CN115920896A - Catalyst for degrading ciprofloxacin and preparation method and application thereof - Google Patents
Catalyst for degrading ciprofloxacin and preparation method and application thereof Download PDFInfo
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- CN115920896A CN115920896A CN202211438002.XA CN202211438002A CN115920896A CN 115920896 A CN115920896 A CN 115920896A CN 202211438002 A CN202211438002 A CN 202211438002A CN 115920896 A CN115920896 A CN 115920896A
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229960003405 ciprofloxacin Drugs 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 230000000593 degrading effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title description 6
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 63
- 238000006731 degradation reaction Methods 0.000 claims abstract description 47
- 230000015556 catabolic process Effects 0.000 claims abstract description 42
- 229940012466 egg shell membrane Drugs 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims description 30
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- 238000000034 method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000012425 OXONE® Substances 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 21
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 abstract description 8
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
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- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a catalyst for degrading ciprofloxacin, which comprises the following components: egg shell membrane biochar KBC800 and CoFe 2 O 4 . The invention prepares KBC800@ CoFe by a hydrothermal method 2 O 4 The magnetic catalyst material is green and environment-friendly, and is KBC800@ CoFe 2 O 4 The magnetic catalyst material has efficient degradation effect on antibiotic pollutants, and under the conditions that the addition amount of the catalyst is 20mg and the addition amount of potassium peroxymonosulfate is 0.1mmol, KBC800@ CoFe 2 O 4 The degradation rate of ciprofloxacin (100mL, 5mg/L, pH = 7) by the PMS system is as high as 95%.Compared with the existing charcoal-based catalyst, the material can more effectively activate potassium monopersulfate at a relatively low dosage so as to realize more efficient degradation and removal of ciprofloxacin.
Description
Technical Field
The invention relates to the field of water treatment, and in particular relates to a catalyst for degrading ciprofloxacin and a preparation method and application thereof.
Background
In recent years, "emerging pollutants" in water environments have gradually turned into a hotspot in environmental chemistry research. With the wide clinical use of antibiotics, a large amount of antibiotics remain in the water body and are discharged all over the world. Ciprofloxacin (Ciprofloxacin, CIP, C) 17 H 18 FN 3 O 3 ) Belongs to the third generation fluoroquinolone antibiotics, and is one of the most widely used antibiotic medicines for human and veterinary use. When the lower metal oxide catalyst is low in activity and poor in stability and is difficult to remove by the traditional sewage treatment process, the lower metal oxide catalyst is continuously discharged into the environment, and when the water containing low-concentration ciprofloxacin is drunk for a long time, human nervousness, nausea and vomiting can be caused; drinking water containing ciprofloxacin at high concentration causes serious side effects such as thrombocytopenia, acute renal failure, leukopenia, etc. The environmental pollution of ciprofloxacin has far-reaching harm, so the degradation treatment of ciprofloxacin is imperative, and a ciprofloxacin degradation catalyst capable of overcoming the defects of the traditional metal oxide catalyst is needed.
The sulfate radical advanced oxidation technology has the characteristic of efficiently degrading pollutants, and therefore has attracted extensive attention in the aspect of removing new organic pollutants in water bodies in recent years. Meanwhile, biochar (biocar, BC) becomes a new catalyst for activating Peroxymonosulfate (PMS) by virtue of large specific surface area and rich functional groups. The doping of metals is considered to be the most effective for improving the catalytic ability of the biocharOne of the effective ways, when the biochar is used as a carrier of the metal catalyst, can prevent the aggregation of metal nanoparticles and provide more active sites to improve the catalytic efficiency. CoFe 2 O 4 Is one of the most commonly used catalysts for inducing PMS activation, and the principle is Co 2+ And Fe 3+ The coupling of (a) can efficiently activate PMS to generate active species:
≡Co 2+ +HSO 5- →≡Co 3+ +SO 4 ·-+OH -
≡Co 3+ +HSO 5- →≡Co 2+ +SO 5 ·-+OH +
≡Fe 3+ +HSO 5- →≡Fe 2+ +SO 5 ·-+H +
≡Fe 2+ +HSO 5- →≡Fe 3+ +SO 4 ·-+OH -
≡Fe 2+ +≡Co 3+ →≡Fe 3+ +≡Co 2+
however, coFe 2 O 4 The nano particles have stronger magnetism and are easy to agglomerate in aqueous solution, so that the exposed active sites are reduced. Mixing CoFe 2 O 4 The catalyst is distributed on carrier materials such as graphene, montmorillonite and biochar, and can improve the catalytic activity of the catalyst. Biochar is used as CoFe 2 O 4 The support of the nanoparticles is CoFe 2 O 4 An efficient method to activate the disadvantages of PMS.
