CN106430516A - Method for degrading antibacterial drug in water based on iron-doped ordered mesoporous cobalt tetroxide-activated monopersulfate - Google Patents
Method for degrading antibacterial drug in water based on iron-doped ordered mesoporous cobalt tetroxide-activated monopersulfate Download PDFInfo
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- CN106430516A CN106430516A CN201610685175.XA CN201610685175A CN106430516A CN 106430516 A CN106430516 A CN 106430516A CN 201610685175 A CN201610685175 A CN 201610685175A CN 106430516 A CN106430516 A CN 106430516A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229940124350 antibacterial drug Drugs 0.000 title abstract 4
- 239000010941 cobalt Substances 0.000 title abstract 2
- 229910017052 cobalt Inorganic materials 0.000 title abstract 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract 2
- 230000000593 degrading effect Effects 0.000 title abstract 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 67
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006731 degradation reaction Methods 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 15
- 230000000844 anti-bacterial effect Effects 0.000 claims description 13
- 229940088710 antibiotic agent Drugs 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 10
- 238000007605 air drying Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical group [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910001429 cobalt ion Inorganic materials 0.000 abstract 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- -1 iron ions Chemical class 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052571 earthenware Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 208000031295 Animal disease Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003640 drug residue Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- B01J35/61—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- 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
- C02F2305/02—Specific form of oxidant
Abstract
The invention discloses a method for degrading an antibacterial drug in water based on iron-doped ordered mesoporous cobalt tetroxide-activated monopersulfate. The method is implemented by the following specific steps: preparing TOM-Co3O4; preparing magnetic TOM-Co3O4/CoFe2O4; thoroughly mixing the magnetic TOM-Co3O4/CoFe2O4 and an antibacterial drug-containing water solution, and transferring to a brown shake flask; adding the monopersulfate; separating the magnetic TOM-Co3O4/CoFe2O4 by using an external magnetic field. By the method provided by the invention, the removal rate of the typical antibacterial drug ciprofloxacin within 60 min exceeds 95%; the dissolution rate of cobalt ions and iron ions is very low, so that the environmental pollution is reduced; a catalyst can be separated for reuse, so that the operating cost is reduced.
Description
Technical field
The invention belongs to technical field of sewage, and in particular to emerging organic pollution and difficult degradation organic contamination in water
Resist in the processing method of thing, more particularly to a kind of single persulfate degradation water based on the order mesoporous Cobalto-cobaltic oxide activation of Fe2O3 doping
The method of bacterium medicine.
Background technology
In recent years, medicine and personal-care supplies（Pharmaceuticals and Personal Care Products,
PPCPs）Become a kind of emerging environmental contaminants, be all detected in the surrounding mediums such as subsoil water, surface water, soil,
And be proved to cause certain harm to environment and human health.Ciprofloxacin（Ciprofloxacin, CIP）Belong to quinolinoness
Class antibacterials, are widely used in the treatment of the mankind and Animal diseases.After the ciprofloxacin of residual enters human body, human body can be produced
Toxic and side effects, and greatly enhance the drug resistance of human body pathogen.On the other hand, after animal has taken in a large amount of ciprofloxacins, with excrement
Urine ejection is external, enters in natural environment, ecosystem is constituted potentially hazardous.Ciprofloxacin is as a kind of people and animals altogether
Medication, drug residue is bigger to human health damage by food chain.Research is had to point out, ciprofloxacin is more difficult to be dropped by microorganism
Solution, and can not effectively be removed by conventional water treatment process.Therefore, the dirt for finding that effective ways solve ciprofloxacin in environment is needed badly
Dye problem.
In recent years, based on potentiometric titrations（SO4 -·）High-level oxidation technology receive the extensive concern of researcher.
Wherein transition metal ionss activate single persulfate（Peroxymonosufate, PMS）System produces Strong oxdiative activity
SO4 -Efficient can carry out at room temperature, without the need for external energy（Ultrasound, thermal source and light source）, before wide application
Scape.But homogeneous list persulfate catalyst system and catalyzing has that catalyst is reclaimed difficult and easily caused raw.
