, after reaction, Fe is obtained3O4-SiO2@Ag3PO4；
（3）By step（2）Obtained Fe3O4-SiO2@Ag3PO4It is distributed in water, to Fe3O4-SiO2@Ag3PO4Dispersion liquid in plus
Enter NaCl solution, after reaction, obtain Fe3O4-SiO2@Ag3PO4/AgCl；
The step（1）In, the Fe3O4The molar ratio of nano particle and the ethyl orthosilicate is 1: 3~5；The water and institute
The volume ratio for stating isopropanol is 1: 2~2.5；
The step（2）In, the Fe3O4-SiO2The quality of carrier and the NaH2PO4The ratio between mole be 0.5g~1g:
0.0025mol~0.0075mol；The AgNO3Molar ratio with the sodium citrate is 2.5~3: 1；
The step（3）In, the Fe3O4-SiO2@Ag3PO4The ratio between the mole of quality and the NaCl be 1g~1.2g:
0.0008mol~0.001mol；
The Fe3O4Nano particle is mainly prepared by solvent-thermal method：By FeCl3It is dissolved in NaAc in ethylene glycol, gained mixes
It closes solution and reacts for 24 hours~36h at 180 DEG C~200 DEG C, after cooling, through separating, cleaning and dry, obtain Fe3O4Nano particle.
2. a kind of preparation method of magnetic composite photocatalyst, comprises the following steps：
（1）By Fe3O4Nano particle is distributed in water, adds in polyethylene glycol 200 and isopropanol, adjusts the pH value of gained mixed liquor
More than 11, add ethyl orthosilicate and reacted, obtain Fe3O4-SiO2Carrier；
（2）By Fe3O4-SiO2Support dispersion adds in NaH into water2PO4Solution after vibration, obtains enrichment PO4 3-Functional group
Fe3O4-SiO2The dispersion liquid of carrier；To AgNO3Ethylene glycol solution in add in sodium citrate ethylene glycol solution, after stirring, obtain
To Ag-C6H8O6Complex solution；By the enrichment PO4 3-The Fe of functional group3O4-SiO2The dispersion liquid of carrier is added to the Ag-
C6H8O6In complex solution, after reaction, Fe is obtained3O4-SiO2@Ag3PO4；
（3）By step（2）Obtained Fe3O4-SiO2@Ag3PO4It is distributed in water, to Fe3O4-SiO2@Ag3PO4Dispersion liquid in plus
Enter NaCl solution, after reaction, obtain Fe3O4-SiO2@Ag3PO4/AgCl；
The step（1）In, the Fe3O4The molar ratio of nano particle and the ethyl orthosilicate is 1: 3~5；The water and institute
The volume ratio for stating isopropanol is 1: 2~2.5；
The step（2）In, the Fe3O4-SiO2The quality of carrier and the NaH2PO4The ratio between mole be 0.5g~1g:
0.0025mol~0.0075mol；The AgNO3Molar ratio with the sodium citrate is 2.5~3: 1；
The step（3）In, the Fe3O4-SiO2@Ag3PO4The ratio between the mole of quality and the NaCl be 1g~1.2g:
0.0008mol~0.001mol；
The Fe3O4Nano particle is mainly prepared by solvent-thermal method：By FeCl3It is dissolved in NaAc in ethylene glycol, gained mixes
It closes solution and reacts for 24 hours~36h at 180 DEG C~200 DEG C, after cooling, through separating, cleaning and dry, obtain Fe3O4Nano particle.
3. the preparation method of magnetic composite photocatalyst according to claim 2, which is characterized in that the step（2）In,
The NaH2PO4The concentration of solution is 0.1mol/L~0.15mol/L, the AgNO3Ethylene glycol solution in AgNO3Concentration
For 0.3mol/L~0.45mol/L, in the ethylene glycol solution of the sodium citrate concentration of sodium citrate for 0.1mol/L~
0.15mol/L；The step（3）In, the concentration of the NaCl solution is 0.1mol/L~0.15mol/L.