The eggshell membrane (ESM) is a membrane with a reticular fiber structure between eggshell and egg white, is composed of calcium carbonate, collagen and microelements, has good biocompatibility, and is rich in hydroxyl (-OH), carboxyl (-COOH), and amino (-NH) 2 ) And the like, which is beneficial to capturing metal ions. Due to its unique structure, abundant surface functional groups and low cost, eggshell membrane has become an important carrier for synthesizing nano materials with different properties.
Has been proved that K 2 CO 3 Can effectively improve the pore structure of the biochar and provide rich mass transfer channels, adsorption and catalytic active sites for the biochar. And in co-pyrolysisIn the process, K 2 CO 3 Can increase the alkalinity of the biochar, is beneficial to the immobilization of heavy metals, and can effectively reduce the leaching of the heavy metals. Thus, adding K 2 CO 3 The pore-forming agent used as the biochar can improve the porosity of the eggshell membrane biochar and is beneficial to the immobilization of heavy metals in the biochar.
Disclosure of Invention
In order to solve the technical problems and overcome the defects of the traditional metal oxide catalyst, the invention provides a catalyst for degrading ciprofloxacin and a preparation method and application thereof 2 CO 3 Preparing porous biochar KBC800 serving as a pore-forming agent and serving as CoFe 2 O 4 Construction of a nanoparticle Carrier, KBC800@ CoFe 2 O 4 The PMS system catalyzes and degrades ciprofloxacin, and provides a safe, green and efficient new method for treating antibiotic-polluted wastewater.
In order to achieve the technical effects, the invention is realized by the following technical scheme: carrier type catalyst KBC800@ CoFe for degrading ciprofloxacin 2 O 4 。
The invention also aims to provide a preparation method of the catalyst for degrading ciprofloxacin, which comprises the following steps:
s1, pretreating to obtain an eggshell membrane, drying and grinding the eggshell membrane into powder, and washing the eggshell membrane with deionized water;
s2, mixing K 2 CO 3 Dissolving in deionized water, adding the eggshell membrane washed by the deionized water in S1, drying the mixture, and pyrolyzing in nitrogen atmosphere to obtain KBC800;
s3, taking Co (NO) 3 ) 2 ﹒6H 2 O and 0.1346g Fe (NO) 3 ) 2 ﹒9H 2 Dissolving O in deionized water to obtain a solution 1; uniformly dispersing the KBC800 obtained in the S2 in deionized water by stirring to obtain a solution 2;
s4, dropwise adding the solution 1 into the solution 2, dropwise adding sodium hydroxide into the mixed solution, placing the mixed solution into an oven for reaction, performing solid-liquid separation on the obtained mixture by adopting a magnet, and using water and ethanolAlternate washing of the resulting solid KBC800@ CoFe 2 O 4 Drying at 60 deg.C;
further, in S2, 1g K is used 2 CO 3 Dissolving in 25-45 mL deionized water, and adding 5g eggshell membrane;
further, 0.0484g Co (NO) is weighed in S2 3 ) 2 ﹒6H 2 O and 0.1346g Fe (NO) 3 ) 2 ﹒9H 2 Dissolving O in 6mL of deionized water to obtain a solution 1;
further, 0.1175g of KBC800 in the S2 is uniformly dispersed in 15mL of deionized water to obtain a solution 2;
the invention has the beneficial effects that:
the invention prepares KBC800@ CoFe by a hydrothermal method 2 O 4 The magnetic catalyst material is green and environment-friendly, and KBC800@ CoFe 2 O 4 The magnetic catalyst material has efficient degradation effect on antibiotic pollutants, and under the conditions that the addition amount of the catalyst is 20mg and the addition amount of potassium peroxymonosulfate is 0.1mmol, KBC800@ CoFe 2 O 4 The degradation rate of (100mL, 5mg/L, pH = 7) ciprofloxacin by the/PMS system can reach 95%. Compared with the existing charcoal-based catalyst, the material can more effectively activate potassium monopersulfate at a relatively low dosage so as to realize the efficient removal of ciprofloxacin.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows eggshell membrane BC800, KBC800, KBC800@ CoFe 2 O 4 Scanning electron microscope images of;