Content of the invention
The invention provides a kind of form magnetic TOM-Co based on the order mesoporous Cobalto-cobaltic oxide of Fe2O3 doping3O4/CoFe2O4Activation
The method of antibacterials in single persulfate degradation water, it is intended to solve catalyst in homogeneous list persulfate activation systems（Transition
Metal ion）Reclaim problem that is difficult and easily causing secondary environmental pollution；Solve currently used heterogeneous spinel-type to urge
Agent specific surface area is little, the relatively low problem of catalytic capability；And heterogeneous TOM-Co3O4It is catalyzed in the single persulfate system of activation
The problem of agent reclaimer operation complexity.
A kind of method of antibacterials in single persulfate degradation water based on the order mesoporous Cobalto-cobaltic oxide activation of Fe2O3 doping,
Carry out according to the following steps：
First, TOM-Co is prepared3O4：
Co (NO is added to after template KIT-6 is fully ground3)2·6H2In the ethanol solution of O, 1 is stirred at ambient temperature
H obtains solution A；
By stepThe forced air drying under the conditions of 60 DEG C of resulting solution A obtains pink solid powder, by this solid powder
End is transferred in crucible, and places it in interior 5 h of roast under the conditions of 200 DEG C of Muffle furnace, the programming rate of the Muffle furnace
For 2 DEG C/min；
By stepBrown solid powder after middle roast is added to Co (NO after being fully ground3)2·6H2The ethanol of O is molten
In liquid, stir 1 h at ambient temperature and obtain solution B；
By stepThe forced air drying under the conditions of 60 DEG C of resulting solution B obtains black solid, and this solid is transferred to earthenware
In crucible, and interior 5 h of roast under the conditions of 450 DEG C of Muffle furnace is placed it in, the programming rate of the Muffle furnace is 2 DEG C/min；
By stepThe black solid powder of middle roast is cooled to room temperature, through adding after being fully ground to filling 2
In the round-bottomed flask of mol/L NaOH solution, under 60 DEG C of water bath condition, 12 h are stirred, by 30 min of solution left standstill after stirring
Supernatant is removed, above step is in triplicate；
By stepAfter products obtained therefrom spends ultra-pure water respectively and ethanol is cleaned repeatedly to pH=7, true under the conditions of 60 DEG C
Again through being fully ground to obtain TOM-Co after sky is dry3O4；
2nd, magnetic TOM-Co is prepared3O4/CoFe2O4：
By TOM-Co3O4It is added to Fe (NO3)3·9H2In O- ethanol solution, 1 h is stirred at ambient temperature；
Preferably, step 2Described in TOM-Co3O4、Fe(NO3)3·9H2The mol ratio of O is 1:1；
Preferably, step 2Described in Fe (NO3)3·9H2The molar concentration of O- ethanol solution is 0.4 mol/L；
By step 2The forced air drying under the conditions of 60 DEG C of solution after stirring obtains black solid powder, by this solid powder
End is transferred in crucible, and places it in interior 5 h of roast under the conditions of 450 DEG C of Muffle furnace, the programming rate of the Muffle furnace
For 2 DEG C/min；
By step 2Black solid powder after middle roast is fully ground to obtain TOM-Co3O4/CoFe2O4, stand-by；
3rd, by magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed with aqueous solution containing ciprofloxacin, is transferred in brown shaking flask；
4th, the brown shaking flask in adding single persulfate to step 3, water-bath oscillating reactionss 30 ~ 120 at 20 ~ 50 DEG C
min；
5th, pass through externally-applied magnetic field separation magnetic TOM-Co3O4/CoFe2O4, the TOM-Co of recovery3O4/CoFe2O4With ethanol and going
Ionized water is cleaned repeatedly and is vacuum dried under the conditions of 60 DEG C, the TOM-Co being recycled3O4/CoFe2O4.
Preferably, stepDescribed in template KIT-6, Co (NO3)2·6H2The mol ratio of O is 1:1.
Preferably, stepDescribed in Co (NO3)2·6H2The molar concentration of O solution is 0.8 mol/L.
Preferably, stepDescribed in the mass ratio of black solid and NaOH solution be 1:100~200.