4. the preparation method of the magnetic composite photocatalyst according to Claims 2 or 3, which is characterized in that the step（1）
In, it is first stood before adjusting pH value, time of repose is 40min~60min, and the feed postition of the ethyl orthosilicate stirs for low speed
It is added dropwise when mixing mixed liquor, mixing speed is 60rpm~80rpm, and time of the reaction is 12h~for 24 hours；
And/or the step（2）In, the NaH2PO4The feed postition of solution to be added dropwise, time of the vibration for for 24 hours~
30h；The feed postition of the ethylene glycol solution of the sodium citrate to be added dropwise, the rate of addition for the drop of 30 drops/min~60/
Min, the speed of the stirring is 800rpm~1000rpm, and the time of the stirring is 45min~60min；The enrichment PO4 3-
The Fe of functional group3O4-SiO2The feed postition of the dispersion liquid of carrier to be added dropwise, the rate of addition for the drop of 30 drops/min~60/
Min, the time of the reaction is 30min~60min；
And/or the step（3）In, the feed postition of the NaCl solution to be added dropwise, the rate of addition for 30 drops/min~
60 drops/min, the time of the reaction is 30min~45min.
5. the preparation method of the magnetic composite photocatalyst according to Claims 2 or 3, which is characterized in that the step（1）
In, it after the completion of the reaction, separated, cleaned and is dried, obtain Fe3O4-SiO2Carrier；It is described to be separated into Magnetic Isolation, institute
State cleaning for ethyl alcohol clean, wash number be 3 times~5 times, the drying for vacuum drying, vacuum drying temperature for 60 DEG C~
80 DEG C, the vacuum drying time is 12h~for 24 hours；
And/or the step（2）In, it after the completion of the reaction, separated, cleaned and is dried, obtain Fe3O4-SiO2@
Ag3PO4；Described to be separated into Magnetic Isolation, using washes of absolute alcohol after first washing, the number of washing is 3 times~5 for the cleaning
Secondary, the wash number of absolute ethyl alcohol is 3 times~5 times, and the drying is vacuum drying, and vacuum drying temperature is 60 DEG C~80
DEG C, the vacuum drying time is 12h~for 24 hours；
And/or the step（3）In, it after the completion of the reaction, separated, washed and is dried, obtain Fe3O4-SiO2@
Ag3PO4/AgCl；Described to be separated into Magnetic Isolation, the washing is washing, and washing times are 3 times~5 times, and the drying is true
Sky is dry, and vacuum drying temperature is 60 DEG C~80 DEG C, and the vacuum drying time is 12h~for 24 hours.
6. the preparation method of the magnetic composite photocatalyst according to Claims 2 or 3, which is characterized in that the Fe3O4It receives
In the preparation process of rice grain, FeCl in the mixed solution3Initial concentration for 0.1mol/L~0.15mol/L, it is described mixed
The initial concentration of NaAc in solution is closed as 0.35mol/L~0.40mol/L, described to be separated into Magnetic Isolation, the cleaning is first
Neutrality is washed to after washes of absolute alcohol, the drying is vacuum drying, and vacuum drying temperature is 60 DEG C~80 DEG C, and vacuum is done
The dry time is 12h~for 24 hours.
7. a kind of magnetic composite photocatalyst as described in claim 1 or the system as any one of claim 2~6
Application of the magnetic composite photocatalyst made from Preparation Method in antibiotic waste water is handled.
8. application according to claim 7, which is characterized in that the application comprises the following steps：It will under illumination condition
The magnetic composite photocatalyst is for antibiotic waste water of degrading, and intensity control is in 30 W/m2~50 W/m2, the antibiotic gives up
The initial concentration of antibiotic is 5mg/L~20mg/L in water, the additive amount of the magnetic composite photocatalyst for 1.0g/L~
3.0g/L, 6~8, the time of the degradation is 60min~90min for the pH value control of the antibiotic waste water.
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