FIG. 2 shows BC800, KBC800, KBC800@ CoFe 2 O 4 N of (A) 2 Adsorption-desorption curves;
FIG. 3 is the present inventionMing KBC800, KBC800@ CoFe 2 O 4 XRD pattern of, KBC800@ CoFe 2 O 4 (ii) a FT-IR spectrum of (A);
FIG. 4 shows KBC800@ CoFe of the present invention 2 O 4 /PMS、KBC800@CoFe 2 O 4 Degradation curves of ciprofloxacin by PMS and KBC 800/PMS;
FIG. 5 shows KBC800@ CoFe of the present invention 2 O 4 Activating potassium peroxymonosulfate to degrade ciprofloxacin under different pH values;
FIG. 6 shows KBC800@ CoFe of the present invention 2 O 4 Activating potassium monopersulfate to degrade ciprofloxacin curves with different concentrations;
FIG. 7 shows different KBC800@ CoFe of the present invention 2 O 4 The curve of degrading ciprofloxacin by activating potassium peroxymonosulfate under the adding amount is obtained;
FIG. 8 shows KBC800@ CoFe of the present invention 2 O 4 And (3) activating potassium monopersulfate with different doses to degrade the ciprofloxacin curve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method comprises the following steps: soaking fresh egg shells in diluted nitric acid solution until the egg shells fall off, washing for multiple times to obtain egg shell membranes, drying in an oven at 80 ℃, and grinding the dried egg shell membranes into powder by using a ball mill; mixing 1g K 2 CO 3 Dissolving the mixture in 25-45 mL of deionized water, and simultaneously soaking 5g of eggshell membrane powder in the K and ultrasonically dispersing the eggshell membrane powder 2 CO 3 Drying the solution in an oven at 80 ℃ for later use;
step two: and (3) putting the dried eggshell membrane into a tubular furnace, and pyrolyzing the eggshell membrane at 800 ℃ for 2h at a heating rate of 10 ℃ per minute in a nitrogen atmosphere. Obtaining black solid KBC800;
step three: dissolving 0.1175g of KBC800 in 15mL of ionized water, performing ultrasonic treatment for 0.5h to prepare C800 suspension, and dissolving 0.0484g (1.6 mmol) of Co (NO) 3 ) 2 ﹒6H 2 O,0.1346g(3.2mmol)Fe(NO 3 ) 2 ﹒9H 2 Dissolving O in 6mL of deionized water;
step four: mixing the two solutions, mechanically stirring at 85 ℃, dripping 5mL (2 mol/L) of sodium hydroxide, and placing the mixed solution in a reaction kettle to react in an oven at 200 ℃ for 12 hours; subjecting the obtained mixture to solid-liquid separation with a magnet, and alternately washing the obtained solid KBC800@ CoFe with water and ethanol 2 O 4 Drying at 60 deg.C until neutral.
KBC800@CoFe 2 O 4 The specific surface area is 740.5821m 2 (ii)/g, total pore volume of 0.148507cm 3 And/g, referring to fig. 1, the surface of the material has mesopore and micropore structures with different sizes, and further observation shows that metal active sites are uniformly attached to the inner wall of the pore channel of the material, so that the structure greatly improves the contact area and is beneficial to the catalytic reaction.
Example 2
The method is used for researching the influence of different systems on the degradation effect of ciprofloxacin and comprises the following specific steps:
(1) Procedure of experiment
0.1mmol of potassium monopersulfate was weighed into 100mL (10 mg/L, pH = 7) of ciprofloxacin solution, and samples were taken at intervals to determine the remaining ciprofloxacin concentration.