Preferably, step 2Described in TOM-Co3O4、Fe(NO3)3·9H2The mol ratio of O is 1:1.
Preferably, step 2Described in Fe (NO3)3·9H2The molar concentration of O- ethanol solution is 0.4 mol/L.
Preferably, the TOM-Co described in step 33O4/CoFe2O4Dosage be per liter of aqueous solution containing ciprofloxacin
10 ~ 200 mg of middle input.
Preferably, the concentration of aqueous solution containing ciprofloxacin described in step 3 is 1 ~ 20 mg/L.
Preferably, single persulfate described in step 4 be Potassium peroxysulfate, single Ammonium persulfate., single sodium peroxydisulfate and
At least one in single persulfuric acid calcium；Described single persulfate is 66 with the mol ratio of ciprofloxacin in aqueous solution:1.
Meaning of the present invention is to solve catalyst in homogeneous list persulfate activation systems（Transition metal ionss）Reclaim tired
Problem that is difficult and easily causing secondary environmental pollution；Solve currently used heterogeneous spinel-type specific surface area of catalyst little,
The relatively low problem of catalytic capability；Solve heterogeneous TOM-Co3O4Catalyst reclaimer operation complexity in the single persulfate system of activation
Problem.Magnetic TOM-Co that the present invention is adopted3O4/CoFe2O4Possess very big specific surface area and abundant pore passage structure, can
While adsorbed target Organic substance, the substantial amounts of oxygen-containing functional group in surface can activate single persulfate further, generate SO4 -Can
Accelerate the oxidative degradation of target contaminant.In TOM-Co3O4/CoFe2O4Use during, metal ions M2+/M3+Valence state turn
Become and the balance between single persulfate decomposition ensure that catalyst is played and continue efficient catalytic performance；TOM-Co3O4/
CoFe2O4With good magnetic and reuse, easy to operate, reduce operating cost.
The present invention has the beneficial effect that：
1.TOM-Co3O4/CoFe2O4During the single persulfate of catalysis, digestion of metallic ion is very low, reduces environment
Secondary pollution.
2.TOM-Co3O4/CoFe2O4SO can be produced with efficient activation list persulfate4 -, easy to operate, energy efficient,
Without the need for carrying out ultraviolet irradiation, ultrasonic cavitation, heating etc. to system.
3.TOM-Co3O4/CoFe2O4There is very big specific surface area and abundant pore passage structure, can be easier and single mistake
Sulfate and organic pollution contact, are greatly enhanced catalytic efficiency.
4.TOM-Co3O4/CoFe2O4Surface is contained abundant oxygen-containing functional group and can be produced with efficient catalytic list persulfate
SO4 -Oxidative degradation Organic substance, clearance is more than 95 %.
5.TOM-Co3O4/CoFe2O4Can be recycled and reused by way of externally-applied magnetic field, be reduced operating cost.
Description of the drawings
Fig. 1 be under different working conditions Ciprofloxacin Concentration percentage ratio with the graph of a relation of time.
Fig. 2 is reuse number of times to TOM-Co3O4/CoFe2O4The impact figure of the single persulfate degraded ciprofloxacin of activation.
Fig. 3 is TOM-Co3O4/CoFe2O4Through the design sketch before and after transmission from one meridian to another magnet adsorption, wherein left figure is to inhale without Magnet
Attached design sketch, right figure is the design sketch through magnet adsorption.
Specific embodiment
Technical solution of the present invention is not limited to specific implementation method exemplified below, also includes any between each specific embodiment
Combination.
Embodiment 1
First, TOM-Co is prepared3O4：
Co (NO is added to after template KIT-6 is fully ground3)2·6H2In O solution, stir at ambient temperature 1 h obtain molten
Liquid A；
Step oneDescribed in template KIT-6, Co (NO3)2·6H2The mol ratio of O is 1:1；
Step oneDescribed in solution with ethanol as solvent；
Step oneDescribed in Co (NO3)2·6H2The molar concentration of O solution is 0.8 mol/L；
By stepThe forced air drying under the conditions of 60 DEG C of resulting solution A obtains pink solid powder, by this solid powder
End is transferred in crucible, and places it in interior 5 h of roast under the conditions of 200 DEG C of Muffle furnace, the programming rate of the Muffle furnace
For 2 DEG C/min；
By stepBrown solid powder after middle roast is added to Co (NO after being fully ground3)2·6H2In O solution,
1 h is stirred under room temperature condition obtains solution B；
Step oneDescribed in solution with ethanol as solvent；
Step oneDescribed in Co (NO3)2·6H2The molar concentration of O solution is 0.8 mol/L；
By stepThe forced air drying under the conditions of 60 DEG C of resulting solution B obtains black solid, and this solid is transferred to earthenware
In crucible, and place it in interior 5 h of roast under the conditions of 450 DEG C of Muffle furnace；
Step oneDescribed in by black solid powder under the conditions of 450 DEG C 5 h of roast, the programming rate of Muffle furnace is 2
℃/min；
By stepThe black solid powder of middle roast is cooled to room temperature, through adding after being fully ground to filling 2
In the round-bottomed flask of mol/L NaOH solution, under 60 DEG C of water bath condition, 12 h are stirred, by 30 min of solution left standstill after stirring
Supernatant is removed, above step is in triplicate；
Step oneDescribed in black solid and 2 mol/L NaOH solution mass ratio be 1:(100~200)；
By stepIn the material that obtains spend ultra-pure water and washing with alcohol respectively to pH=7,60 DEG C of vacuum drying
Black solid is obtained, is stored for future use after this solid is fully ground.
2nd, magnetic TOM-Co is prepared3O4/CoFe2O4：
By TOM-Co3O4It is added to Fe (NO3)3·9H2In O solution, 1 h is stirred at ambient temperature；
Step oneDescribed in TOM-Co3O4、Fe(NO3)3·9H2The mol ratio of O is 1:1；
Step oneDescribed in solution with ethanol as solvent；
Step oneDescribed in Fe (NO3)3·9H2The molar concentration of O solution is 0.4 mol/L；
By step 2The forced air drying under the conditions of 60 DEG C of solution after stirring obtains black solid powder, by this solid powder
End is transferred in crucible, and places it in interior 5 h of roast under the conditions of 450 DEG C of Muffle furnace；
Step 2Described in by black solid powder under the conditions of 450 DEG C 5 h of roast, the programming rate of Muffle furnace is 2
℃/min；
By step 2Black solid powder after middle roast is standby after being fully ground.
3rd, by magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed with aqueous solution containing ciprofloxacin, is transferred in brown shaking flask；
TOM-Co described in step 33O4/CoFe2O4Dosage be 10 ~ 50 mg/L;
Concentration of aqueous solution containing ciprofloxacin described in step 3 is 1 ~ 5 mg/L；
The mixed liquor volume in brown shaking flask that is transferred to described in step 3 is 100 mL.
4th, single persulfate is added：Ciprofloxacin is carried out in brown shaking flask during single persulfate is added to step 3
Degradation reaction；
30 ~ 60 min of water-bath oscillating reactionss under the conditions of keeping reacting liquid temperature to be 20 ~ 30 DEG C, ciprofloxacin in achievable water
Efficiently remove, and obtain containing TOM-Co3O4/CoFe2O4Mixed solution；
Single persulfate described in step 4 is Potassium peroxysulfate, in single Ammonium persulfate., single sodium peroxydisulfate and single persulfuric acid calcium
A kind of or wherein several mixture；
Single persulfate described in step 4 is (10 ~ 50) with the mol ratio of ciprofloxacin in aqueous solution:1.
5th, pass through externally-applied magnetic field separation magnetic TOM-Co3O4/CoFe2O4：By externally-applied magnetic field separation magnetic TOM-Co3O4/
CoFe2O4, the TOM-Co of recovery3O4/CoFe2O4Cleaned with ethanol and deionized water repeatedly and vacuum under the conditions of 60 DEG C
Dry, the TOM-Co being recycled3O4/CoFe2O4；
TOM-Co described in step 53O4/CoFe2O4Cleaned with ethanol and deionized water repeatedly, wash number is no less than
5 times.
Ciprofloxacin percentage situation over time is tested, change curve is shown in accompanying drawing 1.