Weighing 10mg KBC800@ CoFe 2 O 4 Adding into 100mL (10 mg/L, pH = 7) ciprofloxacin solution, adsorbing for 30min, weighing 0.1mmol potassium monopersulfate, adding into the solution, initiating degradation reaction, sampling at certain time interval, and determining the concentration of the residual ciprofloxacin.
Weighing 10mg KBC800@ CoFe 2 O 4 100mL (10 mg/L, pH = 7) of ciprofloxacin solution was added, and samples were taken at intervals to determine the residual ciprofloxacin concentration.
10mg of KBC800 was weighed into 100mL (10 mg/L, pH = 7) of ciprofloxacin solution, and samples were taken at regular intervals to determine the remaining ciprofloxacin concentration.
(2) Results of the experiment
KBC800@CoFe 2 O 4 The adsorption effect is good, but the degradation rate of the ciprofloxacin can only reach 50%. KBC800@ CoFe 2 O 4 The degradation rate of the/PMS system on the ciprofloxacin can reach 90 percent, while the degradation rate of the KBC800/PMS on the ciprofloxacin can only reach 50 percent, which shows that CoFe in the catalyst 2 O 4 The potassium monopersulfate is successfully activated and active species are produced which can degrade ciprofloxacin. Only PMS is added to hardly have degradation effect on ciprofloxacin.
Example 3
The method is used for researching the influence of different solution pH values on the degradation effect of ciprofloxacin and comprises the following specific steps:
(1) Procedure of experiment
10mg/L ciprofloxacin solutions with pH values of 3, 5, 7, 9 and 11 are respectively prepared, and 10mg KBC800@ CoFe is respectively weighed 2 O 4 And 0.3mmol of potassium monopersulfate were simultaneously added to the above ciprofloxacin (50 mL) solution, and samples were taken at regular intervals to determine the remaining ciprofloxacin concentration.
Respectively preparing ciprofloxacin solutions with concentrations of 5mg/L, 10mg/L and 20mg/L, adjusting pH value to 7, and weighing 20mg KBC800@ CoFe 2 O 4 Adding into the 100mL (pH = 7) ciprofloxacin solution, adsorbing for 30min, respectively weighing 0.3mmol potassium monopersulfate, adding into the system, starting degradation reaction, and sampling at certain time intervals to determine the concentration of the residual ciprofloxacin.
(2) Results of the experiment
Under alkaline conditions, KBC800@ CoFe 2 O 4 The PMS system is not greatly influenced by the pH of the solution, and the degradation rate of ciprofloxacin can still be close to 90% when the pH = 11. Under the acidic condition, the degradation efficiency of the system is inhibited, and when the pH =3, the inhibition effect is obvious, but the degradation rate of ciprofloxacin can still be close to 80%. Indicating KBC800@ CoFe 2 O 4 The pH range of the PMS system is wide, and the potential of practical application is large.
When the concentration of the ciprofloxacin is respectively 20mg/L, 10mg/L and 5mg/L, the degradation rate of the system is respectively 70%, 90% and 95%, and the degradation rate of the system on the ciprofloxacin is increased along with the decrease of the concentration of the ciprofloxacin.
Example 4
A preparation method of a novel catalyst for efficiently activating Peroxymonosulfate (PMS) to degrade and remove ciprofloxacin comprises the following steps:
the method is used for researching the influence of the catalyst and the adding amount of potassium peroxymonosulfate on the degradation effect of ciprofloxacin and comprises the following specific steps:
(1) Experimental procedures
Weighing 5mg, 10mg and 20mg KBC800@ CoFe 2 O 4 The solution was added to 100mL (10 mg/L, pH = 7) of ciprofloxacin, 0.1mmol of Potassium Monopersulfate (PMS) was added after 30min of adsorption, the degradation reaction was started, and samples were taken at certain time intervals to determine the remaining ciprofloxacin concentration.
To 100mL (10 mg/L, pH = 7) of ciprofloxacin solution to be treated were added 10mg of KBC800@ CoFe 2 O 4 After adsorbing for 30min, respectively adding 0.05mmol, 0.1mmol and 0.2mmol potassium hydrogen peroxymonosulfate, starting degradation reaction, and sampling at certain time intervals to determine the concentration of the residual ciprofloxacin.