Embodiment 2：
Present embodiment as different from Example 1 in step 3 the concentration of target contaminant ciprofloxacin be 5 ~ 10 mg/L, its
His step and parameter are same as Example 1.
Embodiment 3：
Present embodiment as different from Example 1 in step 3 the concentration of target contaminant ciprofloxacin be 10 ~ 20 mg/L,
Other steps and parameter are same as Example 1.
Embodiment 4：
Present embodiment TOM-Co in step 3 as different from Example 13O4/CoFe2O4Dosage be 50 ~ 100 mg/L,
Other steps and parameter are same as Example 1.
Embodiment 5：
Present embodiment TOM-Co in step 3 as different from Example 13O4/CoFe2O4Dosage be 100 ~ 200 mg/
L, other steps and parameter are same as Example 1.
Embodiment 6：
Present embodiment as different from Example 1 in step 4 single persulfate and target contaminant mol ratio for (50 ~
100):1, other steps and parameter same as Example 1.
Embodiment 7：
Present embodiment as different from Example 1 in step 4 single persulfate with containing ciprofloxacin mol ratio for (100 ~
200):1, other steps and parameter same as Example 1.
Embodiment 8：
Present embodiment as different from Example 1 in step 4 temperature of reaction system be 30 ~ 50 DEG C, other steps and parameter
Same as Example 1.
Embodiment 9：
The TOM-Co that present embodiment is added in step 3 as different from Example 13O4/CoFe2O4For by outer in step 5
Plus the TOM-Co that magnetic field is reclaimed3O4/CoFe2O4, other steps and parameter same as Example 1.
Embodiment 10：Multiple reuse of catalyst（TOM-Co3O4/CoFe2O4）Activation PMS is pressed to ciprofloxacin degradation experiment
Following methods are carried out：
By magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed with aqueous solution containing ciprofloxacin, is transferred in brown shaking flask；
TOM-Co described in step 33O4/CoFe2O4For passing through externally-applied magnetic field recycled materials in step 5；
TOM-Co described in step 33O4/CoFe2O4Dosage be 100 mg/L；
Concentration of aqueous solution containing ciprofloxacin described in step 3 is 5 mg/L；
The mixed liquor volume in brown shaking flask that is transferred to described in step 3 is 100 mL.
2nd, single persulfate is added：Ciprofloxacin is carried out in brown shaking flask during single persulfate is added to step 3
Degradation reaction；
60 min of water-bath oscillating reactionss under the conditions of keeping reacting liquid temperature to be 25 ± 1 DEG C, in achievable water, ciprofloxacin is efficient
Remove, and obtain containing TOM-Co3O4/CoFe2O4Mixed solution；
Single persulfate described in step 4 is Potassium peroxysulfate, in single Ammonium persulfate., single sodium peroxydisulfate and single persulfuric acid calcium
A kind of or wherein several mixture；
Single persulfate described in step 4 is 66 with the mol ratio of ciprofloxacin in aqueous solution:1.
3rd, pass through externally-applied magnetic field separation magnetic TOM-Co3O4/CoFe2O4：By externally-applied magnetic field separation magnetic TOM-Co3O4/
CoFe2O4, the TOM-Co of recovery3O4/CoFe2O4Cleaned with ethanol and deionized water repeatedly and vacuum under the conditions of 60 DEG C
Dry, the TOM-Co being recycled3O4/CoFe2O4；
TOM-Co described in step 53O4/CoFe2O4Cleaned with ethanol and deionized water repeatedly, wash number is no less than
5 times.
The different TOM-Co of reuse number of times3O4/CoFe2O4When testing with persulfate synergistic sorption ciprofloxacin, ring third is husky
The graph of a relation of star residual concentration and time is shown in accompanying drawing 2.
TOM-Co after multiple recovery can be seen from accompanying drawing 23O4/CoFe2O4Remain in that very high catalytic performance, the 5th
The TOM-Co of secondary recovery3O4/CoFe2O4Under conditions of coexisting with single persulfate, in 60 min, the clearance of ciprofloxacin is still high
Reach 90 more than %.As can be seen here, TOM-Co3O4/CoFe2O4Possesses good reuse.