(2) Results of the experiment
When the catalyst dosage is increased from 5mg to 10mg, the degradation rate of the system is increased from 60% to 90%, indicating that the increase of the catalytic active sites generates more active species in the system. When the dosage of the catalyst is increased from 10mg to 15mg, the degradation rate of the system is not obviously increased, which indicates that the catalytic active sites in the system are saturated.
When the adding amount of potassium monopersulfate is increased from 0.05mmol to 0.1mmol, the degradation rate of the system is increased from 65% to 90%, which shows that the utilization rate of the catalytic active sites is improved. When the adding amount of potassium monopersulfate is increased from 0.1mmol to 0.2mmol, the degradation rate of the system is not obviously increased, which indicates that the utilization rate of the catalytic active sites in the system is saturated.
KBC800@ CoFe when the catalyst addition amount is 20mg, the potassium monopersulfate addition amount is 0.1mmol, and the initial concentration of ciprofloxacin is 5mg/L (100mL, pH = 7) 2 O 4 The PMS system has the highest degradation rate of ciprofloxacin, which can reach 95%. The degradation efficiency is higher than that of most cobalt and iron-based catalysts reported in the literature.
Example 5
The working principle of the catalyst provided by the invention is as follows:
from FIG. 1 (a), the eggshell membrane is a reticular fiber structure; FIG. 1 (b) shows that C800 has smooth surface and no porous channel structure; as shown in fig. 1 (c), a plurality of channels of different sizes are distributed inside the KBC800. Demonstration K 2 CO 3 The egg shell membrane biochar generates a porous structure. From FIG. 1 (d) (e) (f), KBC800@ CoFe 2 O 4 The inner wall of the plurality of pores uniformly adhered with solid particles proves that the CoFe 2 O 4 The catalyst is successfully loaded on the KBC800 and is uniformly distributed, so that the structure greatly improves the contact area and is beneficial to the catalytic reaction.
From FIG. 2 (a), BC800 (without K added) 2 CO 3 The obtained eggshell membrane biochar) has small specific surface area and almost no pore path structure; from FIG. 2 (b), K 2 CO 3 The specific surface area of the eggshell membrane biochar is greatly improved by adding the chitosan; from FIG. 2 (c), KBC800@ CoFe 2 O 4 The specific surface area is reduced compared with that of KBC800, and a large amount of pores still exist. (BC 800 specific surface area 1.4209m 2 (ii)/g; the specific surface area of KBC800 is 829.7382m 2 /g；KBC800@CoFe 2 O 4 The specific surface area is 740.5821m 2 /g。)
From the comparison between FIG. 3 (a) and FIG. 3 (b), KBC800@ CoFe is known 2 O 4 In the XRD pattern of (A) and (B), the standard cards PDF #79-1744CoFe appear 2 O 4 The characteristic peaks of the middle (113), (024), (725) and (208) planes prove that CoFe 2 O 4 Load is successfully applied to KBC800.KBC800@ CoFe 2 O 4 In the Fourier spectrum of (1), 3410cm -1 The peak at (A) is caused by tensile vibration generated by adsorption of-OH on the catalyst, 876cm -1 (Co-O bond) and 589cm -1 (Fe-O bond) two peaks, confirming the presence of CoFe in the catalyst prepared 2 O 4 。
As can be seen from fig. 4: KBC800@ CoFe 2 O 4 /PThe degradation rate of the MS system to the ciprofloxacin reaches more than 90 percent, and KBC800@ CoFe is independently added 2 O 4 Only 50% of ciprofloxacin can be removed, and the addition of potassium monopersulfate has little effect on removing ciprofloxacin, so that the addition of the catalyst and the potassium monopersulfate plays an important role in the degradation process. Unsupported CoFe 2 O 4 The KBC800 still has the adsorption effect on the ciprofloxacin, but hardly activates the potassium monopersulfate, and proves that CoFe 2 O 4 The addition of the compound improves the activation effect of the material on potassium peroxymonosulfate.