Comparative example 1 individually adds TOM-Co3O4/CoFe2O4The adsorption experiment of ciprofloxacin is carried out by the following method：
First, TOM-Co is prepared3O4：Identical with 1 step one of embodiment；
2nd, magnetic TOM-Co is prepared3O4/CoFe2O4：Identical with 1 step 2 of embodiment；
3rd, by magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed with aqueous solution containing ciprofloxacin, is transferred in brown shaking flask, keeps
Reacting liquid temperature is 60 min of water-bath oscillating reactionss under the conditions of 25 ± 1 DEG C, and obtains containing TOM-Co3O4/CoFe2O4Mixing
Solution；
TOM-Co described in step 33O4/CoFe2O4Dosage be 100 mg/L；
Concentration of aqueous solution containing ciprofloxacin described in step 3 is 5 mg/L；
The mixed liquor volume in brown shaking flask that is transferred to described in step 3 is 100 mL.
4th, pass through externally-applied magnetic field separation magnetic TOM-Co3O4/CoFe2O4：By externally-applied magnetic field separation magnetic TOM-Co3O4/
CoFe2O4, the TOM-Co of recovery3O4/CoFe2O4After being cleaned with ethanol and deionized water repeatedly and in condition under the conditions of 60 DEG C
Lower vacuum drying, the TOM-Co being recycled3O4/CoFe2O4, then complete and individually add TOM-Co3O4/CoFe2O4Husky to ring third
The adsorption experiment of star；
TOM-Co described in step 43O4/CoFe2O4Cleaned with ethanol and deionized water repeatedly, wash number is no less than 5 times.
Ciprofloxacin percentage situation over time is tested, change curve is shown in accompanying drawing 1.
Comparative example 2 individually adds single persulfate and the oxidation experiment of ciprofloxacin is carried out by the following method：
First, ciprofloxacin aqueous solution is prepared：Configure certain density ciprofloxacin aqueous solution and be transferred in brown shaking flask；
Concentration of aqueous solution containing ciprofloxacin described in step one is 5 mg/L；
The mixed liquor volume in brown shaking flask that is transferred to described in step one is 100 mL.
2nd, single persulfate is added：Reaction liquid temperature is kept in the brown shaking flask that single persulfate is added to step one
Spend for 60 min of water-bath oscillating reactionss under the conditions of 25 ± 1 DEG C, can achieve individually to add oxidation of single persulfate to ciprofloxacin
Experiment；
Single persulfate described in step 4 is potassium hydrogen persulfate；
Single persulfate described in step 4 is 66 with the mol ratio of ciprofloxacin in aqueous solution:1.
By comparative example 1, comparative example 1 and comparative example 2, it can be found that：Using TOM-Co of the present invention3O4/
CoFe2O4When in the single persulfate adsorption aqueous solution of collaboration, ciprofloxacin is used alone than the two, with more preferable adsorption effect.
Below the preferred embodiments of the invention are only listed, and protection scope of the present invention is not restricted to this, this area
Any change that technical staff is made within the scope of the invention as claimed is each fallen within the scope of the present invention.
Claims (9)
1. in a kind of single persulfate degradation water based on the activation of Fe2O3 doping order mesoporous Cobalto-cobaltic oxide antibacterials method, its
It is characterised by, specifically carries out according to the following steps：
First, TOM-Co is prepared3O4：
Co (NO is added to after template KIT-6 is fully ground3)2·6H2In the ethanol solution of O, 1 is stirred at ambient temperature
H obtains solution A；
By stepThe forced air drying under the conditions of 60 DEG C of resulting solution A obtains pink solid powder, by this pressed powder
It is transferred in crucible, and interior 5 h of roast under the conditions of 200 DEG C of Muffle furnace is placed it in, the programming rate of the Muffle furnace is
2 ℃/min；
By stepBrown solid powder after middle roast is added to Co (NO after being fully ground3)2·6H2The ethanol solution of O
In, stir 1 h at ambient temperature and obtain solution B；
By stepThe forced air drying under the conditions of 60 DEG C of resulting solution B obtains black solid, and this solid is transferred to crucible
Interior, and interior 5 h of roast under the conditions of 450 DEG C of Muffle furnace is placed it in, the programming rate of the Muffle furnace is 2 DEG C/min；
By stepThe black solid powder of middle roast is cooled to room temperature, through adding after being fully ground to filling 2 mol/
In the round-bottomed flask of L NaOH solution, under 60 DEG C of water bath condition, 12 h are stirred, 30 min of solution left standstill after stirring is gone
Supernatant, above step is in triplicate；
By stepAfter products obtained therefrom spends ultra-pure water respectively and ethanol is cleaned repeatedly to pH=7, true under the conditions of 60 DEG C
Again through being fully ground to obtain TOM-Co after sky is dry3O4；
2nd, magnetic TOM-Co is prepared3O4/CoFe2O4：
By TOM-Co3O4It is added to Fe (NO3)3·9H2In O- ethanol solution, 1 h is stirred at ambient temperature；
Preferably, step 2Described in TOM-Co3O4、Fe(NO3)3·9H2The mol ratio of O is 1:1；
Preferably, step 2Described in Fe (NO3)3·9H2The molar concentration of O- ethanol solution is 0.4 mol/L；
By step 2The forced air drying under the conditions of 60 DEG C of solution after stirring obtains black solid powder, by this solid powder
End is transferred in crucible, and places it in interior 5 h of roast under the conditions of 450 DEG C of Muffle furnace, the programming rate of the Muffle furnace
For 2 DEG C/min；
By step 2Black solid powder after middle roast is fully ground to obtain TOM-Co3O4/CoFe2O4, stand-by；
3rd, by magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed with aqueous solution containing ciprofloxacin, is transferred in brown shaking flask；
4th, the brown shaking flask in adding single persulfate to step 3, water-bath oscillating reactionss 30 ~ 120 at 20 ~ 50 DEG C
min；
5th, pass through externally-applied magnetic field separation magnetic TOM-Co3O4/CoFe2O4, the TOM-Co of recovery3O4/CoFe2O4With ethanol and go from
Sub- water is cleaned repeatedly and is vacuum dried under the conditions of 60 DEG C, the TOM-Co being recycled3O4/CoFe2O4.
2. in degradation water as claimed in claim 1 antibacterials method, it is characterised in that step oneDescribed in template
KIT-6、Co(NO3)2·6H2The mol ratio of O is 1:1.
3. in degradation water as claimed in claim 1 antibacterials method, it is characterised in that step oneDescribed in Co
(NO3)2·6H2The molar concentration of O solution is 0.8 mol/L.
4. in degradation water as claimed in claim 1 antibacterials method, it is characterised in that step oneDescribed in black solid
Body is 1 with the mass ratio of NaOH solution:100~200.
5. in degradation water as claimed in claim 1 antibacterials method, it is characterised in that step 2Described in TOM-
Co3O4、Fe(NO3)3·9H2The mol ratio of O is 1:1.
6. in degradation water as claimed in claim 1 antibacterials method, it is characterised in that step 2Described in Fe
(NO3)3·9H2The molar concentration of O- ethanol solution is 0.4 mol/L.
7. in degradation water as claimed in claim 1 antibacterials method, it is characterised in that the TOM- described in step 3
Co3O4/CoFe2O4Dosage be in per liter of aqueous solution containing ciprofloxacin input 10 ~ 200 mg.
8. in degradation water as claimed in claim 1 antibacterials method, it is characterised in that husky containing ring third described in step 3
Star concentration of aqueous solution is 1 ~ 20 mg/L.
9. in degradation water as claimed in claim 1 antibacterials method, it is characterised in that the single persulfuric acid described in step 4
Salt is Potassium peroxysulfate, at least one of single Ammonium persulfate., single sodium peroxydisulfate and single persulfuric acid calcium；Described single persulfate with
In aqueous solution, the mol ratio of ciprofloxacin is 66:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108726640A (en) * | 2017-04-20 | 2018-11-02 | 华中科技大学 | A kind of method of electrochemistry collaboration persulfate removal Organic Pollutants in Wastewater |
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