As can be seen from fig. 5: under alkaline conditions, KBC800@ CoFe 2 O 4 The degradation of ciprofloxacin by the PMS system is not greatly influenced by pH. Under the acidic condition, the oxidation of free radicals in the system is inhibited, and the degradation effect of the system on ciprofloxacin is relatively obviously inhibited when the pH =3, but the degradation rate can still reach 80%.
As shown in FIG. 6, the activity site and the active species availability increased with the decrease of the ciprofloxacin concentration, KBC800@ CoFe 2 O 4 The degradation effect of the PMS system on the ciprofloxacin is improved.
From fig. 7, it is known that: with the addition of the catalyst increased in a proper amount, the active sites in the system are increased, namely KBC800@ CoFe 2 O 4 The degradation effect of the PMS system on the ciprofloxacin is improved.
From fig. 8, it is known that: with the addition of potassium monopersulfate increased, more active substances, KBC800@ CoFe, are generated in the system 2 O 4 The degradation effect of the PMS system on the ciprofloxacin is improved.
The above phenomena show that: KBC800@ CoFe prepared by hydrothermal method 2 O 4 The magnetic catalyst material is green and efficient, and has a rapid degradation effect on antibiotic pollutant ciprofloxacin.
In conclusion, the invention prepares KBC800@ CoFe by a hydrothermal method 2 O 4 The magnetic catalyst material is green and environment-friendly, and KBC800@ CoFe 2 O 4 The magnetic catalyst material has efficient degradation effect on antibiotic pollutants, and the dosage of the catalyst is 10mg, KBC800@ CoFe under the condition that the adding amount of potassium hydrogen peroxymonosulfate is 0.1mmol 2 O 4 The degradation rate of (100mL, 5mg/L, pH = 7) ciprofloxacin by the PMS system can reach 95 percent
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A catalyst for degrading ciprofloxacin comprises egg shell membrane derived biochar KBC800 supported CoFe 2 O 4 (KBC800@CoFe 2 O 4 )。
2. The method for preparing the ciprofloxacin degradation catalyst according to claim 1, which is characterized by specifically comprising the following steps:
s1, pretreating to obtain an eggshell membrane, and drying and grinding the eggshell membrane into powder for later use;
s2, adding K 2 CO 3 Dissolving in deionized water, adding an egg shell membrane washed by the deionized water, drying the mixture, and pyrolyzing in nitrogen atmosphere to obtain KBC800;
s3, taking Co (NO) 3 ) 2 ﹒6H 2 O and 0.1346g Fe (NO) 3 ) 2 ﹒9H 2 Dissolving O in deionized water to obtain a solution 1; uniformly dispersing KBC800 in deionized water by stirring to obtain a solution 2;
s4, dropwise adding the solution 1 into the solution 2, dropwise adding sodium hydroxide into the mixed solution, placing the mixed solution into an oven for reaction, and performing solid-liquid separation on the obtained mixture by adopting a magnet; washing the obtained solid KBC800@ CoFe alternately with water and ethanol 2 O 4 And dried at 60 ℃.
3. The method for preparing the ciprofloxacin degradation catalyst of claim 1, wherein K in S2 is 2 CO 3 The mass ratio of the egg shell membrane to the egg shell membrane is 1:5.
4. The method for preparing the ciprofloxacin degradation catalyst of claim 1, wherein 1g K is added in S2 2 CO 3 Dissolving in 25-45 mL deionized water, and adding 5g eggshell membrane.
5. The method for preparing the ciprofloxacin degradation catalyst of claim 1, wherein the S3 comprises CoFe 2 O 4 The mass ratio of the carbon to the biochar carrier is 1 3+ And Co 2+ Is 2:1.
6. The method for preparing the ciprofloxacin degradation catalyst of claim 1, wherein 0.0484g Co (NO) is weighed in S3 3 ) 2 ﹒6H 2 O and 0.1346g Fe (NO) 3 ) 2 ﹒9H 2 O, dissolved in 6mL of deionized water to give solution 1.
7. The method for preparing a ciprofloxacin catalyst of claim 1, wherein in S3, 0.1175g of KBC800 is uniformly dispersed in 15mL of deionized water to obtain solution 2.
8. Use of the ciprofloxacin degradation catalyst of claim 1 in sewage treatment.
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